TW202208507A - Curable resin composition, cured film, laminate, cured film production method and semiconductor device - Google Patents

Abstract

This curable resin composition contains: at least one type of resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polyamide-imide, and polyamide-imide precursors; a compound B having at least one group selected from an N-hydroxyamino group, an N-hydroxyimino group, an N-hydroxyamide group and an N-hydroxyimide group; and an organometallic complex.

Description

Curable resin composition, cured film, laminate, manufacturing method of cured film, and semiconductor device

The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing the cured film, and a semiconductor device.

Resins such as polyimide, polybenzoxazole, and polyimide imide have excellent heat resistance and insulating properties, and are therefore suitable for various applications. Although it does not specifically limit as said use, if the semiconductor device for encapsulation is mentioned, the use as a material of an insulating film or a sealing material, or a protective film can be mentioned. Moreover, it is also used as a base film of a flexible substrate, a coverlay film, or the like.

For example, in the above-mentioned applications, resins such as polyimide, polybenzoxazole, polyimide, etc. are selected from the group consisting of polyimide, polybenzoxazole, polyimide, polyamide The form of curable resin composition of the resin of at least 1 sort(s) selected from the group of an imide precursor, a polybenzoxazole precursor, and a polyimide precursor is used. By applying such a curable resin composition to a base material, for example, by coating or the like to form a photosensitive film, it is possible to form a cured product on the base material by exposing, developing, heating, etc. as necessary. The above-mentioned polyimide precursor, polybenzoxazole precursor and polyimide imide precursor are cyclized by heating, for example, and in the cured product, they become polyimide, polybenzoxazole, respectively , Polyamide imide. Since the curable resin composition can be applied by a known coating method, etc., it can be said that it is excellent in suitability for production, and the design of the shape, size, and application position of the applied curable resin composition at the time of application, for example, is free. high degree. In addition to the high performance of polyimide, polybenzoxazole, polyimide imide, etc., from the viewpoint of being excellent in suitability for these productions, the above-mentioned curable resin composition is expected to be more widely used in the industry. application expansion.

For example, Patent Document 1 describes a negative-type photosensitive resin composition containing (A) a polyimide precursor, (B) an imide compound having a specific structure, and (C) a photopolymerization initiator.

[Patent Document 1] Japanese Patent Laid-Open No. 2019-185031

When forming a pattern made of a curable resin composition, it is required to improve the resolution.

An object of the present invention is to provide a curable resin composition having excellent resolution during pattern formation, a cured film obtained by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and A semiconductor device including the above cured film or the above laminate.

式（1-1）、式（1-2）或式（1-3）中，R¹¹ 及R¹² 分別獨立地表示未經取代的碳數1～7的脂肪族烴基、作為取代基具有選自包括一級胺鹽結構、二級胺鹽結構、三級胺基、三級胺鹽結構、四級銨基及脂肪族雜環基之群組中之至少1種取代基之碳數1～7的脂肪族烴基、或具有選自包括羥基、烷氧基、硫醇基及烷硫基之群組中之至少1種取代基之碳數2～7的脂肪族烴基，R²¹ 及R²² 分別獨立地表示可以具有取代基之碳數1～7的脂肪族烴基，R³¹ 及R³² 分別獨立地表示可以具有取代基之碳數1～7的脂肪族烴基，R³³ 表示可以具有取代基之碳數1～7的脂肪族烴基。 ＜9＞如＜1＞至＜8＞之任一項所述之硬化性樹脂組成物，其中，上述化合物B的含有莫耳量相對於上述有機金屬錯合物的含有莫耳量的比例為30～500%。 ＜10＞如＜1＞至＜9＞之任一項所述之硬化性樹脂組成物，其係用於形成供負型顯影之感光膜。 ＜11＞如＜1＞至＜10＞之任一項所述之硬化性樹脂組成物，其係用於形成再配線層用層間絕緣膜。 ＜12＞一種硬化膜，其係將＜1＞至＜11＞之任一項所述之硬化性樹脂組成物硬化而成。 ＜13＞一種積層體，其係包含2層以上＜12＞所述之硬化膜，在任意上述硬化膜彼此之間包含金屬層。 ＜14＞一種硬化膜之製造方法，其係包括：膜形成製程，將＜1＞至＜11＞之任一項所述之硬化性樹脂組成物適用於基板而形成膜。 ＜15＞如＜14＞所述之硬化膜之製造方法，其係包括：曝光製程，對上述膜進行曝光；以及顯影製程，對上述膜進行顯影。 ＜16＞如＜15＞所述之硬化膜之製造方法，其中，在上述曝光中所使用的曝光光包含波長為405nm的光。 ＜17＞如＜15＞或＜16＞所述之硬化膜之製造方法，其中，上述曝光係藉由雷射直接成像法進行的曝光。 ＜18＞如＜14＞至＜17＞之任一項所述之硬化膜之製造方法，其係包括：加熱製程，將上述膜在50～450℃下進行加熱。 ＜19＞一種半導體器件，其係包括＜12＞所述之硬化膜或＜13＞所述之積層體。 [發明效果]Examples of typical embodiments of the present invention are shown below. <1> A curable resin composition comprising: selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyimide imide and polyimide. At least one resin in the group of amide imide precursors, having a resin selected from the group consisting of N-hydroxyimide group, N-hydroxyimide group, N-hydroxyimide group and N-hydroxyimide group A compound B of at least one group in the group, and an organometallic complex. <2> The curable resin composition according to <1>, further comprising a photopolymerization initiator. <3> The curable resin composition according to <1> or <2>, which further contains a crosslinking agent. <4> The curable resin composition according to any one of <1> to <3>, wherein the organometallic complex is a metallocene compound. <5> The curable resin composition according to any one of <1> to <4>, wherein the organometallic complex is a titanium compound. <6> The curable resin composition according to any one of <1> to <5>, wherein the organometallic complex has photoradical polymerization initiation energy. <7> The curable resin composition according to any one of <1> to <6>, wherein the compound B has a compound selected from the group consisting of N-hydroxyamino group, N-hydroxyimino group and N-hydroxyl group A compound of at least one group in the group of amide groups. <8> The curable resin composition according to any one of <1> to <6>, wherein the compound B includes a compound having an N-hydroxyimide group, and further includes a compound selected from the group consisting of formula ( At least one compound selected from the group consisting of a compound represented by 1-1), a compound represented by formula (1-2), and a compound represented by formula (1-3). [Chemical formula 1]

In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and have an optional substituent as a substituent. Carbon number 1-7 of at least one substituent selected from the group consisting of primary amine salt structure, secondary amine salt structure, tertiary amine group, tertiary amine salt structure, quaternary ammonium group and aliphatic heterocyclic group aliphatic hydrocarbon group, or an aliphatic hydrocarbon group with carbon number of 2 to 7 having at least one substituent selected from the group consisting of hydroxyl, alkoxy, thiol and alkylthio groups, R ²¹ and R ²² are respectively Each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, R ³¹ and R ³² each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and R ³³ represents an optionally substituted aliphatic hydrocarbon group. Aliphatic hydrocarbon group having 1 to 7 carbon atoms. <9> The curable resin composition according to any one of <1> to <8>, wherein the ratio of the molar content of the compound B to the molar content of the organometallic complex is: 30 to 500%. <10> The curable resin composition according to any one of <1> to <9>, which is used for forming a photosensitive film for negative development. <11> The curable resin composition according to any one of <1> to <10>, which is used for forming an interlayer insulating film for a rewiring layer. <12> A cured film obtained by curing the curable resin composition according to any one of <1> to <11>. <13> A layered body comprising two or more layers of the cured films described in <12> and including a metal layer between any of the cured films. <14> A method for producing a cured film, comprising: a film formation process wherein the curable resin composition according to any one of <1> to <11> is applied to a substrate to form a film. <15> The manufacturing method of the cured film as described in <14>, which comprises: an exposure process, which exposes the said film; and a development process, which develops the said film. <16> The manufacturing method of the cured film as described in <15> whose exposure light used for the said exposure contains light of wavelength 405nm. <17> The manufacturing method of the cured film as described in <15> or <16> whose said exposure is exposure by the laser direct imaging method. <18> The manufacturing method of the cured film as described in any one of <14> to <17>, which comprises a heating process which heats the said film at 50-450 degreeC. <19> A semiconductor device comprising the cured film described in <12> or the laminated body described in <13>. [Inventive effect]

According to the present invention, there are provided a curable resin composition having excellent resolution during pattern formation, a cured film obtained by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a method comprising: The semiconductor device of the said cured film or the said laminated body.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments. In this specification, the numerical range shown using the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit, respectively. In this specification, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved. In the notation of groups (atomic groups) in this specification, the notation of substituted and unsubstituted includes groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic acid" and "methacrylate" "Acrylic" or "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content means the total mass of the components after removing the solvent from all the components of the composition. In addition, in this specification, the solid content concentration refers to the mass percentage of other components other than the solvent with respect to the total mass of a composition. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values by gel permeation chromatography (GPC measurement). In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and using guard columns HZ-L and TSKgel Super HZM-M as columns , TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, these molecular weights shall be those obtained by measuring using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise stated, the detection in GPC measurement shall be the thing obtained by using the wavelength 254nm detector of UV rays (ultraviolet rays). In this specification, when describing the positional relationship of each layer constituting the layered product as "upper" or "lower", other layers may be provided on the upper side or lower side of the standard layer among the plurality of layers concerned. That is, a third layer or element may be further interposed between the standard layer and the above-mentioned other layers, and the standard layer and the above-mentioned other layers do not need to be in contact with each other. Also, unless otherwise specified, the direction in which the layers of the substrate are stacked is referred to as "up", or in the presence of a photosensitive film, the direction from the substrate toward the photosensitive film is referred to as "up", and the opposite direction is referred to as "up" Down". In addition, the setting of the up-down direction is for the convenience of this specification, and in an actual aspect, the "up" direction in this specification may be different from the vertical direction. In the present specification, unless otherwise specified, the composition may contain two or more kinds of compounds corresponding to the components as each component contained in the composition. In addition, unless otherwise stated, the content of each component in the composition means the total content of all the compounds corresponding to the component. In this specification, unless otherwise stated, the temperature is 23° C., the air pressure is 101,325 Pa (one air pressure), and the relative humidity is 50% RH. In this specification, the combination of the preferred aspects is the more preferred aspect.

(curable resin composition) The curable resin composition of the present invention (also simply referred to as "the composition of the present invention".) contains a compound selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor , at least one resin in the group of polyamideimide and polyamideimide precursors, having a resin selected from the group consisting of N-hydroxylamine group, N-hydroxylimide group, N-hydroxylamide group and Compound B of at least one group in the group of N-hydroxyimide groups, and an organometallic complex. Below, will be selected from the group comprising polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide precursor At least one of the resins, also referred to as "specific resins", will have a resin selected from the group consisting of N-hydroxylamine, N-hydroxyimino, N-hydroxyimino, and N-hydroxyimino The compound B of at least one group is also referred to as "specific compound".

The curable resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and is preferably used for forming a film for exposure and development using a developer containing an organic solvent. Moreover, it is preferable that the curable resin composition of this invention is used for forming the photosensitive film for negative image development. In the present invention, negative tone development refers to development in which a non-exposed portion is removed by development in exposure and development, and positive tone development refers to development in which an exposed portion is removed by development. As the method of the above-mentioned exposure, the above-mentioned developer, and the method of the above-mentioned development, for example, the exposure method described in the exposure process in the description of the manufacturing method of the cured film described later, the developer described in the development process, and developing method.

The resulting pattern of the curable resin composition of the present invention is excellent in resolution. Although the mechanism by which the above-mentioned effect is obtained is not clear, it is presumed as follows.

Conventionally, organic titanium compounds and the like have been added to curable resin compositions for the purpose of improving chemical resistance. However, when patterning is performed using a curable resin composition including an organometallic complex, the organometallic complex may be aggregated in the film and the resolution may be lowered. The curable resin composition of the present invention contains a specific compound in addition to the organometallic complex. It is considered that the organometallic complex contained in the curable resin composition is dispersed in a nearly uniform state in the film due to the strong interaction between the specific compound and the organometallic complex. As a result, it is presumed that the curable resin composition of the present invention has excellent resolution. Here, in Patent Document 1, there is neither description nor suggestion of the technical idea of improving the resolution by using a specific compound and an organometallic complex in combination.

Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

＜Specific resin＞ The curable resin composition of the present invention comprises a compound selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyimide and polyimide At least one resin (specific resin) in the group of amine precursors. The curable resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin. Moreover, it is preferable that a specific resin has a radically polymerizable group. When the specific resin has a radically polymerizable group, it is preferable that the curable resin composition contains a photoradical polymerization initiator described later as a sensitizer, and a photoradical polymerization initiator described later is included as a sensitizer and contains The radical crosslinking agent described later is more preferable, the photoradical polymerization initiator described later is contained as a sensitizer, the radical crosslinking agent described later is contained, and the sensitizer described later is further more preferably contained. From such a curable resin composition, for example, a negative photosensitive film is formed. In addition, the specific resin may have a polarity conversion group such as an acid-decomposable group. When a specific resin has an acid-decomposable group, it is preferable that a curable resin composition contains the photoacid generator mentioned later as a photosensitizer. For example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed from such a curable resin composition.

式（2）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價的有機基團，R¹¹⁵ 表示4價的有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基團。[Polyimide Precursor] The type of the polyimide precursor used in the present invention is not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). [Chemical formula 2]

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent hydrogen Atom or a monovalent organic group.

A ¹ and A ² in the formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. R ¹¹¹ in the formula (2) represents a divalent organic group. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including linear or branched aliphatic groups having 2 to 20 carbon atoms. , Cyclic aliphatic groups with 6 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by a combination of these are preferred, and groups containing aromatic groups with 6 to 20 carbon atoms are more preferred. good. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO- which may be substituted by a fluorine atom. Or a group formed by a combination of two or more of the above. The preferred ranges of these are as described above.

Preferably R ¹¹¹ is derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, it includes a group consisting of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. The diamine of the group is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. As an example of an aromatic group, the following are mentioned.

式中，A係單鍵或選自可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO₂ -、-NHCO-或該等的組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO₂ -中之基團為更佳，-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -或-C（CH₃ ）₂ -為進一步較佳。 式中，*表示與其他結構的鍵結部位。[Chemical formula 3]

In the formula, A is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO- Or the group in these combinations is preferably, single bond or selected from alkylene with 1 to 3 carbon atoms which can be substituted by fluorine atom, -O-, -C(=O)-, -S- or The group in -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ - is further preferred good. In the formula, * represents a bonding site with other structures.

Specifically, as the diamine, at least one diamine selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4- Diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-amine cyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; m- or p-phenylenediamine, diaminotoluene, 4,4' - or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diamine Diphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3 ,3'-Diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) ) Hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis (3-Amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfane, Bis(4-amino-3-hydroxyphenyl) benzene, 4,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-( 4-aminophenoxy) phenyl] bis[4-(3-aminophenoxy) phenyl] bis[4-(2-aminophenoxy) phenyl] bis[4-(2-aminophenoxy) phenyl] bis, 1 ,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl Di, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3 ,3'-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl Phenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4- Aminophenyl) fluoride, 4,4'-dimethyl-3,3'-diaminodiphenylene, 3,3',5,5'-tetramethyl-4,4'-diamine diphenylmethane, 2,4- and 2,5 -Diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl yl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4- Aminophenyl)ethane, diaminobenzylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminobenzoic acid) phenyl) hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4 -aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminobenzene) oxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4- (4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4, 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4, 4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl Di, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4 '-Diaminobiphenyl, 4,4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotriphenyl 𠯤 and 4,4'-diamino-p-tetraphenyl.

Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. WO 2017/038598 are also preferred.

In addition, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO- which may be substituted by a fluorine atom. Or a group formed by a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO ₂ - which may be substituted by a fluorine atom. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價的有機基團，R⁵⁰ ～R⁵⁷ 中的至少1個為氟原子、甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價的有機基團，可以舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式5]

式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子或三氟甲基。 作為提供式（51）或（61）的結構之二胺化合物，可以舉出2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用一種或者組合使用兩種以上。In addition, it is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 4]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Examples of the monovalent organic groups of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 6), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 10). Fluorinated alkyl groups of numbers 1 to 6), etc. [Chemical formula 5]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group. As the diamine compound providing the structure of formula (51) or (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine can be mentioned Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.

In addition to this, the following diamines can also be preferably used. [Chemical formula 6]

式（5）中，R¹¹² 係單鍵或選自可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -及-NHCO-以及該等的組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -中之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之群組中之2價的基團為進一步較佳。R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [Chemical formula 7]

In formula (5), R ¹¹² is a single bond or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ - and -NHCO- And the groups in these combinations are preferably single bonds or selected from alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, -S- and -SO ₂ - The group in is more preferably selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ - The divalent group in the group is further preferred.

式（O）中，R¹¹⁵ 表示4價的有機基團。R¹¹⁵ 的較佳範圍與式（2）中的R¹¹⁵ 同義，較佳範圍亦相同。Specifically, as ^R115 , the tetracarboxylic acid residue etc. which remain after removing the anhydride group from the tetracarboxylic dianhydride are mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 8]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferable range of R ¹¹⁵ is synonymous with R ¹¹⁵ in formula (2), and the preferable range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' - Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6, 7-Naphthalenetetracarboxylic dianhydride, 1,4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2 ,3-dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4, 4-tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10- Perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride Anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4- A pyromellitic dianhydride, and these C1-6 alkyl groups and C1-6 alkoxy derivatives.

Moreover, as a preferable example, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. WO 2017/038598 can also be mentioned.

It is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. As a polymerizable group, it is a group which can carry out a crosslinking reaction by the action of heat, a radical, etc., and a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoyl group. azole group, blocked isocyanate group, methylol group, amine group. As a radically polymerizable group which a polyimide precursor etc. have, the group which has an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like, and the group represented by the following formula (III) is better.

[Chemical formula 9]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a polyalkeneoxy group. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecylene, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy, ethylidene, propylidene, trimethylene, -CH ₂ CH ( OH) CH ₂ - and polyalkeneoxy are more preferable, and polyalkoxy is further preferable. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkaneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. When the polyalkeneoxy group contains a plurality of alkeneoxy groups with different alkylene groups, the arrangement of the alkeneoxy groups in the polyalkeneoxy group may be random, or may be an arrangement with blocks , and can also be an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2-10, more preferably 2-6, 2-5 2 to 4 are further preferred, 2 or 3 are particularly preferred, and 2 is the most preferred. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. In addition, the number of alkeneoxy groups (the number of repetitions of the polyalkeneoxy groups) contained in the polyalkeneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyetheneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a polytetramethyleneoxy group, or a polytetramethyleneoxy group. A group formed by bonding an oxy group and a plurality of propeneoxy groups is preferable, polyethoxy group or polypropoxy group is more preferable, and polyethoxy group is further preferable. In the group formed by the bonding of the above-mentioned plural ethoxy groups and plural propoxy groups, the ethoxy groups and the propoxy groups may be arranged randomly, or they may be arranged in blocks, or they may be arranged in the form of Alternating and other patterns. The preferable aspect of the repeating number of the ethoxy group etc. in these groups is as mentioned above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two, or three carbons constituting an aryl group, preferably one carbon. Specifically, an aromatic group having 6 to 20 carbon atoms having an acidic group, and an aralkyl group having 7 to 25 carbon atoms having an acidic group can be mentioned. More specifically, the phenyl group which has an acidic group and the benzyl group which has an acidic group are mentioned. The acidic group is preferably an OH group. More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a straight-chain or branched-chain alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group. The carbon number of the alkyl group is preferably from 1 to 30. The alkyl group may be any of straight chain, branched chain and cyclic. Examples of straight-chain or branched-chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. base, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethyl oxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy, 2-(2-(2-(2-methoxyethoxy) yl)ethoxy)ethoxy)ethoxy and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl, and bicyclic Hexyl and Pinenyl. Among them, the cyclohexyl group is the most suitable from the viewpoint of achieving high sensitivity. In addition, as the alkyl group substituted with an aromatic group, a straight-chain alkyl group substituted with an aromatic group described later is preferable. As the aromatic group, specifically, a substituted or unsubstituted benzene ring, naphthalene ring, cyclopentadiene ring, indene ring, azulene ring, heptavine ring, indene ring, perylene ring, fused pentaene ring Benzene ring, acenaphthene ring, phenanthrene ring, anthracene ring, condensed tetraphenyl ring, anthracene ring, bi-triphenylene ring, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, Thiazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring , 呔𠯤 ring, naridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acridine ring, phenanthrene ring, thien ring, chromene ring, Kou Yamaguchi star ring, phenothia ring, phenothia 𠯤 ring or brown 𠯤 ring. The benzene ring is the best.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylamino propyl methacrylate is mentioned.

At least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes under the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group, but an acetal group, a ketal group, a silyl group, and a silyl ether group are included. , a tertiary alkyl ester group, etc. are preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesion to the substrate. Specifically, as the diamine component, aspects such as bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane are used.

式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示2價的有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基團，R¹¹³ 及R¹¹⁴ 中的至少一者為包含聚合性基之基團，兩者為聚合性基為較佳。The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors and the like used in the present invention preferably has a repeating unit precursor represented by formula (2-A). By setting it as such a structure, the width|variety of exposure latitude can be enlarged further. Formula (2-A) [Chemical Formula 10]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. group, at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both are preferably a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are each independently synonymous with A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same. R ¹¹² is synonymous with R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating structural unit represented by the formula (2), or may contain two or more types. In addition, structural isomers of the repeating unit represented by the formula (2) may also be included. In addition, the polyimide precursor may, of course, contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units except the terminal polyimide precursor may be the repeating units represented by the formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and further preferably 22,000 to 25,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersion degree of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly specified. For example, 4.5 or less is better, 4.0 or less is more preferred, 3.8 or less is further preferred, 3.2 or less is further preferred, and 3.1 or less is preferred. In order to be more preferable, 3.0 or less is still further preferable, and 2.95 or less is particularly preferable. In this specification, the dispersion degree of molecular weight is a value calculated by a weight average molecular weight/number average molecular weight meter.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer whose main component is an organic solvent. In this specification, the alkali-soluble polyimide means that 0.1 g or more of polyimide is dissolved in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C, and from the viewpoint of pattern formation, 0.5 g or more is dissolved. Polyimide of g or more is preferable, and it is more preferable to dissolve polyimide of 1.0 g or more. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less. Moreover, from the viewpoint of the film strength and insulating properties of the obtained organic film, a polyimide-based polyimide having a plurality of imide structures in the main chain is preferable. In this specification, the "main chain" refers to the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains.

-Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has a fluorine atom. The fluorine atom is preferably included in, for example, R ¹³² in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later, and it is included as a fluorinated alkyl group described later. R ¹³² in the repeating unit represented by the formula (4) or R ¹³¹ in the repeating unit represented by the formula (4) described later is more preferable. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g.

-Silicon atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has a silicon atom. For example, it is preferable that the silicon atom is included in R ¹³¹ in the repeating unit represented by the formula (4) described later, and it is included in the compound represented by the formula (4) described later as the organic modified (poly)siloxane structure described later. R ¹³¹ in the repeating unit is more preferred. In addition, the silicon atom or the organic modified (poly)siloxane structure may be included in the side chain of the polyimide, but it is preferably included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01-5 mol/g, more preferably 0.05-1 mol/g.

-Ethylene unsaturated bond- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have an ethylenically unsaturated bond in the side chain, but it is preferable to have an ethylenically unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is preferably included in R ¹³² in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later, as having an ethylenically unsaturated bond It is more preferable that the group is included in R ¹³² in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later. Among these, it is preferable that an ethylenically unsaturated bond is included in R ¹³¹ in the repeating unit represented by the formula (4) described later, and the group having an ethylenically unsaturated bond is included in the formula ( 4) R ¹³¹ in the repeating unit represented is better. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, and the like, which are directly bonded to an aromatic ring and have a vinyl group which may be substituted, and (meth)acryloyl groups. group, a (meth)acryloyloxy group, a group represented by the following formula (IV), and the like.

[Chemical formula 11]

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH- , (poly)alkaneoxy with 2-30 carbon atoms (the carbon number of the alkylene group is 2-12 is better, 2-6 is better, 2 or 3 is particularly preferred; the repeating number system 1-12 is Preferably, 1 to 6 are more preferred, 1 to 3 are particularly preferred) or a group formed by combining two or more of these.

式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等中的2個以上鍵結而成之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（III）中的R²⁰¹ 所鍵結之氧原子的鍵結部位。 式（R1）～（R3）中，L中之碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣與上述的R²¹ 中之碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣相同。 式（R1）中，X係氧原子為較佳。 式（R1）～（R3）中，*與式（IV）中的*同義，較佳態樣亦相同。 式（R1）所表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有異氰酸酯基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸酯基乙酯等）進行反應而得到。 式（R2）所表示之結構例如藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥基乙酯等）進行反應而得到。 式（R3）所表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有縮水甘油基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸縮水甘油酯等）進行反應而得到。 作為聚伸烷氧基，從溶劑溶解性及耐溶劑性的觀點而言，聚伸乙氧基、聚伸丙氧基、聚三亞甲氧基、聚四亞甲氧基或由複數個伸乙氧基和複數個伸丙氧基鍵結而成之基團為較佳，聚伸乙氧基或聚伸丙氧基為更佳，聚伸乙氧基為進一步較佳。在由上述複數個伸乙氧基和複數個伸丙氧基鍵結而成之基團中，伸乙氧基和伸丙氧基可以無規排列，亦可以形成嵌段而排列，亦可以排列成交替等圖案狀。該等基團中的伸乙氧基等的重複數的較佳態樣如上所述。Among these, R ²¹ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by the formula (R1). [Chemical formula 12]

In the formulae (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkaneoxy group having 2 to 30 carbon atoms, or two or more of these. X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom bonded to R ²⁰¹ in formula (III). In the formulae (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkaneoxy group having 2 to 30 carbon atoms in L is the same as the carbon number in the above-mentioned R ²¹ . The preferable aspects of the alkylene group having 2 to 12 or the (poly)alkaneoxy group having 2 to 30 carbon atoms are the same. In the formula (R1), an X-based oxygen atom is preferable. In formulas (R1) to (R3), * is synonymous with * in formula (IV), and the preferred embodiments are also the same. The structure represented by the formula (R1) is obtained, for example, by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate, etc.). obtained by the reaction. The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.). get. From the viewpoint of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyetheneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a polytetramethyleneoxy group, or a polytetramethyleneoxy group. A group formed by bonding an oxy group and a plurality of propeneoxy groups is preferable, polyethoxy group or polypropoxy group is more preferable, and polyethoxy group is further preferable. In the group formed by the bonding of the above-mentioned plural ethoxy groups and plural propoxy groups, the ethoxy groups and the propoxy groups may be arranged randomly, or they may be arranged in blocks, or they may be arranged in the form of Alternating and other patterns. The preferable aspect of the repeating number of the ethoxy group etc. in these groups is as mentioned above.

In formula (IV), * represents a bonding site with other structures, and a bonding site with the main chain of polyimide is preferable.

The amount of the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g. In addition, from the viewpoint of production suitability, the amount of the ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.0005 to 0.05 mol/g.

-Crosslinkable groups other than ethylenically unsaturated bonds - The polyimide may have crosslinkable groups other than ethylenically unsaturated bonds. Examples of crosslinkable groups other than ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. It is preferable that the crosslinkable group other than the ethylenically unsaturated bond is contained in R ¹³¹ in the repeating unit represented by the formula (4) described later, for example. The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g. In addition, from the viewpoint of production suitability, the amount of the crosslinkable groups other than the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g good.

-Polarity Conversion Group- The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable groups in the polyimide are the same as the acid-decomposable groups described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiments are also the same.

-Acid value- When the polyimide is used for alkali development, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g from the viewpoint of improving the developability The above is further preferred. Further, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. In addition, when polyimide is used for development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of polyimide is 2 to 35 mgKOH/g, which is relatively low. Preferably, 3-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is further preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Moreover, as an acid group contained in polyimide, the acid group with a pKa of 0-10 is preferable, and the acid group with a pKa of 3-8 is more preferable from the viewpoint of both storage stability and developability. The pKa is represented by the negative logarithm pKa of the equilibrium constant Ka taking into account the dissociation reaction that releases hydrogen ions from the acid. In this specification, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, refer to the values described in "Revision 5th Edition Chemical Handbook Basic Edition" edited by the Chemical Society of Japan. In addition, when the acid group is, for example, a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As the acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

-Phenolic hydroxyl group- From the viewpoint of making the developing speed by an alkali developer suitable, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is preferably contained in, for example, R ¹³² in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later. The amount of the phenolic hydroxyl groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.

式（4）中，R¹³¹ 表示2價的有機基團，R¹³² 表示4價的有機基團。 當具有聚合性基時，聚合性基可以位於R¹³¹ 及R¹³² 中的至少一者上，如下述式（4-1）或式（4-2）所示，亦可以位於聚醯亞胺的末端。 式（4-1） [化學式14]

式（4-1）中，R¹³³ 為聚合性基，其他基團與式（4）同義。 式（4-2） [化學式15]

R¹³⁴ 及R¹³⁵ 中的至少一者為聚合性基，當不是聚合性基的情況下為有機基團，其他基團與式（4）同義。The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable to include a repeating unit represented by the following formula (4). [Chemical formula 13]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When it has a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or may be located on the polyimide end. Formula (4-1) [Chemical Formula 14]

In formula (4-1), R ¹³³ is a polymerizable group, and the other groups are synonymous with formula (4). Formula (4-2) [Chemical Formula 15]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are synonymous with formula (4).

The polymerizable group is synonymous with the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like. R ¹³¹ represents a divalent organic group. As a divalent organic group, the same as R ¹¹¹ in formula (2) can be exemplified, and the preferable range is also the same. Moreover, as ^R131 , the diamine residue which remains after removing the amine group of a diamine is mentioned. As a diamine, an aliphatic, cycloaliphatic, or aromatic diamine etc. are mentioned. As a specific example, the example of ^R111 in Formula (2) of a polyimide precursor can be mentioned.

From the viewpoint of more effectively suppressing warpage during calcination, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, one molecule contains a total of two or more diamine residues of either an ethylene glycol chain or a propylene glycol chain, or both, and more preferably a diamine residue that does not contain an aromatic ring.

As a diamine containing two or more ethylene glycol chains and propylene glycol chains in total in one molecule, or both, JEFFAMINE (registered trademark) KH-511, ED-600, and ED-900 can be mentioned. , ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2- Aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2- Amines and the like, but are not limited to these.

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, the same as R ¹¹⁵ in formula (2) can be exemplified, and the preferable range is also the same. For example, four bonders of the tetravalent organic group exemplified as R ¹¹⁵ are bonded to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

Moreover, as R ¹³² , the tetracarboxylic acid residue etc. which remain after removing the anhydride group from the tetracarboxylic dianhydride are mentioned. As a specific example, the example of R ¹¹⁵ in the formula (2) of the polyimide precursor can be mentioned. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group in at least one of R ¹³¹ and R ¹³² . More specifically, as R ¹³¹ , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminobenzene) can be mentioned as preferred examples base) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA- 1) to (DA-18), as R ¹³² , the above-mentioned (DAA-1) to (DAA-5) can be mentioned as more preferable examples.

Moreover, it is also preferable that polyimide has a fluorine atom in a structural unit. The content of the fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

Moreover, in order to improve the adhesiveness with a board|substrate, polyimide may be copolymerized with the aliphatic group which has a siloxane structure. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

In addition, in order to improve the storage stability of the composition, it is preferable to seal the main chain ends of the polyimide with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, and a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8 -Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7 -aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 -aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminosalicylic acid Benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol , 4-aminothiophenol, etc. Two or more kinds of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

- Imidization rate (ring closure rate) - The imidization rate (also referred to as "ring closure rate") of polyimide is 70% from the viewpoints of film strength, insulating properties, etc. of the obtained organic film The above is better, more than 80% is more preferable, and more than 90% is more preferable. The upper limit of the imidization rate is not particularly limited, as long as it is 100% or less. The said imidization rate is measured by the following method, for example. The infrared absorption spectrum of the polyimide was measured, and the peak intensity P1 in the vicinity of 1377 cm ⁻¹ was determined as an absorption peak derived from the structure of the imide. Next, after heat-treating this polyimide at 350 degreeC for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 of the vicinity of 1377 cm ^-1 was calculated|required. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

All of the polyimides may contain a repeating unit represented by the above formula (4) containing one R ¹³¹ or R ¹³² , or may contain two or more different types of R ¹³¹ or R ¹³² The repeating unit represented by the formula (4) Represents the repeating unit. Moreover, in addition to the repeating unit represented by said formula (4), polyimide may contain other kinds of repeating structural units. As another kind of repeating unit, the repeating unit etc. which are represented by the above-mentioned formula (2) are mentioned, for example.

The polyimide can be synthesized, for example, by a method of reacting a tetracarboxylic dianhydride and a diamine compound (a part of which is substituted with a monoamine end capping agent) at a low temperature; A method of reacting dianhydride (part of replacement with acid anhydride or monochloride compound or monoactive ester compound capping agent) and diamine compound; obtain diester by tetracarboxylic dianhydride and alcohol, and then make it with diamine compound A method in which the amine (a part of which is replaced by a monoamine end-capping agent) is reacted in the presence of a condensing agent; the diester is obtained from a tetracarboxylic dianhydride and an alcohol, and the remaining dicarboxylic acid is then chlorinated and allowed to A method of reacting it with a diamine (a part of which is replaced by a monoamine end-capping agent), etc., to obtain a polyimide precursor, and a method of completely imidizing it using a known imidization reaction method ; Or, a method of stopping the imidization reaction in the middle to introduce a part of the imide structure; and a method of introducing a part of the imide structure by mixing a fully imidized polymer and the polyimide precursor . As a commercial item of polyimide, Durimide (registered trademark) 284 (manufactured by FUJIFILM Co., Ltd.) and Matrimide 5218 (manufactured by HUNTSMAN) can be exemplified.

The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight into 5,000 or more, the folding endurance of the film after hardening can be improved. In order to obtain an organic film excellent in mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Moreover, when two or more types of polyimide are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is within the above-mentioned range.

式（3）中，R¹²¹ 表示2價的有機基團，R¹²² 表示4價的有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價的有機基團。[Polybenzoxazole Precursor] Although the structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, it is preferable to include a repeating unit represented by the following formula (3). [Chemical formula 16]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ are respectively synonymous with R ¹¹³ in formula (2), and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a linear or branched (preferably linear) aliphatic The dicarboxylic acid consisting of a group group and 2 -COOH is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and further preferably 4 to 15, 5 to 10 is particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of the dicarboxylic acid containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. , tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoro Glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methyl Glutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctane Diacid, azelaic acid, sebacic acid, hexafluorodecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, behenanedioic acid , tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptacosanedioic acid, hexadecanedioic acid, nonacosanedioic acid, triacosanedioic acid, three Undecanedioic acid, tridocosanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulae, and the like.

（式中，Z為碳數1～6的烴基，n為1～6的整數。）[Chemical formula 17]

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferable, and the following dicarboxylic acids consisting only of an aromatic group and two -COOH are more preferable.

式中，A表示選自包括-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之群組中之2價的基團，*分別獨立地表示與其他結構的鍵結部位。[Chemical formula 18]

In the formula, A represents selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ A divalent group in the group of -, * each independently represents a bonding site with other structures.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as that of R ¹¹⁵ in the above formula (2), and the preferable range is also the same. R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'- Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl Amino-3,3'-dihydroxydiphenyl, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2 ,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino- -3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-Diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino- 4,4'-Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino -4,6-Dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.

式中，X₁ 表示-O-、-S-、-C（CF₃ ）₂ -、-CH₂ -、-SO₂ -、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價的取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R¹²² 係由上述式表示之結構亦為較佳。當R¹²² 為由上述式表示之結構的情況下，在共計4個*及#中，任意2個為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位，且其他2個為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位，且2個#為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位，或者2個*為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位，且2個#為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位，且2個#為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位為進一步較佳。[Chemical formula 19]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. In addition, the structure in which R ¹²² is represented by the above formula is also preferable. When R ¹²² is a structure represented by the above formula, of the total of 4 * and #, any 2 are a bonding site to the nitrogen atom to which R ¹²² in the formula (3) is bonded, and the other 2 One is preferably a bonding site with an oxygen atom bonded to R ¹²² in the formula (3), and two * are bonding sites with an oxygen atom bonded with R ¹²² in the formula (3), and 2 # are bonding sites with nitrogen atoms bonded to R ¹²² in formula (3), or 2 * are bonding sites with nitrogen atoms bonded with R ¹²² in formula (3), and 2 # are the bonding sites with the oxygen atom bonded to R ¹²² in the formula (3), and 2 * are the bonding sites with the oxygen atom bonded with R ¹²² in the formula (3). , and 2 # is the bonding site with the nitrogen atom bonded to R ¹²² in the formula (3), which is more preferable.

[Chemical formula 20]

In formula (As), R ₁ is hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond or selected from the following An organic group in the group of formula (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different. R ₃ is any one of a hydrogen atom, a straight-chain or branched-chain alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different.

（式（A-sc）中，*表示鍵結於上述式（A-s）所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環。）[Chemical formula 21]

(In the formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, that is, on R ₃ , brings the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it is considered to be a cause of high cyclization rate when hardened at low temperature. It is particularly preferable from the viewpoint that the effect is further improved.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, the effects of high transparency to i-rays and high cyclization rate during curing at low temperature are maintained, which is preferable.

In addition, in the above formula (As), it is more preferable that R ₁ is an alkylene group or a substituted alkylene group. Specific examples of the alkylidene and substituted alkylene groups of R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, among which, while maintaining high transparency to i-rays and -CH ₂ - and -CH(CH ₃ ) have the effect of high cyclization rate when hardened at a low temperature and can obtain a polybenzoxazole precursor excellent in the balance of sufficient solubility to a solvent. -, -C(CH ₃ ) ₂ - is more preferable.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A No. 2013-256506. The contents are incorporated into this manual.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, which are incorporated into the present specification. middle. Of course, it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3). In addition, it is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another kind of repeating structural unit from the viewpoint of being able to suppress the occurrence of warpage accompanying ring closure.

式（SL）中，Z具有a結構和b結構，R^1s 為氫原子或碳數1～10的烴基，R^2s 為碳數1～10的烴基，R^3s 、R^4s 、R^5s 、R^6s 中的至少1個為芳香族基，其餘為氫原子或碳數1～30的有機基團，其分別可以相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合，亦可以為無規聚合。關於Z部分的莫耳%，a結構為5～95莫耳%、b結構為95～5莫耳%，a+b為100莫耳%。[Chemical formula 22]

In formula (SL), Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R ^2s is a hydrocarbon group with 1 to 10 carbon atoms, R ^3s , R ^4s , R ^5s , R ^6s At least one of them is an aromatic group, and the rest are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mol % of the Z part, the a structure is 5 to 95 mol %, the b structure is 95 to 5 mol %, and a+b is 100 mol %.

In the formula (SL), as preferable Z, those in which R ^5s and R ^6s in the b structure are phenyl groups can be mentioned. In addition, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

When the diamine residue represented by the formula (SL) is included as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride is also included as the repeating structural unit. is better. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in the formula (2).

For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly specified, for example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is further preferred, and 2.2 or less is preferred. for further better.

式（X）中，R¹³³ 表示2價的有機基團，R¹³⁴ 表示4價的有機基團。 當具有聚合性基或酸分解性基等極性轉換基時，聚合性基或酸分解性基等極性轉換基可以位於R¹³³ 及R¹³⁴ 中的至少一者上，亦可以如下述式（X-1）或式（X-2）所示，位於聚苯并㗁唑的末端。 式（X-1） [化學式24]

式（X-1）中，R¹³⁵ 及R¹³⁶ 中的至少一者為聚合性基或酸分解性基等極性轉換基，當不是聚合性基或酸分解性基等極性轉換基時為有機基，其他基團與式（X）同義。 式（X-2） [化學式25]

式（X-2）中，R¹³⁷ 為聚合性基或酸分解性基等極性轉換基，其他為取代基，其他基團與式（X）同義。[Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferable, and is represented by the following The compound represented by formula (X) and having a polymerizable group is more preferable. As the above-mentioned polymerizable group, a radically polymerizable group is preferable. Moreover, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid-decomposable group. [Chemical formula 23]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When there is a polar conversion group such as a polymerizable group or an acid-decomposable group, the polar conversion group such as a polymerizable group or an acid-decomposable group may be located on at least one of R ¹³³ and R ¹³⁴ , or it may be shown in the following formula (X- 1) or shown in formula (X-2), it is located at the end of polybenzoxazole. Formula (X-1) [Chemical Formula 24]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polar conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polar conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group , and other groups are synonymous with formula (X). Formula (X-2) [Chemical Formula 25]

In the formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, the other groups are substituent groups, and the other groups are synonymous with the formula (X).

The polarity conversion group such as a polymerizable group or an acid-decomposable group is synonymous with the polymerizable group described in the above-mentioned polymerizable group contained in the polyimide precursor or the like.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic or an aromatic group is mentioned. As a specific example, the example of ^R121 in Formula (3) of a polybenzoxazole precursor is mentioned. In addition, its preferable example is the same as that of ^R121 .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include R ¹²² in the formula (3) of the polybenzoxazole precursor. In addition, its preferable example is the same as that of R ¹²² . For example, four bonders of the tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical formula 26]

The oxazole rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more. When the oxazolylization ratio is 85% or more, the film shrinkage due to the ring closure generated during oxazolylization by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

All of the polybenzoxazoles may contain a repeating structural unit of the above formula (X) containing one R ¹³¹ or R ¹³² , or may contain two or more different types of R ¹³¹ or R ¹³² The repeating structural unit of the above formula (X) repeating unit. Moreover, in addition to the repeating unit of the said formula (X), a polybenzoxazole may contain other kinds of repeating structural units.

Polybenzoxazole is prepared, for example, by mixing a bisaminophenol derivative with a dicarboxylic acid dichloride and a dicarboxylic acid derivative selected from the group consisting of dicarboxylic acids containing R ¹³³ or the above-mentioned dicarboxylic acids, and the like. The compound is reacted to obtain a polybenzoxazole precursor, which is obtained by oxazoleization by a known oxazole method. Moreover, in the case of a dicarboxylic acid, in order to improve reaction yield etc., the active ester type dicarboxylic acid derivative obtained by making 1-hydroxy-1,2,3-benzotriazole etc. react in advance can be used.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight into 5,000 or more, the folding endurance of the film after hardening can be improved. In order to obtain an organic film excellent in mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Moreover, when containing two or more types of polybenzoxazoles, it is preferable that the weight average molecular weight of at least one type of polybenzoxazoles is in the said range.

式（PAI-2）中，R¹¹⁷ 表示3價的有機基團，R¹¹¹ 表示2價的有機基團，A² 表示氧原子或-NH-，R¹¹³ 表示氫原子或1價的有機基團。[Polyamide imide precursor] It is preferable that the polyamide imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical formula 27]

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group .

In formula (PAI-2), R ¹¹⁷ can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or by single bonds or linking groups. A group formed by linking two or more of these groups is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms. Preferably, an aromatic group, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by a single bond or a linking group, an aromatic group having 6 to 20 carbon atoms, or A group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two of these The linking group formed by the above-mentioned bonds is preferable, and the linking group formed by bonding two or more of the above is even more preferable. good. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Also, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups of the above-mentioned tricarboxylic acid compound may be acid anhydrided. As the tricarboxylic acid compound which may be halogenated to be used in the production of the polyamide imide precursor, branched aliphatic, cyclic, or aromatic tricarboxylic acid compounds, etc. can be mentioned. Only one type of these tricarboxylic acid compounds may be used, or two or more types may be used.

Specifically, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, Aromatic group having 6 to 20 carbon atoms, or a tricarboxylic acid compound of a group formed by combining two or more of these groups through a single bond or a linking group is preferred, including aromatic groups having 6 to 20 carbon atoms. A tricarboxylic acid compound of a group or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group is more preferable.

In addition, specific examples of the tricarboxylic acid compound include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6 -Naphthalene tricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are composed of single bonds, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or phenylene-linked compounds, etc. These compounds can be compounds anhydrided with two carboxyl groups (for example, trimellitic anhydride), or can be halogenated compounds with at least one carboxyl group (for example, trimellitic anhydride ammonium chloride).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in the above formula (2), respectively, and the preferred embodiments are also the same.

The polyamidoimide precursor may also contain other repeating units. As another repeating unit, the repeating unit represented by the above-mentioned formula (2), the repeating unit represented by the following formula (PAI-1), etc. are mentioned. [Chemical formula 28]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In formula (PAI-1), R ¹¹⁶ can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or by a single bond or a linking group. A group formed by linking two or more of these groups is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms. Preferably, an aromatic group, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by a single bond or a linking group, an aromatic group having 6 to 20 carbon atoms, or A group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two of these The linking group formed by the above-mentioned bonds is preferable, and the linking group formed by bonding two or more of the above is even more preferable. good. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Moreover, it is preferable that R ¹¹⁶ is derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound. The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, but it is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. As the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated and used in the production of the polyamide imide precursor, linear or branched aliphatic and cyclic aliphatic compounds can be exemplified. aromatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds, etc. Only one kind of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more kinds thereof may be used.

Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a carbon number of 3 to 20. A cyclic aliphatic group, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these through a single bond or a linking group is a dicarboxylic acid compound or dicarboxylic acid dicarboxylic acid The halide compound is preferably a dicarboxylic acid containing an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group Compounds or dicarboxylic acid dihalide compounds are more preferred.

Further, specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetra Fluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylsuccinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanedioic acid acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, tenanedioic acid Heptanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, tetracosanedioic acid, tetracosanedioic acid , Pentadecanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Nonacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid Dodecanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, Benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of a dicarboxylic acid dihalide compound, the compound of the structure in which two carboxyl groups are halogenated among the specific examples of the above-mentioned dicarboxylic acid compound can be mentioned.

In the formula (PAI-1), the meaning of R ¹¹¹ is the same as that of R ¹¹¹ in the above formula (2), and the preferred aspects are also the same.

Moreover, it is also preferable that the polyamide imide has a fluorine atom in the structural unit. The content of fluorine atoms in the polyamide imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, the polyamide imide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesiveness with the substrate. Specifically, as the diamine component, aspects such as bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane are used.

As an embodiment of the polyamide imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) can be mentioned. The total content of repeating units is 50 mol% or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all repeating units except the terminal polyamide imide precursor may be repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1) Any one of the repeating unit and the repeating unit represented by formula (2). In addition, as another embodiment of the polyamide imide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be given as: More than 50 mol% of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, except that all repeating units in the terminal polyamide imide precursor may be the repeating units represented by the formula (PAI-2) or the repeating units represented by the formula (PAI-1). Any of the repeating units.

The weight average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, further preferably 10,000 to 50,000. Moreover, as for the number average molecular weight (Mn), 800-250,000 are preferable, 2,000-50,000 are more preferable, 4,000-25,000 are still more preferable.

The molecular weight dispersion of the polyamide imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[Polyamide imide] The polyimide imide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide imide soluble in a developer whose main component is an organic solvent. In this specification, the alkali-soluble polyamide imide means that 0.1 g or more of the polyamide imide is dissolved at 23° C. with respect to 100 g of a 2.38 mass % tetramethylammonium aqueous solution, and it is considered from the viewpoint of pattern formation. In other words, it is better to dissolve more than 0.5 g of polyamide imide, and it is more preferred to dissolve more than 1.0 g of polyamide imide. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less. In addition, from the viewpoint of the film strength and insulating properties of the obtained organic film, the polyamide imide is a polyamide imide having a plurality of amide bonds and a plurality of amide imine structures in the main chain. is better.

-Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has a fluorine atom. The fluorine atom is preferably included in, for example, R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, and is included in the repeating unit represented by the formula (PAI-3) described later as a fluorinated alkyl group. R ¹¹⁷ or R ¹¹¹ in is more preferable. The amount of fluorine atoms relative to the total mass of the polyamide imide is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g.

-Ethylene Unsaturation - From the viewpoint of the film strength of the obtained organic film, the polyimide imide may have an ethylenic unsaturated bond. The polyamide imide may have an ethylenically unsaturated bond at the end of the main chain or may have an ethylenically unsaturated bond in the side chain, but it is preferable to have an ethylenically unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, and is included in the formula (PAI-3) described later as a group having an ethylenically unsaturated bond -3) R ¹¹⁷ or R ¹¹¹ in the repeating unit represented is more preferable. The preferable aspect of the group having an ethylenically unsaturated bond is the same as the preferable aspect of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

The amount of the ethylenically unsaturated bond relative to the total mass of the polyamide imide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.

-Crosslinkable groups other than ethylenically unsaturated bonds - The polyamide imide may have crosslinkable groups other than ethylenically unsaturated bonds. Examples of the bridging group other than the ethylenically unsaturated bond in the polyimide imide include the same groups as the bridging group other than the ethylenically unsaturated bond in the above-mentioned polyimide. It is preferable that the crosslinkable group other than the ethylenically unsaturated bond is contained in R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, for example. The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyamide imide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.

-Polarity Conversion Group- The polyamide imide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamide imide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiments are also the same.

-Acid value- When the polyamide imide is used for alkali development, the acid value of the polyamide imide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, from the viewpoint of improving the developability , 70mgKOH/g or more is further preferred. Further, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. In addition, when the polyimide imide is used for development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide imide is 2 ∼35 mgKOH/g is preferable, 3∼30 mgKOH/g is more preferable, and 5∼20 mgKOH/g is further preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Moreover, as an acid group contained in a polyimide imide, the same group as the acid group in the above-mentioned polyimide can be mentioned, and the preferable aspect is also the same.

-Phenolic hydroxyl group- From the viewpoint of making the developing speed by an alkali developer suitable, it is preferable that the polyimide imide has a phenolic hydroxyl group. The polyamide imide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is preferably contained in, for example, R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later. The amount of the phenolic hydroxyl groups relative to the total mass of the polyamide imide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.

式（PAI-3）中，R¹¹¹ 及R¹¹⁷ 分別與式（PAI-2）中的R¹¹¹ 及R¹¹⁷ 同義，較佳的態樣亦相同。 當具有聚合性基的情況下，聚合性基可以位於R¹¹¹ 及R¹¹⁷ 中的至少一者上，亦可以位於聚醯胺醯亞胺的末端。The polyimide imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an imide bond, but includes a repeating unit represented by the following formula (PAI-3) is better. [Chemical formula 29]

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and the preferred embodiments are also the same. In the case of having a polymerizable group, the polymerizable group may be located on at least one of R ¹¹¹ and R ¹¹⁷ , or may be located at the terminal of the polyimide imide.

In addition, in order to improve the storage stability of the composition, it is preferable to seal the main chain ends of the polyamide imide with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, and a monoactive ester compound. The preferred aspect of the blocking agent is the same as the preferred aspect of the blocking agent in the above-mentioned polyimide.

-imidization rate (ring closure rate)- From the viewpoints of film strength, insulating properties, etc. of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyamide imide is preferably 70% or more, and preferably 80% or more. Better, more than 90% is better. The upper limit of the imidization rate is not particularly limited, as long as it is 100% or less. The above-mentioned imidization rate is measured by the same method as the ring-closure rate of the above-mentioned polyimide.

All of the polyimide imides may contain repeating units represented by the above formula (PAI-3) containing one R ¹¹¹ or R ¹¹⁷ , or may contain the above formula containing two or more different types of R ¹³¹ or R ¹³² (PAI-3) represents the repeating unit. Moreover, in addition to the repeating unit represented by the said formula (PAI-3), the polyamide imide may contain other kinds of repeating units. As another kind of repeating unit, the repeating unit etc. which are represented by the above-mentioned formula (PAI-1) or (PAI-2) are mentioned.

The polyamidoimide can be synthesized by, for example, a method of obtaining a polyamidoimide precursor by a known method and completely imidizing it by a known imidization reaction method. , or stop the imidization reaction on the way, and introduce a part of the imide structure, and by mixing the fully imidized polymer and its polyimide precursor, introduce a part of the imide structure. method.

The weight average molecular weight (Mw) of the polyamide imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight into 5,000 or more, the folding endurance of the film after hardening can be improved. In order to obtain an organic film excellent in mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Moreover, when two or more types of polyimide are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is within the above-mentioned range.

[Method for producing polyimide precursor, etc.] A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. It is preferably obtained by reacting with diamine after halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent. In the production method of a polyimide precursor or the like, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately defined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

Moreover, it is also preferable to synthesize using a non-halogen-based catalyst without using the above-mentioned halogenating agent. As the above-mentioned non-halogen-based catalyst, a known amination catalyst that does not contain a halogen atom can be used without particular limitation, and examples thereof include boroxine compounds, N-hydroxy compounds, and tertiary amines. , Phosphate esters, amine salts, urea compounds, etc., carbodiimide compounds. As said carbodiimide compound, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, etc. are mentioned. In the production method of a polyimide precursor or the like, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately defined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

-Capping agent- When producing polyimide precursors, etc., in order to further improve storage stability, it is preferable to seal the ends of polyimide precursors, etc. . As the blocking agent, it is more preferable to use a monoamine, and preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8- Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7- aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5- aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4- Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-Aminothiophenol, etc. Two or more kinds of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

-Solid Precipitation- When producing a polyimide precursor or the like, a process of precipitating a solid may be included. Specifically, a solid can be deposited by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a soluble solvent such as a polyimide precursor such as tetrahydrofuran. Then, the polyimide precursor or the like is dried to obtain a powdery polyimide precursor or the like.

〔content〕 The content of the specific resin in the composition of the present invention is preferably 20 mass % or more, more preferably 30 mass % or more, more preferably 40 mass % or more, and 50 mass % or more with respect to the total solid content of the composition for further better. Furthermore, the content of the resin in the composition of the present invention is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % or less with respect to the total solid content of the composition. The following is more preferable, and 95 mass % or less is still more preferable. The composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range.

Moreover, it is also preferable that the curable resin composition of this invention contains at least two resins. Specifically, the curable resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, but preferably contains two or more specific resins. When the curable resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor and a dianhydride-derived structure (R ¹¹⁵ in the above formula (2)) is different. Two or more polyimide precursors are preferred.

<Specific compound> The curable resin composition of the present invention contains at least one group selected from the group consisting of N-hydroxyamino groups, N-hydroxyimino groups, N-hydroxyimino groups, and N-hydroxyimino groups Compound B (specific compound). The specific compound may contain in total at least one group selected from the group consisting of N-hydroxyamino group, N-hydroxyimino group, N-hydroxyimino group, and N-hydroxyimino group, or may contain Two or more, preferably only one is contained.

式（N-1）中，*分別獨立地表示與其他結構的鍵結部位，與氫原子、氮原子或碳原子的鍵結部位為較佳。[N-hydroxylamino group] In the present invention, the N-hydroxylamino group means a group represented by the following formula (N-1). However, the structure corresponding to the N-hydroxyimino group or the N-hydroxyimino group described later is assumed not to correspond to the N-hydroxyamino group. [Chemical formula 30]

In the formula (N-1), * each independently represents a bonding site with another structure, and a bonding site with a hydrogen atom, a nitrogen atom or a carbon atom is preferable.

在式（N1-1）或式（N1-2）中，*分別獨立地表示與其他結構的鍵結部位，為與碳原子的鍵結部位為較佳。Furthermore, in the present invention, when the specific compound contains an N-hydroxyamino group, it is preferable that the specific compound contains a structure represented by the following formula (N1-1) or formula (N1-2). [Chemical formula 31]

In the formula (N1-1) or the formula (N1-2), * each independently represents a bonding site with other structures, and is preferably a bonding site with a carbon atom.

在式（N1-3）中，*分別獨立地表示與其他結構的鍵結部位，與氫原子或碳原子的鍵結部位為較佳，與碳原子的鍵結部位為更較佳。Furthermore, in the present invention, when the specific compound includes the structure represented by the formula (N1-1), the specific compound includes the structure represented by the following formula (N1-3) as the structure represented by the above formula (N1-1). The structure is better. [Chemical formula 32]

In the formula (N1-3), * each independently represents a bonding site with other structures, a bonding site with a hydrogen atom or a carbon atom is preferable, and a bonding site with a carbon atom is more preferable.

在式（N-1-1）中，R^N11 及R^N12 分別獨立地表示氫原子或1價的取代基，R^N11 及R^N12 可以鍵結而形成環結構。 在式（N-1-2）中，R^N13 及R^N14 分別獨立地表示氫原子或1價的取代基，R^N13 及R^N14 可以鍵結而形成環結構。When the specific compound contains an N-hydroxyamino group, the specific compound is preferably a compound represented by any one of the following formulae (N-1-1) and (N-1-2). [Chemical formula 33]

In formula (N-1-1), R ^N11 and R ^N12 each independently represent a hydrogen atom or a monovalent substituent, and R ^N11 and R ^N12 may be bonded to form a ring structure. In formula (N-1-2), R ^N13 and R ^N14 each independently represent a hydrogen atom or a monovalent substituent, and R ^N13 and R ^N14 may be bonded to form a ring structure.

In formula (N-1-1), R ^N11 and R ^N12 each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group and are selected from the group consisting of -O-, -C(=O)-, -S-, -S (=O) ₂ - and -NR ^N - (R ^N is a hydrogen atom or a hydrocarbon group, a hydrogen atom is preferably a group) The group represented by the combination of at least one group is preferable, and the hydrocarbon group is preferable. good. In addition, in formula (N-1-1), the aspect in which R ^N11 and R ^N12 are bonded to form a ring structure is also one of the preferred aspects of the present invention, and the ring structure formed may be an alicyclic structure , may be an aromatic ring structure, may be a heterocyclic structure, or may be a hydrocarbon ring structure. As a hetero atom in the said heterocyclic structure, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, a silicon atom, etc. are mentioned. In addition, the above-mentioned ring structure is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 6-membered ring structure. Among these, as the above-mentioned ring structure, an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure is preferable, a benzene ring structure or a pyridine ring structure is more preferable, and a benzene ring structure is further preferable. As the hetero atom in the above-mentioned aromatic heterocyclic structure, a nitrogen atom is preferable. In addition, the above-mentioned ring structure may be substituted with the following well-known substituents: a hydrocarbon group which may be substituted with a halogen atom, a halogen atom, a carboxyl group, an amido group, a nitro group, and the like.

In formula (N-1-2), it is preferable that one of R ^N13 and R ^N14 represents a hydrogen atom, and the other represents a monovalent substituent. As the monovalent substituent in R ^N13 and R ^N14 , a hydrocarbon group is preferred, a hydrocarbon group having 1 to 10 carbon atoms is more preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred. for further better. When the carbon number of the above-mentioned alkyl group is 3 or more, a branched structure or a ring structure may be included, and a cyclic alkyl group may be used.

式（N-2）中，*分別獨立地表示與其他結構的鍵結部位，與碳原子的鍵結部位為較佳。[N-hydroxyimino group] In the present invention, the N-hydroxyimino group means a group represented by the following formula (N-2). [Chemical formula 34]

In formula (N-2), * each independently represents a bonding site with other structures, and a bonding site with a carbon atom is preferable.

式（N2-1）或式（N2-2）中，*表示與其他結構的鍵結部位，與碳原子的鍵結部位為較佳。 式（N2-2）中，R^N2 表示可以被取代之烷基或芳香族烴基，烷基、鹵烷基或苯基為更佳。在本說明書中，鹵烷基係指烷基的氫原子的一部分被鹵素原子取代之烷基，烷基的所有氫原子被鹵素原子取代之烷基為較佳。 當R^N2 係可以被取代之烷基的情況下，R^N2 的碳數係1～10為較佳，1～4為更佳，1或2為進一步較佳，1為特佳。 當R^N2 係芳香族烴基的情況下，R^N2 的碳數係6～20為較佳，6～12為更佳。Furthermore, in the present invention, when the specific compound contains an N-hydroxyimino group, it is preferable that the specific compound contains a structure represented by the following formula (N2-1) or formula (N2-2). [Chemical formula 35]

In the formula (N2-1) or the formula (N2-2), * represents a bonding site with other structures, and a bonding site with a carbon atom is preferable. In the formula (N2-2), R ^N2 represents an optionally substituted alkyl group or an aromatic hydrocarbon group, preferably an alkyl group, a haloalkyl group or a phenyl group. In the present specification, the haloalkyl group refers to an alkyl group in which a part of the hydrogen atoms of the alkyl group is replaced by a halogen atom, and an alkyl group in which all the hydrogen atoms of the alkyl group are replaced by a halogen atom is preferably an alkyl group. When R ^N2 is an alkyl group that can be substituted, the carbon number of R ^N2 is preferably 1-10, more preferably 1-4, more preferably 1 or 2, and particularly preferably 1. When R ^N2 is an aromatic hydrocarbon group, the carbon number of R ^N2 is preferably 6-20, more preferably 6-12.

式（N2-3）中，*分別獨立地表示與其他結構的鍵結部位，與碳原子的鍵結部位為較佳。Moreover, in the present invention, when the specific compound includes the structure represented by the formula (N2-1), the specific compound includes the structure represented by the following formula (N2-3) as the structure represented by the above formula (N2-1). The structure is better. [Chemical formula 36]

In formula (N2-3), * each independently represents a bonding site with other structures, and a bonding site with a carbon atom is preferable.

式（N-2-1）中，R^N21 及R^N22 分別獨立地表示1價的有機基團。When the specific compound contains an N-hydroxyimino group, the specific compound is preferably a compound represented by the following formula (N-2-1). [Chemical formula 37]

In formula (N-2-1), R ^N21 and R ^N22 each independently represent a monovalent organic group.

In formula (N-2-1), R ^N21 and R ^N22 independently represent a cyano group, a hydrocarbon group, or a hydrocarbon group and are selected from the group consisting of -O-, -C(=O)-, -S-, -S( =O) ₂ and -NR ^N - (R ^N is a hydrogen atom or a hydrocarbon group, a hydrogen atom is preferred) The group represented by the combination of at least one group is preferably a cyano group, a hydrocarbon group, Or a group represented by -C(=O)OR (R is a hydrocarbon group) is more preferable. When R ^N21 and R ^N22 are hydrocarbon groups, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an alkyl group, an alkenyl group, or an aromatic hydrocarbon group. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. When the carbon number of the above-mentioned alkyl group is 3 or more, a branched structure or a ring structure may be included, and a cyclic alkyl group may be used as the above-mentioned alkenyl group. Alkenyl groups of ~4 are more preferred. As the above-mentioned aromatic hydrocarbon group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. In addition, the above-mentioned hydrocarbon group may be substituted with a known substituent such as a halogen atom. As R in the group represented by the above -C(=O)OR, an alkyl group is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is even more preferable. When the carbon number of the above-mentioned alkyl group is 3 or more, a branched structure or a ring structure may be included, and a cyclic alkyl group may be used as a preferred aspect of the present invention, and one of R ^N21 and R ^N22 can be cyano. group, the other is the aspect represented by the group represented by -C(=O)OR, or the aspect in which both R ^N21 and R ^N22 are alkyl groups.

式（N-3）中，*分別獨立地表示與其他結構的鍵結部位，與氫原子、氮原子或碳原子的鍵結部位為較佳。[N-hydroxyamide group] In the present invention, the N-hydroxyamide group means a group represented by the following formula (N-3). However, the structure corresponding to the N-hydroxyimide group described later is assumed not to correspond to the N-hydroxyimide group. [Chemical formula 38]

In formula (N-3), * each independently represents a bonding site with other structures, and a bonding site with a hydrogen atom, a nitrogen atom, or a carbon atom is preferable.

式（N3-1）～式（N3-3）中，*表示與其他結構的鍵結部位，與氫原子或碳原子的鍵結部位為較佳，與碳原子的鍵結部位為更佳。Furthermore, in the present invention, when the specific compound contains an N-hydroxyamide group, the specific compound contains a structure represented by the following formula (N3-1), formula (N3-2) or formula (N3-3): better. [Chemical formula 39]

In the formulas (N3-1) to (N3-3), * represents a bonding site with other structures, and a bonding site with a hydrogen atom or a carbon atom is preferable, and a bonding site with a carbon atom is more preferable.

式（N3-4）中，*分別獨立地表示與其他結構的鍵結部位，與氫原子或碳原子的鍵結部位為較佳，與碳原子的鍵結部位為更佳。Moreover, in the present invention, when the specific compound includes the structure represented by the formula (N3-1), the specific compound includes the structure represented by the following formula (N3-4) as the structure represented by the above formula (N3-1). The structure is better. [Chemical formula 40]

In the formula (N3-4), * each independently represents a bonding site with other structures, a bonding site with a hydrogen atom or a carbon atom is preferable, and a bonding site with a carbon atom is more preferable.

式（N-3-1）中，R^N31 表示1價的有機基，R^N32 表示氫原子或1價的有機基團，R^N31 及R^N32 表示可以鍵結而形成環結構。When the specific compound contains an N-hydroxyamide group, the specific compound is preferably a compound represented by the following formula (N-3-1). [Chemical formula 41]

In formula (N-3-1), R ^N31 represents a monovalent organic group, R ^N32 represents a hydrogen atom or a monovalent organic group, and R ^N31 and R ^N32 are capable of bonding to form a ring structure.

式（N-3-2）中，R^N33 分別獨立地表示氫原子或1價的取代基，R^N34 分別獨立地表示氫原子或1價的取代基。 式（N-3-2）中，R^N33 係氫原子為較佳。當R^N33 係1價的取代基的情況下，R^N33 係公知的取代基即可，例如，可以舉出烷基、芳基、鹵素原子、羧基、胺基等。 式（N-3-3）中，R^N34 係氫原子為較佳。當R^N34 係1價的取代基的情況下，可以舉出與R^N33 相同的取代基。In the formula (N-3-1), the R ^N31 -based hydrocarbon group is preferable, the hydrocarbon group having 1 to 10 carbon atoms is more preferable, and the hydrocarbon group having 1 to 4 carbon atoms is even more preferable. As the above-mentioned hydrocarbon group, an alkyl group is preferable. When the carbon number of the said alkyl group is 3 or more, a branch structure or a ring structure may be contained, and a cyclic alkyl group may be sufficient as it. In the formula (N-3-1), R ^N31 is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom. The preferred aspect in the case where R ^N31 is a hydrocarbon group is the same as the preferred aspect of R ^N31 described above. In addition, in formula (N-3-1), the aspect in which R ^N31 and R ^N32 are bonded to form a ring structure is also one of the preferred aspects of the present invention, and the ring structure formed may be a saturated ring structure , can also be an unsaturated ring structure, but an unsaturated ring structure is preferred. In addition, the above-mentioned ring structure is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 6-membered ring structure. Among the above ring structures, other ring structures may be further condensed to form a condensed ring structure. As said other ring structure, a benzene ring is mentioned. In addition, the above-mentioned ring structure may be substituted with the following well-known substituents: a hydrocarbon group which may be substituted with a halogen atom, a halogen atom, a carboxyl group, an amido group, a nitro group, and the like. When R ^N31 and R ^N32 are bonded to form a ring structure, the compound represented by the formula (N-3-1) is represented by the following formula (N-3-2) or the following formula (N-3-3) The compound is preferred. [Chemical formula 42]

In formula (N-3-2), R ^N33 each independently represents a hydrogen atom or a monovalent substituent, and R ^N34 each independently represents a hydrogen atom or a monovalent substituent. In the formula (N-3-2), R ^N33 is preferably a hydrogen atom. When R ^N33 is a monovalent substituent, R ^N33 may be a known substituent, and examples thereof include an alkyl group, an aryl group, a halogen atom, a carboxyl group, an amino group, and the like. In the formula (N-3-3), R ^N34 is preferably a hydrogen atom. When R ^N34 is a monovalent substituent, the same substituent as that of R ^N33 can be mentioned.

式（N-4）中，*分別獨立地表示與其他結構的鍵結部位，與碳原子的鍵結部位為較佳。[N-hydroxyimide group] In the present invention, the N-hydroxyimide group means a group represented by the following formula (N-4). [Chemical formula 43]

In the formula (N-4), * each independently represents a bonding site with other structures, and a bonding site with a carbon atom is preferable.

式（N4-1）～式（N4-3）中，*表示與其他結構的鍵結部位，與氫原子或碳原子的鍵結部位為較佳。Furthermore, in the present invention, when the specific compound contains an N-hydroxyimide group, the specific compound contains a structure represented by the following formula (N4-1), formula (N4-2) or formula (N4-3) is better. [Chemical formula 44]

In formula (N4-1) to formula (N4-3), * represents a bonding site with other structures, and a bonding site with a hydrogen atom or a carbon atom is preferable.

式（N-4-1）中，R^N41 及R^N42 分別獨立地表示1價的有機基，R^N41 及R^N42 可以鍵結而形成環結構。When the specific compound contains an N-hydroxyimide group, the specific compound is preferably a compound represented by the following formula (N-4-1). [Chemical formula 45]

In formula (N-4-1), R ^N41 and R ^N42 each independently represent a monovalent organic group, and R ^N41 and R ^N42 may be bonded to form a ring structure.

式（N-4-2）、式（N-4-3）及式（N-4-4）中，R^N43 分別獨立地表示氫原子或1價的有機基，R^N44 分別獨立地表示氫原子或1價的有機基，R^N45 分別獨立地表示氫原子或1價的有機基。R ^N41 and R ^N42 each independently represent a monovalent organic group, preferably a hydrocarbon group, and more preferably a hydrocarbon group having 1 to 10 carbon atoms. The aspect in which R ^N41 and R ^N42 are bonded to form a ring structure is also one of the preferred aspects of the present invention. The formed ring structure is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring. Among the above ring structures, other ring structures may be further condensed to form a condensed ring structure. As said other ring structure, a benzene ring is mentioned. In addition, the above-mentioned ring structure may be substituted with the following well-known substituents: a hydrocarbon group which may be substituted with a halogen atom, a halogen atom, a carboxyl group, an amido group, a nitro group, and the like. When R ^N41 and R ^N42 are bonded to form a ring structure, the specific compound is any one of the following formula (N-4-2), formula (N-4-3) and formula (N-4-4) The compounds represented are preferred. [Chemical formula 46]

In formula (N-4-2), formula (N-4-3) and formula (N-4-4), R ^N43 each independently represents a hydrogen atom or a monovalent organic group, and R ^N44 each independently represents hydrogen atom or a monovalent organic group, and R ^N45 each independently represents a hydrogen atom or a monovalent organic group.

In the formula (N-4-2), R ^N43 is preferably a hydrogen atom. When R ^N43 is a monovalent substituent, R ^N43 may be a known substituent, and examples thereof include an alkyl group, an aryl group, a halogen atom, a carboxyl group, an amino group, and the like. In the formula (N-4-3), R ^N44 is preferably a hydrogen atom. When R ^N44 is a monovalent substituent, the same substituent as that of R ^N43 can be mentioned. In the formula (N-4-4), R ^N45 is preferably a hydrogen atom. When R ^N45 is a monovalent substituent, the same substituent as that of R ^N43 can be mentioned.

(preferable form) Among them, from the viewpoint of resolution, the specific compound has at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, and an N-hydroxyamide group The compound is preferred. N-Hydroxyamine, N-Hydroxyimino and N-Hydroxyimino have lower electron-withdrawing properties than N-Hydroxyimino, so they have strong interaction with organometallic complexes and are easy to inhibit organometallic Aggregation of the complex is considered to be easy to improve the resolution. In addition, from the viewpoint of chemical resistance, the specific compound is preferably a compound having an N-hydroxyimide group. Compared with other structures, the N-hydroxyimide group has a large number of carbonyl groups, so it is hydrophilic. Therefore, in order to improve the hydrophilicity of a cured film, it is estimated that the solubility in an organic solvent falls and chemical resistance improves. Moreover, the aspect which contains the compound which has an N-hydroxyimide group and the compound C mentioned later is also one of preferable aspects of this invention from the viewpoint of both chemical resistance and resolution.

[Molecular weight] The molecular weight of the specific compound is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 47 or more, and more preferably 75 or more.

[化學式48]

[Specific Examples] Hereinafter, specific examples of the specific compound are shown, but the specific compound is not limited thereto. [Chemical formula 47]

[Chemical formula 48]

〔content〕 The content of the specific compound in the composition of the present invention is preferably 0.01 to 20 mass %, more preferably 0.05 to 10 mass %, and even more preferably 0.1 to 5 mass % with respect to the total solid content of the composition. In addition, the molar content ratio of the specific compound with respect to the molar content of the organometallic complex is preferably 30 to 500%, more preferably 50 to 450%, and even more preferably 80 to 400. The composition of the present invention may contain one specific compound alone, or two or more specific compounds may be used in combination. When two or more specific compounds are used in combination, it is preferable that the total contained mass or the total contained molar amount is within the above-mentioned range.

<Organometallic complex> The curable resin composition of the present invention contains an organometallic complex. Organometallic complexes only need to be organic complex compounds containing metal atoms, but complex compounds containing metal atoms and organic groups are preferred, and complex compounds in which organic groups are coordinated to metal atoms More preferred, metallocene compounds are further preferred. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl derivatives which may have substituents as η5-coordinators. Although it does not specifically limit as said organic group, The group which consists of a hydrocarbon group or a combination of a hydrocarbon group and a hetero atom is preferable. As a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are a cyclic group. The above-mentioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably a 5-membered ring cyclic group. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The organometallic complex is not particularly limited, and it is preferably a compound containing a metal corresponding to a Group 4 element, and more preferably at least one compound selected from the group consisting of a titanium compound, a zirconium compound, and a hafnium compound. Preferably, at least one compound selected from the group consisting of titanium compounds and zirconium compounds is further preferred, and titanium compounds are particularly preferred.

The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, but it is preferable to contain only one metal atom. When the organometallic complex contains two or more metal atoms, only one metal atom may be contained, or two or more metal atoms may be contained.

Organometallic complexes are preferably ferrocene compounds, titanocene compounds, zirconocene compounds or hafnocene compounds, more preferably titanocene compounds, zirconocene compounds or hafnocene compounds, A titanocene compound or a zirconocene compound is further preferred, and a titanocene compound is particularly preferred.

The aspect that the organometallic complex has the initiation energy of photo-radical polymerization is also one of the preferred aspects of the present invention. According to the present invention, it is considered that by using the specific compound, the organometallic complex is dispersed in the film in a nearly uniform state. Therefore, it is considered that when the organometallic complex has photoradical polymerization initiation energy, aggregation of the local radical polymerization initiator caused by the aggregation of the organometallic complex can be suppressed. It is considered that by suppressing aggregation of the radical polymerization initiator, the degree of polymerization of the specific resin or the crosslinking agent is also likely to be in a nearly uniform state in the film. Therefore, it is thought that the generation|occurence|production of a development residue, the disconnection of a pattern, etc. are hard to generate|occur|produce, and it is thought that exposure sensitivity and resolution are easy to improve. In the present invention, having photoradical polymerization initiation energy means that a radical capable of initiating radical polymerization can be generated by irradiation of light. For example, when a composition comprising a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, the presence or absence of radical crosslinking can be determined by The disappearance of the linking agent can confirm the presence or absence of photoradical polymerization initiation energy. When confirming the disappearance, an appropriate method can be selected according to the type of the radical crosslinking agent, for example, IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography) may be used to confirm. When the organometallic complex has the initiation energy of photo-radical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnium compound. A titanocene compound or a zirconocene compound is further preferred, and a titanocene compound is particularly preferred. When the organometallic complex does not have the initiation energy of photo-radical polymerization, the organometallic complex is selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium halide compounds, chelated titanium compounds, At least one compound selected from the group consisting of a zirconocene compound and a hafnocene compound is preferred, and at least one compound selected from the group consisting of a titanocene compound, a zirconocene compound and a hafnocene compound is more preferred. Preferably, at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds is further preferred, and titanocene compounds are particularly preferred.

The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

式（P）中，M為金屬原子，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。As an organometallic complex, the compound represented by following formula (P) is mentioned. [Chemical formula 49]

In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the above Rs are each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

In the formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, and a titanium atom or a zirconium atom is further preferable , titanium atoms are particularly good. As the aromatic group in R in the formula (P), an aromatic group having 6 to 20 carbon atoms is mentioned, and an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a phenyl group and a 1-naphthyl group are mentioned. Or 2-naphthyl, etc. As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl, ethyl, propyl, octyl, etc. are exemplified. base, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. As a halogen atom in said R, F, Cl, Br, and I are mentioned. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl group, ethyl group, and propyl group are mentioned. base, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. The above R may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, Aryloxycarbonyl, aryloxy, monoalkylamine, dialkylamine, monoarylamine and diarylamine, etc.

Specific examples of the organometallic complex are not particularly limited, and tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate)titanium can be exemplified. , Diisopropoxy bis(acetone acetone) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl) ) phenyl) titanium, titanium pentamethylcyclopentadienyl trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium and the following compound. [Chemical formula 50]

In addition to this, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass % or more, more preferably 1.0 mass % or more, and particularly preferably 1.5 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When two or more kinds are used, the total amount is preferably within the above range.

＜Other resin＞ The composition of the present invention may contain the above-mentioned specific resin and other resin (hereinafter, also simply referred to as "other resin") different from the specific resin. Examples of other resins include polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin, etc. . For example, by further adding an acrylic resin, a composition excellent in coatability can be obtained, and an organic film excellent in solvent resistance can be obtained. For example, by adding to the composition an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base in place of or in addition to the crosslinking agent described later, the coating of the composition can be improved. properties, solvent resistance of organic films, etc.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more, relative to the total solid content of the composition. Preferably, 2 mass % or more is further more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still more preferable. In addition, the content of other resins in the composition of the present invention is preferably 80 mass % or less, more preferably 75 mass % or less, more preferably 70 mass % or less, and 60 mass % or less with respect to the total solid content of the composition. % or less is more preferable, and 50 mass % or less is still more preferable. Moreover, as a preferable aspect of the composition of this invention, the aspect in which content of other resin is low can also be set as an aspect. In the above aspect, the content of other resins is preferably 20 mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, and 5 mass % or less, based on the total solid content of the composition. It is more preferable, and 1 mass % or less is even more preferable. The lower limit of the content is not particularly limited, as long as it is 0 mass % or more. The composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range.

式（1-1）、式（1-2）或式（1-3）中，R¹¹ 及R¹² 分別獨立地表示未經取代的碳數1～7的脂肪族烴基、作為取代基具有選自包括一級胺鹽結構、二級胺鹽結構、三級胺基、三級胺鹽結構、四級銨基及脂肪族雜環基之群組中之至少1種取代基之碳數1～7的脂肪族烴基、或具有選自包括羥基、烷氧基、硫醇基及烷硫基之群組中之至少1種取代基之碳數2～7的脂肪族烴基，R²¹ 及R²² 分別獨立地表示可以具有取代基之碳數1～7的脂肪族烴基，R³¹ 及R³² 分別獨立地表示可以具有取代基之碳數1～7的脂肪族烴基，R³³ 表示可以具有取代基之碳數1～7的脂肪族烴基。<Compound C> The curable resin composition of the present invention may contain a compound selected from the group consisting of the compound represented by the formula (1-1), the compound represented by the formula (1-2), and the compound represented by the formula (1-3). At least 1 compound in the group (also referred to as "Compound C"). It is considered that the compound C inhibits aggregation of the organometallic complex by interacting with the specific compound and the organometallic complex. Therefore, it is considered that when the composition contains the compound C, the resolution at the time of pattern formation is improved. In particular, when the curable resin composition contains a compound of an N-hydroxyimide group as a specific compound, the curable resin composition further contains the compound C from the viewpoint of achieving both improvement in resolution and chemical resistance. better. [Chemical formula 51]

In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and have an optional substituent as a substituent. Carbon number 1-7 of at least one substituent selected from the group consisting of primary amine salt structure, secondary amine salt structure, tertiary amine group, tertiary amine salt structure, quaternary ammonium group and aliphatic heterocyclic group aliphatic hydrocarbon group, or an aliphatic hydrocarbon group with carbon number of 2 to 7 having at least one substituent selected from the group consisting of hydroxyl, alkoxy, thiol and alkylthio groups, R ²¹ and R ²² are respectively Each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, R ³¹ and R ³² each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and R ³³ represents an optionally substituted aliphatic hydrocarbon group. Aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[R ¹¹ and R ¹² ] In formula (1-1), R ¹¹ and R ¹² are each independently an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or a substituent having a structure selected from the group consisting of primary amine salts. , the aliphatic hydrocarbon group of carbon number 1-7 of at least one substituent in the group of secondary amine salt structure, tertiary amine group, tertiary amine salt structure and quaternary ammonium group is preferably, unsubstituted The aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable. As the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R ¹¹ and R ¹² , an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferable, and an unsubstituted one having 2 to 7 carbon atoms is preferable. Saturated aliphatic hydrocarbon groups are more preferred, and ethyl, isopropyl, tert-butyl or cyclohexyl groups are more preferred.

As a substituent in R ¹¹ and R ¹² , as a group selected from the group consisting of primary amine salt structure, secondary amine salt structure, tertiary amine group, tertiary amine salt structure, quaternary ammonium group and aliphatic heterocyclic group The aliphatic hydrocarbon group having 1 to 7 carbon atoms in at least one of the substituents in the group, and the saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above substituents are preferred. In addition, the aliphatic hydrocarbon group may have a plurality of the aforementioned substituents, but it is preferable to have only one of the aforementioned substituents.

The primary amine salt structure in the above-mentioned substituent refers to a salt structure including a primary amine group (-NH ₂ ) and an acid, and a salt structure of a primary amine group and an inorganic acid is preferred, and examples include a hydrochloride salt structure and the like. As the secondary amine salt structure in the above-mentioned substituents, it refers to the salt structure including the secondary amine group (-NRH, R represents an organic group.) and an acid, and the salt structure of the secondary amine group and an inorganic acid is preferred, A hydrochloride structure etc. are mentioned. Examples of the secondary amine group constituting the above-mentioned secondary amine salt structure in the above-mentioned substituent include a monoalkylamine group, a monoarylamine group, and the like, and a monoalkylamine group having 1 to 4 carbon atoms is preferred. The tertiary amine salt structure in the above substituents refers to the salt structure including the tertiary amine group (-NR ₂ , R independently represents an organic group.) and the acid, and the tertiary amine group and the salt structure of the inorganic acid are relatively Preferably, the hydrochloride structure etc. are mentioned. As the tertiary amine group in the above-mentioned substituents or the tertiary amine constituting the tertiary amine, a dialkylamine group is preferable, and the carbon number of the two alkyl groups is independently a dialkylamine group of 1 to 4. More preferably, a dimethylamine group is more preferable. Furthermore, when one of R ¹¹ and R ¹² has any one of a primary amine salt structure, a secondary amine salt structure, a tertiary amine, and a tertiary amine salt structure as a substituent, R ¹¹ and R ¹² The other is preferably the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. As a substituent, an aliphatic hydrocarbon group having at least one carbon number selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine, and a tertiary amine salt structure is included as a substituent, and the terminal has These substituents are preferably linear or branched saturated aliphatic hydrocarbon groups having 2 to 7 carbon atoms, and linear or branched saturated aliphatic hydrocarbon groups having 3 to 5 carbon atoms having these substituents at the terminal. A hydrocarbon group is more preferable, and a straight-chain saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms having these substituents at the terminal is further preferable.

式（A-1）中，R^A1 ～R^A3 分別獨立地表示烴基，R^A1 ～R^A3 中至少2個可以鍵結而形成環結構，X表示相對陰離子，*表示與碳數1～7的脂肪族烴基的鍵結部位。 式（A-1）中，R^A1 ～R^A3 分別獨立地係芳香族烴基或烷基為更佳，苯基或碳數1～4的烷基為更佳，碳數1～4的烷基為進一步較佳，甲基為特佳。 R^A1 ～R^A3 均為甲基的態樣亦是本發明的較佳態樣之一。 作為R^A1 ～R^A3 中至少2個鍵結而形成之環結構，可以舉出環己環等飽和脂肪族烴環、環己烯環等不飽和脂肪族烴環、嗎啉環等飽和脂肪族雜環等。 式（A-1）中，X表示相對陰離子，可以為1價的陰離子亦可以為2價以上的陰離子，但1價的陰離子為較佳。 又，X沒有特別限定，但鹵化物離子或甲苯磺酸陰離子為較佳，鹵化物離子為更佳。 作為上述鹵化物離子，可以舉出氟化物離子、鹽化物離子、臭化物離子、碘化物離子等，鹽化物離子為較佳。 又，當R¹¹ 及R¹² 中的一方具有四級銨作為取代基的情況下，R¹¹ 及R¹² 中的另一方係上述未經取代之碳數1～7的脂肪族烴基為較佳。 作為取代基具有四級銨之碳數1～7的脂肪族烴基，係在末端具有四級銨之碳數2～7的直鏈狀或支鏈狀的飽和脂肪族烴基為較佳，在末端具有四級銨之碳數3～5的直鏈狀或支鏈狀的飽和脂肪族烴基為更佳，在末端具有四級銨之碳數3～5的直鏈狀的飽和脂肪族烴基為進一步較佳。As the quaternary ammonium group among the above-mentioned substituents, a group represented by the following formula (A-1) is preferable. [Chemical formula 52]

In formula (A-1), R ^A1 to R ^A3 each independently represent a hydrocarbon group, at least two of R ^A1 to R ^A3 may be bonded to form a ring structure, X represents a relative anion, and * represents a compound having 1 to 7 carbon atoms. Bonding site of aliphatic hydrocarbon groups. In formula (A-1), R ^A1 to R ^A3 are each independently an aromatic hydrocarbon group or an alkyl group, more preferably, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. For further preference, methyl is particularly preferred. The aspect in which R ^A1 to R ^A3 are all methyl groups is also one of the preferred aspects of the present invention. Examples of the ring structure formed by at least two of R ^A1 to R ^A3 being bonded to each other include saturated aliphatic hydrocarbon rings such as cyclohexene rings, unsaturated aliphatic hydrocarbon rings such as cyclohexene rings, and saturated aliphatic rings such as morpholine rings. Heterocycle etc. In formula (A-1), X represents a counter anion, and may be a monovalent anion or a divalent or more anion, but a monovalent anion is preferable. In addition, X is not particularly limited, but a halide ion or a toluenesulfonic acid anion is preferable, and a halide ion is more preferable. As said halide ion, a fluoride ion, a halide ion, an odoride ion, an iodide ion, etc. are mentioned, and a halide ion is preferable. Moreover, when one of R ¹¹ and R ¹² has quaternary ammonium as a substituent, the other of R ¹¹ and R ¹² is preferably the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. The aliphatic hydrocarbon group having 1 to 7 carbon atoms in quaternary ammonium as the substituent is preferably a linear or branched saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms in the terminal of quaternary ammonium. A straight-chain or branched-chain saturated aliphatic hydrocarbon group having 3-5 carbon atoms in quaternary ammonium is more preferable, and a straight-chain saturated aliphatic hydrocarbon group having 3-5 carbon atoms having quaternary ammonium at the terminal is further better.

As a hetero atom in the aliphatic heterocyclic group in the said substituent, an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned, Oxygen atom is preferable. The said aliphatic heterocyclic group may have only 1 hetero atom, and may have 2 or more. The above-mentioned aliphatic heterocyclic group is preferably a 5-membered ring structure or a 6-membered ring structure, more preferably a 5-membered ring structure. The said aliphatic heterocyclic group may further have well-known substituents, such as an alkyl group. As the aliphatic heterocyclic group, 2,2-dimethyl-1,3-dioxolan-4-yl is preferable. Moreover, when one of R ¹¹ and R ¹² has an aliphatic heterocyclic group as a substituent, it is preferable that the other of R ¹¹ and R ¹² has an aliphatic heterocyclic group as a substituent. The aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an aliphatic heterocyclic group as a substituent is preferably a saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms having an aliphatic heterocyclic group at the terminal, and having an aliphatic heterocyclic ring at the terminal A linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in the group is more preferable, and a methyl group having an aliphatic heterocyclic group is further preferable.

R ¹¹ and R ¹² may each independently be an aliphatic hydrocarbon group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, and an alkylthio group. The above-mentioned aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the above-mentioned substituents, but the aspect having only one of the above-mentioned substituents is also one of the preferred aspects of the present invention. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable. As the above-mentioned alkylthio group, an alkylthio group having 1 to 10 carbon atoms is preferable, and an alkylthio group having 1 to 4 carbon atoms is more preferable. As the aliphatic hydrocarbon group having 2 to 7 carbon atoms, a saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 2 to 4 carbon atoms is more preferable. Examples of the aliphatic hydrocarbon group having 2 to 7 carbon atoms having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, and an alkylthio group include hydroxyethyl group and hydroxypropyl group. group, methoxyethyl, ethoxyethyl, methoxypropyl, ethoxypropyl, etc., but not limited thereto.

[R ²¹ and R ²² ] R ²¹ and R ²² each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. R ²¹ and R ²² are preferably unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms, or aliphatic hydrocarbon groups having 1 to 7 carbon atoms having an amine group or a quaternary ammonium group as a substituent. The aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable. Preferred embodiments of the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above-mentioned substituent in R ²¹ and R ²² are the same as those of R ¹¹ and R ¹² , respectively. The aspect shown in the description is the same.

[R ³¹ and R ³² ] R ³¹ and R ³² each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. R ³¹ and R ³² are preferably unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amine group or a quaternary ammonium group as a substituent. The aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable. Preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above substituent in R ³¹ and R ³² are the same as those of R ¹¹ and R ¹² , respectively. The aspect shown in the description is the same.

[R ³³ ] R ³³ represents an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an unsubstituted saturated hydrocarbon group having 1 to 7 carbon atoms An aliphatic hydrocarbon group is more preferable, and a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable. As R ³³ , methyl, ethyl, propyl, isopropyl, butyl or tertiary butyl is preferable, and ethyl is more preferable.

In addition, it is preferable that the compound C does not contain a radical polymerizable group such as a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, an alkoxyalkyl group, a hydroxyalkyl group, an alkane Oxysilyl and silanol groups.

Specific examples of compound C include the following compounds (1) to (27), but are not limited thereto. In addition, among these compounds, compounds (1) to (12) are particularly preferred from the viewpoint of resolution. [Chemical formula 53]

From the viewpoint of resolution, the content of Compound C is preferably 10 to 50,000 ppm, more preferably 30 to 20,000 ppm, and even more preferably 70 to 15,000 ppm relative to the total mass of the curable resin composition. When the curable resin composition contains two or more kinds of compounds C, the above-mentioned content mass is the total mass of all the compounds C.

＜Solvent＞ The curable resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfites, amides, ureas, and alcohols.

As esters, preferable ones include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. , ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., alkoxy Methyl acetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate ethyl acetate, etc.)), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropanoate, etc. (for example, 3-methoxypropionate) Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters ( For example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, 2-methoxypropionate Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate Esters and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropanoate, etc.) , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate , ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

As the ethers, preferred ones include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl seleux acetate, ethyl seleux Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol Monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc.

As ketones, preferable ones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucan, Dihydro-levoglucan, etc.

As cyclic hydrocarbons, preferable examples include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfites, preferable ones include, for example, dimethyl sulfene.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide amide, N-formylmorpholine, N-acetylmorpholine, etc.

Preferable examples of the ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxyl Ethyl-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, Polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol alcohol and diacetone alcohol.

From the viewpoint of improvement of the properties of the coating surface, etc., it is also preferable that two or more kinds of solvents are mixed.

In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl xelousel acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol A solvent selected from the group consisting of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more of them is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone in combination. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferable.

From the viewpoint of coatability, the content of the solvent is preferably set to an amount in which the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass. The total solid content concentration is more preferably an amount of 5 to 75 mass %, and the total solid content concentration of the curable resin composition of the present invention is more preferably an amount of 10 to 70 mass %. More preferably, the total solid content concentration of the resin composition is 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, it is preferable that the total is within the above-mentioned range.

＜Sensitizer＞ The composition of the present invention preferably contains a photosensitizer. It is assumed that the photosensitive agent does not contain the above-mentioned organometallic complex and has a compound having photoradical polymerization initiation energy. The composition of the present invention preferably contains a photopolymerization initiator.

[Photopolymerization initiator] In the composition of the present invention, it is preferable to contain a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. Moreover, it can also be an activator which produces|generates active radicals by some action with the sensitizer excited by light.

In the present invention, the compound corresponding to the organometallic complex does not correspond to the photosensitizer and the photoradical polymerization initiator.

When the organometallic complex has initiating energy for photo-radical polymerization, it is also preferable that the composition of the present invention does not actually contain a radical polymerization initiator other than the above-mentioned organometallic complex. The radical polymerization initiators other than the above-mentioned organometallic complexes are not substantially contained means that, in the composition of the present invention, the content of other radical polymerization initiators other than the above-mentioned organometallic complexes is relative to the above-mentioned organic metal complexes. The total mass of the metal complex is 5 mass % or less, preferably 3 mass % or less, more preferably 1 mass % or less, and still more preferably 0.1 mass %. Furthermore, when the composition of the present invention contains an organometallic complex having a radical polymerization initiation energy, it is also preferable that the composition of the present invention contains the above-mentioned organometallic complex and a photoradical polymerization initiator. According to this aspect, the generation of the above-mentioned development residue, the disconnection of the pattern, and the like can be suppressed, and the exposure sensitivity is also improved. When the composition of the present invention contains an organometallic complex having no photo-radical polymerization initiating energy, it is preferable that the composition of the present invention contains a photo-radical polymerization initiator. It is considered that since the composition of the present invention contains the specific resin, aggregation of the organometallic complex can be suppressed. It is presumed that by suppressing the aggregation of organometallic complexes that do not have photoradical polymerization initiation energy, the increase in the plasticity of the local film caused by aggregation can be suppressed, and the increase in the local degree of polymerization in the aggregation site can also be suppressed. big. As a result, it is presumed that the occurrence of the variation in sensitivity due to the location of the film can be suppressed, and the resolution can be improved. When the composition of the present invention contains an organometallic complex and a photoradical polymerization initiator, the content of the organometallic complex relative to the total content of the organometallic complex and the photoradical polymerization initiator is 20 to 80 mass % is preferable, and 30 to 70 mass % is more preferable. In addition, as the above-mentioned photoradical polymerization initiator, an oxime compound described later is preferable.

Preferably, the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L•mol ^-1 •cm ^-1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorptivity of a compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole structure, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaaryl Oxime compounds such as biimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds , organic boron compounds, etc. For details of these, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated in the present specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated in the present specification. Among the commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, as the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCURE 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, compounds described in Japanese Patent Laid-Open No. 2009-191179 can also be used, the absorption maximum wavelength being matched to a light source with a wavelength of 365 nm or 405 nm.

As an acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide etc. are mentioned. In addition, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both are manufactured by BASF) can be used.

As a photoradical polymerization initiator, an oxime compound can be mentioned more preferably. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator.

As specific examples of the oxime compound, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, and the compounds described in JP 2006-342166 A can be used .

Examples of preferable oxime compounds include compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-Tosyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 54]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open 2012- Photo-radical polymerization initiator 2) described in Gazette 014052. In addition, TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 55]

As a photopolymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compounds described in JP 2014-137466 A and the compounds described in JP 06636081 .

As the photopolymerization initiator, an oxime compound having at least one benzene ring in a carbazole ring serving as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. Compound (C-3) and the like described in paragraph 0101 of Laid-Open Publication No. 2013-164471.

As an optimum oxime compound, the oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene - Compounds in the group of present-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

Further preferred photo-radical polymerization initiators are trihalomethyltriazole compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium Salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds It is further preferable to use at least one compound among them, it is even more preferable to use a metallocene compound or an oxime compound, and it is still more preferable to use an oxime compound.

In addition, N,N'- benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl Aromatic ketones such as base-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, quinones such as alkyl anthraquinones and condensed aromatic rings, benzoin alkyl ethers Benzoin ether compounds such as benzoin, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 56]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, a carbon atom Alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group having 2 to 12 carbon atoms, and 2 to carbon carbon group interrupted by one or more oxygen atoms The alkyl group of 18 and the phenyl group or biphenyl group substituted by at least one of the alkyl groups of 1 to 4 carbon atoms, R ^I01 is a group represented by formula (II) or the same group as R ^I00 , R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen atom.

[Chemical formula 57]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 of the above formula (I).

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used as the photoradical polymerization initiator.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 30% by mass relative to the total solid content of the composition of the present invention. 15 mass %, more preferably 1.0 to 10 mass %. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably within the above-mentioned range.

[Photoacid generator] Moreover, in the composition of this invention, it is also preferable to contain a photoacid generator as a photosensitizer. By containing a photoacid generator, for example, acid is generated in the exposed part of the photosensitive film, and the solubility of the exposed part to a developing solution (for example, an alkaline aqueous solution) increases, and a positive pattern in which the exposed part is removed by the developing solution can be obtained. In addition, it is also possible to adopt an aspect in which the composition contains a photoacid generator and a crosslinking agent other than the radical crosslinking agent described later, for example, the crosslinking of the crosslinking agent is accelerated by the acid generated in the exposed portion. In response, the exposed portion is less likely to be removed by the developing solution than the non-exposed portion. In this aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinonediazide compounds, diazonium salts, phosphonium salts, pernium salts, onium salt compounds such as iodonium salts, and imidosulfonates. Sulfonate compounds such as acid salts, oxime sulfonates, diazobis, diazo, o-nitrobenzyl sulfonates, etc.

Examples of the quinonediazide compound include a sulfonic acid in which quinonediazide is bonded to a polyhydroxy compound via an ester, and a sulfonic acid in which quinonediazide is bonded to a polyamine compound via a sulfonamide. An acid, a sulfonic acid in which quinonediazide is bonded to the polyhydroxy polyamine compound through at least one of an ester bond and a sulfonamide bond, and the like. In the present invention, for example, it is preferable that 50 mol% or more of the whole functional groups of these polyhydroxy compounds or polyamine compounds are substituted with quinonediazide groups.

In the present invention, as the quinonediazide, any of 5-naphthoquinonediazidesulfonyl group and 4-naphthoquinonediazidesulfonyl group can be preferably used. The 4-naphthoquinonediazide sulfonate compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of 5-naphthoquinonediazide sulfonate compound extends to the g-ray region of mercury lamp, which is suitable for g-ray exposure. In the present invention, it is preferable to select the 4-naphthoquinonediazidesulfonate compound and the 5-naphthoquinonediazidesulfonate compound according to the exposure wavelength. In addition, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule may be contained, or a 4-naphthoquinonediazidesulfonyl group may be contained. A nitrogen sulfonate compound and a 5-naphthoquinonediazide sulfonate compound.

The above-mentioned naphthoquinonediazide compound can be synthesized by esterification of a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the above-mentioned naphthoquinonediazide compound, for example, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, the salts or ester compounds of the compounds, etc.

As the onium salt compound or the sulfonate compound, the compounds described in paragraphs 0064 to 0122 of JP-A No. 2008-013646 can be mentioned.

It is also preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) described later The represented oxime sulfonate compounds are preferred.

[Chemical formula 58]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When there are a plurality of X ³ , they may be the same or different. The alkyl group and the alkoxy group in the above-mentioned X ³ may have a substituent. As the alkyl group in the above-mentioned X ³ , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in the above-mentioned X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned X ³ , a chlorine atom or a fluorine atom is preferable. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of ^X3 may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. The halogenated alkoxy group of 5, the phenyl group which may be substituted with W, the naphthyl group which may be substituted with W, or the anthracenyl group which may be substituted with W are preferred. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group with a carbon number of 6-20, a halogenated aryl group with a carbon number of 6-20.

In formula (OS-1), m3 is ³ , ^X3 is a methyl group, the substitution position of X3 is an ortho position, ^R34 is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- Compounds of 2-oxonorkanylmethyl or p-tolyl are particularly preferred.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include paragraphs 0064 to 0068 of JP 2011-209692 A, and paragraphs 0158 to JP 2015-194674 The following compounds described in 0167 are incorporated into this specification.

[Chemical formula 59]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are plural R ^s2 which independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen. Atom, sometimes there are plural R ^s6 each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, and ns represents 1 Or 2, ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), the alkyl group (preferably carbon number 1-30), aryl group (preferably carbon number 6-30) or heteroaryl group represented by R ^s1 ( (preferably having 4 to 30 carbon atoms) may have a substituent T.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably with a carbon number of 1-12) or an aryl group (preferably with a carbon number of 6-30), A hydrogen atom or an alkyl group is more preferable. Among the two or more R ^s2 that sometimes exist in the compound, one or two are preferably alkyl, aryl or halogen atoms, one is preferably alkyl, aryl or halogen atom, and one is preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferred that it is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a substituent T. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring including Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is 2. better. In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent . In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In addition, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the above formula (OS-104) ) represented by the compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compounds indicated are particularly preferred. [Chemical formula 60]

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom or an alkane having 1 to 8 carbon atoms group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen atom or methyl group. In the formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxymethyl group , phenyl or chlorophenyl, preferably an alkyl group with 1 to 8 carbon atoms, a halogen atom or a phenyl group, preferably an alkyl group with 1 to 8 carbon atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms , methyl is particularly good.

In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferable. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z) of the oxime may be any of them, or a mixture may be used. Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include paragraph numbers 0088 to 0095 of JP 2011-209692 A, JP 2015-A The compounds described in paragraphs 0168 to 0194 of Gazette 194674 are incorporated in the present specification.

As another preferable aspect of the oxime sulfonate compound containing at least one oxime sulfonate group, the compound represented by following formula (OS-101) and formula (OS-102) is mentioned.

[Chemical formula 61]

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group group, cyano group, aryl group or heteroaryl group. The aspect where R ^u9 is a cyano group or an aryl group is more preferable, and the aspect where R ^u9 is a cyano group, a phenyl group, or a naphthyl group is more preferable. In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7 - , R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkyl group carbonyl, arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may each be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom, or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, the aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the above-mentioned substituents may further have a substituent.

More preferably, the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any of them, respectively, or a mixture may be used. Specific examples of the compound represented by the formula (OS-101) include those described in paragraphs 0102 to 0106 of JP 2011-209692 A, and paragraphs 0195 to 0207 of JP 2015-194674 A compounds, which are incorporated into this specification. Among the above compounds, b-9, b-16, b-31 and b-33 are preferred.

In addition to this, a commercial item can also be used as a photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG- 699 (all made by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (all made by IGM Resins B.V.), Irgacure 250, Irgacure 270, Irgacure 290 (all made by BASF), MBZ-101 (all made by Midori Kagaku Co.) ., Ltd. manufacture) and so on.

Moreover, the compound represented by the following structural formula is also mentioned as a preferable example. [Chemical formula 62]

As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), the specification of US Pat. No. 3,905,815, JP 46-4605, JP 48-036281 No., Japanese Patent Laid-open No. 55-032070, Japanese Patent Laid-open No. 60-239736, Japanese Patent Laid-open No. 61-169835, Japanese Patent Laid-open No. 61-169837, Japanese Patent Laid-open No. 62-058241, Japanese Patent Laid-open No. 61-169837 Compounds described in No. Sho 62-212401, JP Sho 63-070243, JP Sho 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970), etc., are particularly mentioned. The oxazole compound substituted by trihalomethyl group: S-triazole compound. More preferably, at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-tris-tris-s-tris-s-tris-derivatives, and specifically, for example, 2,4,6-tris (Monochloromethyl)-s-tris-tris, 2,4,6-tris (dichloromethyl)-s-tris, 2,4,6-tris (trichloromethyl)-s-tris, 2-Methyl-4,6-bis(trichloromethyl)-s-tris, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris, 2-(α, α,β-Trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-phenyl-4,6-bis(trichloromethyl)-s-tris, 2 -(p-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl) )-s-tris-tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-[1-(p-methoxyphenyl)-2,4 -Butadienyl]-4,6-bis(trichloromethyl)-s-tris-tris, 2-styryl-4,6-bis(trichloromethyl)-s-tris, 2-( p-Methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) -s-tris𠯤, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris𠯤, 2-(4-naphthoxynaphthyl)-4,6-bis(tris chloromethyl)-s-tris-tris, 2-phenylsulfanyl-4,6-bis(trichloromethyl)-s-tris-tris, 2-benzylsulfanyl-4,6-bis(trichloromethyl) -s-Tris(Tris), 2,4,6-Tris(dibromomethyl)-s-Tris, 2,4,6-Tris(Tribromomethyl)-s-Tris, 2-Methyl-4 , 6-bis (tribromomethyl)-s-tris, 2-methoxy-4,6-bis (tribromomethyl)-s-tris, etc.

As the photoacid generator, an organic borate compound can also be used. Specific examples of the organic borate compound include Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686, and Japanese Patent Laid-Open No. 9-188686. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech'98. Proceeding April 19-22 , 1998, "Chicago" etc., the organoborate complexes described in Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, and Japanese Patent Laid-Open No. 6-175561 Or organoboron oxonium complexes, the organoboronium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, and those described in Japanese Patent Laid-Open No. 9-188710 Organoboronium phosphonium complexes, Japanese Patent Laid-Open No. 6-348011, Japanese Laid-Open No. 7-128785, Japanese Laid-Open No. 7-140589, Japanese Laid-Open No. 7-306527, Japanese Laid-Open No. 7-292014 Gazette, etc. Organoboron transition metal coordination complexes, etc.

As the photoacid generator, a dioxane compound can also be used. As the dibasic compound, the compounds and diazodibasic compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318 and the like can be mentioned.

Examples of the above-mentioned onium salt compounds include diazonium salts described in S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal et al, Polymer, 21,423 (1980), and U.S. Patent No. 4,069,055 No. specification, ammonium salts described in Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in each specification of US Patent No. 4,069,055, US Patent No. 4,069,056, European Patent No. 104,143, US Patent No. 339,049 , each specification of U.S. Patent No. 410,201, the iodonium salt described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, US Patent No. Permamate salts described in the respective specifications of No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10(6), 1307 (1977), J.V.Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979) Selenium salts, C.S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988 ), onium salts such as arsenic salts, pyridinium salts, etc.

式（RI-I）中，Ar11表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z11^- 表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式（RI-II）中，Ar21、Ar22各自獨立地表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z21^- 表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式（RI-III）中，R31、R32、R33各自獨立地表示可以具有1～6個取代基之碳數20以下的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面而言，芳基為較佳。作為較佳的取代基，可以舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z31^- 表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。Examples of the onium salt include those represented by the following general formulae (RI-I) to (RI-III). [Chemical formula 63]

In formula (RI-I), Ar11 represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents, and as preferred substituents, an alkyl group with 1 to 12 carbon atoms, an alkyl group with 1 to 12 carbon atoms, and Alkenyl group of 12, alkynyl group of carbon number 1-12, aryl group of carbon number 1-12, alkoxy group of carbon number 1-12, aryloxy group of carbon number 1-12, halogen atom, carbon number of 1-12 12 alkylamine group, carbon number 1-12 dialkylamine group, carbon number 1-12 alkyl amido group or aryl amido group, carbonyl group, carboxyl group, cyano group, sulfonyl group, carbon number 1-12 thioalkyl groups, 1-12 carbon atoms thioaryl groups. Z11 ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, and sulfate ion. In terms of this aspect, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion are preferred. In the formula (RI-II), Ar21 and Ar22 each independently represent an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group with 1 to 12 carbon atoms. , alkenyl with 1 to 12 carbons, alkynyl with 1 to 12 carbons, aryl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, aryloxy with 1 to 12 carbons, halogen atoms , C 1-12 alkylamine group, carbon number 1-12 dialkylamine group, carbon number 1-12 alkyl amide group or aryl amide group, carbonyl, carboxyl, cyano, sulfonic acid Acyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z21 ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, and sulfate ion. In terms of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable. In formula (RI-III), R31, R32, and R33 each independently represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group with a carbon number of 20 or less that may have 1 to 6 substituents. In terms of stability, aryl groups are preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms. Alkoxy group of 12, aryloxy group of carbon number 1-12, halogen atom, alkylamine group of carbon number 1-12, dialkylamine group of carbon number 1-12, alkyl group of carbon number 1-12 An amido group or an aryl amido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, and sulfate ion. In terms of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable.

[化學式65]

[化學式66]

[化學式67]

Specific examples include the following. [Chemical formula 64]

[Chemical formula 65]

[Chemical formula 66]

[Chemical formula 67]

When a photoacid generator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and more preferably 2 to 15% by mass relative to the total solid content of the composition of the present invention. better. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more types of photoacid generators are contained, it is preferable that the total is within the above-mentioned range.

[Photobase generator] The curable resin composition of the present invention may contain a photobase generator as a photosensitizer. When the curable resin composition contains a photobase generator and a crosslinking agent, which will be described later, for example, the alkali generated in the exposed portion promotes the cyclization of the specific resin, promotes the crosslinking reaction of the crosslinking agent, and the like. A state in which the exposed portion is less likely to be removed by the developing solution than the non-exposed portion. In this aspect, a negative pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base by exposure, and a known one can be used. For example, M.Shirai and M.Tsunooka, Prog.Polym.Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev. , 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol. , 13, 153 (2000); M.Winkle, and K.Graziano, J.Photopolym.Sci.Technol., 3,419 (1990); M.Tsunooka, H.Tachi, and S.Yoshitaka, J.Photopolym.Sci.Technol. , 9, 13 (1996); K.Suyama, H.Araki, M.Shirai, J.Photopolym.Sci.Technol., 19,81 (2006), there can be mentioned transition metal compound complexes, compounds with ammonium Substances with structures such as salts, ionic compounds such as those in which amidine moieties are latentized by forming salts with carboxylic acids, ionic compounds, urethane derivatives, and oxime ester derivatives , a nonionic compound in which a base component such as an acyl compound is latentized by a urethane bond, an oxime bond, or the like. In the present invention, examples of the photobase generator include carbamate derivatives, amide derivatives, amide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, and oxime derivatives. as a better example.

Although it does not specifically limit as a basic substance which generate|occur|produces from a photobase generator, The compound which has an amine group, especially polyamines, such as a monoamine and a diamine, and an amidine, etc. are mentioned. From the viewpoint of the imidization rate, it is preferable that the above-mentioned basic substance has a large pKa in DMSO (dimethylsulfoxide) of the conjugated acid. The above-mentioned pKa is preferably 1 or more, more preferably 3 or more. The upper limit of the above pKa is not particularly limited, but 20 or less is preferable. Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of an acid, and can be found in Determination of Organic Structures by Physical Methods (Authors: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; Editing: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) or Data for Biochemical Research (authors: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software of ACD/pKa (manufactured by ACD/Labs) was used as pKa.

From the viewpoint of the storage stability of the curable resin composition, as the photobase generator, a photobase generator that does not contain a salt in its structure is preferable, and the photobase generator generates on the nitrogen atom of the alkali moiety. No charge is preferred. As a photobase generator, the base generated is preferably potentialized by covalent bonds, and the mechanism of base generation is that the covalent bond between the nitrogen atom of the generated base part and the adjacent atom is cut to generate the base The mechanism is better. If it is a photobase generator which does not contain a salt in a structure, since a photobase generator can be made neutral, a solvent solubility becomes more favorable, and a service life is extended. From these reasons, the amine produced from the photobase generator used in the present invention is preferably a primary amine or a secondary amine. In addition, from the viewpoint of the chemical resistance of the pattern, it is preferable that the photobase generator contains a salt in the structure as the photobase generator.

In addition, from the above-mentioned reasons, as a photobase generator, as described above, the generated base is preferably latentized by a covalent bond, and the generated base is preferably formed by an amide bond, a urethane bond, and an oxime bond. Potentially better. As the photobase generator of the present invention, for example, the photobase generator having a cinnamamide structure disclosed in Japanese Patent Laid-Open No. 2009-080452 and International Publication No. 2009/123122, such as Japanese Patent Laid-Open No. 2006- Photobase generators with urethane structure disclosed in Gazette 189591 and JP 2008-247747 A, such as those disclosed in JP 2007-249013 Gazette and JP 2008-003581 Gazette having oxime The structure, the photobase generator of the carbamoyl oxime structure, etc., are not limited to these, In addition, the structure of a well-known photobase generator can be used.

In addition, examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP 2012-093746 A, and paragraph 0022 of JP 2013-194205 A. The compounds described in to 0069, the compounds described in paragraphs 0026 to 0074 of JP 2013-204019 A, and the compounds described in paragraph 0052 of International Publication No. 2010/064631 are exemplified.

In addition to this, as a photobase generator, a commercial item can be used. Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB- 174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

When a photobase generator is contained, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and 2 to 15 mass % with respect to the total solid content of the curable resin composition of the present invention. for further better. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, it is preferable that the total is within the above-mentioned range.

<Thermal polymerization initiator> The composition of the present invention may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or promote the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the crosslinking agent also proceeds in the heating process described later, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass % with respect to the total solid content of the composition of the present invention. %. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount thereof is preferably within the above range.

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the effect of generating an acid by heating to promote a compound selected from the group consisting of a hydroxymethyl group, an alkoxymethyl group or an oxymethyl group, an epoxy compound, an oxetane compound, and a benzoyl group Cross-linking reaction of at least one of the 𠯤 compounds.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, when the drying (pre-baking: about 70 to 140° C.) after applying the composition to the substrate is selected, no acid is generated, and the final heating (curing: about 70° C.) after patterning is performed in the subsequent exposure and development. 100 to 400° C.) which generates an acid as a thermal acid generator can suppress the decrease in sensitivity at the time of development, so it is preferable. The thermal decomposition onset temperature was determined as the peak temperature of the exothermic peak with the lowest temperature when the thermal acid generator was heated to 500° C. in a pressure-resistant capsule at 5° C./min. Q2000 (manufactured by TA Instruments) etc. are mentioned as an apparatus used when measuring the thermal decomposition onset temperature.

The acid-based strong acid generated from the thermal acid generator is preferably, for example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid; alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, Halogenated alkyl sulfonic acids such as methanesulfonic acid are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Laid-Open No. 2013-072935.

Among them, from the viewpoint of less residue in the organic film and less likely to degrade the physical properties of the organic film, those that generate alkyl sulfonic acids having 1 to 4 carbon atoms or halogenated alkyl sulfonic acids having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid is preferred. Acid (4-hydroxyphenyl) dimethyl perionate, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethyl perionium, benzyl (4-hydroxyphenyl) methyl methanesulfonate bismuth, benzyl (4-((methoxycarbonyl)oxy)phenyl)methyl methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methylmethanesulfonate) (4-hydroxyphenyl) dimethylsulfanium trifluoromethanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) dimethylsulfanium trifluoromethanesulfonate, trifluoromethane Benzyl sulfonate (4-hydroxyphenyl) methyl sulfamate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methyl sulfamate, trifluoromethanesulfonic acid (4- Hydroxyphenyl)methyl((2-methylphenyl)methyl)strontium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene )-2-(o-tolyl)propionitrile and 2,2-bis(3-(methanesulfonamido)-4-hydroxyphenyl)hexafluoropropane are preferable as the thermal acid generator.

Moreover, the compound described in the 0059 paragraph of Japanese Unexamined Patent Application Publication No. 2013-167742 is also preferable as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of the specific resin. Since crosslinking reaction is accelerated|stimulated by containing 0.01 mass part or more, the mechanical property and solvent resistance of an organic film can be improved further. In addition, from the viewpoint of the electrical insulating properties of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is still more preferable.

＜Onium salt＞ The curable resin composition of the present invention may further contain an onium salt. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt. The type and the like of the onium salt are not particularly limited, and preferred examples thereof include ammonium salts, iminium salts, peronium salts, iodonium salts, and phosphonium salts. Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and periconium salts, iodonium salts, or phosphonium salts are preferred from the viewpoint of compatibility with polymers .

The onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bound through a covalent bond. That is, the onium salt can be an intramolecular salt having a cationic part and an anionic part in the same molecular structure, or an intermolecular salt formed by ion bonding of cationic and anionic molecules of different molecules, but the intermolecular salt is better. Moreover, in the curable resin composition of this invention, the said cation part or cation molecule and the said anion part or anion molecule may be bonded by an ionic bond, and may dissociate. As the cation in the onium salt, ammonium cation, pyridinium cation, perium cation, iodonium cation or phosphonium cation are preferred, and at least one cation selected from the group consisting of tetraalkylammonium cation, pericynium cation and iodonium cation is better.

The onium salt used in the present invention may be a thermal base generator described later. The thermal base generator refers to a compound that generates a base by heating, and examples thereof include compounds that generate a base when heated to 40° C. or higher. Examples of the onium salt include the onium salts described in paragraphs 0122 to 0138 of International Publication No. 2018/043262, and the like. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30 mass % or less, more preferably 20 mass % or less, further preferably 10 mass % or less, and may be 5 mass % or less, or 4 mass % or less. One or two or more of the onium salts can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Heat base generator> The curable resin composition of this invention may further contain a heat base generator. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a thermal base generator. The other thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt. As a thermal alkali generator other than the above-mentioned onium salt, a nonionic thermal alkali generator can be mentioned. As a nonionic thermal base generator, the compound represented by Formula (B1) or Formula (B2) is mentioned. [Chemical formula 68]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. In addition, Rb ¹ , Rb ² and Rb ³ do not all have a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited to this.

In the formulae (B1) and (B2), about Rb ¹ , Rb ² and Rb ³ , it is preferable that at least one of them contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. The single ring system is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. Monocyclic cyclohexane ring and benzene ring are preferable, and cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (having 2 to 24 carbon atoms) is better, 2-18 is better, 3-12 is further better), aryl (carbon number 6-22 is better, 6-18 is better, 6-10 is further better) or aryl Alkyl (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12) is preferred. These groups may have a substituent within a range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring to be formed, a nitrogen-containing heterocyclic ring having 4 to 7 members is preferable. Rb ¹ and Rb ² are especially preferably straight-chain, branched or cyclic alkyl groups that may have substituents (the number of carbons is preferably 1-24, more preferably 2-18, and more preferably 3-12) , a cycloalkyl group that may have a substituent (preferably carbon number 3-24, more preferably 3-18, and more preferably 3-12) is more preferable, and a cyclohexyl group that may have a substituent is further preferable.

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and aryl (preferably having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms). is more preferable, 6-10 is further preferable), alkenyl (carbon number 2-24 is preferable, 2-12 is more preferable, 2-6 is further preferable), arylalkyl (carbon number 7- 23 is better, 7-19 is better, 7-12 is further better), arylalkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better) , alkoxy (carbon number 1-24 is preferred, 2-18 is more preferred, 3-12 is further preferred), aryloxy (carbon number 6-22 is preferred, 6-18 is more preferred, 6 to 12 are more preferred) or arylalkoxy (the number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and more preferably 7 to 12). Among them, cycloalkyl (preferably carbon number of 3 to 24, more preferably 3 to 18, and even more preferably 3 to 12), arylalkenyl and arylalkoxy are preferred. Rb ³ may further have a substituent within a range in which the effects of the present invention are exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 69]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in the formula (B1), respectively. Rb ¹³ is alkyl (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), arylalkyl (carbon number 7-23 is preferred) , 7 to 19 are more preferable, and 7 to 12 are further preferable), and may have a substituent within the scope of exerting the effect of the present invention. Among them, Rb ¹³ -series arylalkyl groups are preferred.

Rb ³³ and Rb ³⁴ are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having a carbon number of 2 to 12). preferably, 2-8 is more preferred, 2-3 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), arylalkyl (The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 11), and a hydrogen atom is more preferable.

Rb ³⁵ is alkyl (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), arylalkyl (carbon number 7-23 is preferred) , 7-19 are more preferable, 7-12 are further preferable), aryl group is preferable.

It is also preferable that the compound represented by the formula (B1-1) is the compound represented by the formula (B1-1a). [Chemical formula 70]

Rb ¹¹ and Rb ¹² are synonymous with Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably having 2 to 12 carbon atoms, and 2 ～6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), arylalkyl (carbon number is better) 7-23 are preferable, 7-19 are more preferable, 7-11 are further preferable), hydrogen atom or methyl group is preferable. Rb ¹⁷ is an alkyl group (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), arylalkyl (carbon number 7-23 is preferred) , 7-19 are more preferable, 7-12 are further preferable), among which aryl group is preferable.

The molecular weight of the nonionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

The following compounds can be mentioned as a specific example of a compound which is a thermal base generator among the above-mentioned onium salts or a specific example of a thermal base generator other than the above-mentioned onium salt.

[Chemical formula 71]

[Chemical formula 72]

[Chemical formula 73]

The content of other thermal alkali generators is preferably 0.1 to 50 mass % with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass % or more, and even more preferably 1 mass % or more. The upper limit is more preferably 30 mass % or less, and even more preferably 20 mass % or less. One type or two or more types of thermal alkali generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

＜Crosslinking agent＞ The curable resin composition of the present invention preferably contains a crosslinking agent. As a crosslinking agent, a radical crosslinking agent and other crosslinking agents are mentioned.

<Radical crosslinking agent> The curable resin composition of the present invention preferably further contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. The radically polymerizable group is preferably a group containing an ethylenically unsaturated bond. As a group containing the said ethylenically unsaturated bond, the group which has an ethylenically unsaturated bond, such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, is mentioned. Among these, as the group containing the above-mentioned ethylenically unsaturated bond, a (meth)acryloyl group is preferable, and a (meth)acryloyl group is more preferable from the viewpoint of reactivity.

The radical crosslinking agent should just be a compound which has one or more ethylenically unsaturated bonds, and a compound which has two or more is more preferable. The compound having two ethylenically unsaturated bonds is preferably a compound having two of the above-mentioned groups containing an ethylenically unsaturated bond. Moreover, from the viewpoint of the film strength of the obtained pattern, it is preferable that the curable resin composition of this invention contains the compound which has 3 or more ethylenically unsaturated bonds as a radical crosslinking agent. As the above-mentioned compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 3 to 15 ethylenically unsaturated bonds is more preferable. The compound of 6 is more preferable. In addition, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, more preferably 3 to 15, and 3 or more Compounds with ∼10 pieces are more preferable, and compounds with 3 to 6 pieces are particularly preferable. Moreover, from the viewpoint of the film strength of the obtained pattern, it is preferable that the curable resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds. good.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl groups, amine groups, and sulfanyl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. The addition reactant, or the dehydration condensing reactant with monofunctional or polyfunctional carboxylic acid, etc. In addition, the addition of unsaturated carboxylates or amides having electron-withdrawing substituents such as isocyanate groups or epoxy groups to monofunctional or polyfunctional alcohols, amines, and thiols can also be preferably used. Reactants, as well as unsaturated carboxylic acid esters or amides with detachable substituents such as halogeno group or tosyloxy group and monofunctional or polyfunctional alcohols, amines, Substitution reactants of thiols. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, and allyl ether can also be used in place of the above-mentioned unsaturated carboxylic acid. As a specific example, reference can be made to the descriptions of paragraphs 0113 to 0122 of JP 2016-027357 A, which are incorporated in the present specification.

In addition, it is also preferable that the radical crosslinking agent is a compound having a boiling point of 100° C. or higher under normal pressure. Examples of this include adding ethylene oxide or propylene oxide to polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, and neopentyl glycol di(meth)acrylate. (Meth)acrylate, Neopentaerythritol tri(meth)acrylate, Neotaerythritol tetra(meth)acrylate, Dipivalerythritol penta(meth)acrylate, Dipivalerythritol hexa (Meth)acrylate, Hexylene glycol (meth)acrylate, Trimethylolpropane tris(acrylooxypropyl)ether, tris(acrylooxyethyl)isocyanurate, glycerin or trihydroxy Compounds that have been (meth)acrylated on polyfunctional alcohols such as methyl ethane, such as Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193. Urethane (meth)acrylates described in the gazettes, polyesters described in Japanese Patent Laid-Open No. 48-064183, Japanese Patent Laid-Open No. 49-043191, and Japanese Patent Laid-Open No. 52-030490 Acrylates, polyfunctional acrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, or methacrylates, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making a compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid are also mentioned.

In addition, as a preferable radical crosslinking agent other than the above-mentioned ones, those having a pyrene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used A compound or cardo resin having two or more ethylenically unsaturated bond-containing groups.

In addition, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, or Japanese Patent Publication No. Hei 02 can also be cited. - Vinylphosphonic acid-based compounds and the like described in Gazette No. 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of Adhesion Association of Japan, vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used. incorporated into this manual.

In addition, as described in Japanese Patent Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples thereof, ethylene oxide or propylene oxide was added to a polyfunctional alcohol, and then ( Meth)acrylated compounds can also be used as free-radical crosslinkers.

In addition, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as a radical crosslinking agent, and these contents are incorporated in the present specification.

As the radical crosslinking agent, dipeotaerythritol triacrylate (available as a commercial item: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipeotaerythritol tetraacrylate (available as a commercial item as KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd. -310; manufactured by Nippon Kayaku Co., Ltd.), dipivaloerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomeric forms can also be used.

Commercially available products of the radical crosslinking agent include, for example, SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy-extended chains, and as a tetrafunctional acrylate having four ethoxy-extended chains SR-209, 231, 239 manufactured by Sartomer Company, Inc., a bifunctional methacrylate, DPCA-60, a hexafunctional acrylate having 6 pentenoxy chains, manufactured by Nippon Kayaku Co., Ltd. , TPA-330 as trifunctional acrylate having 3 isobutenyloxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M- 40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As a radical crosslinking agent, for example, the aminomethyl group described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Acrylic acid esters, ethylene oxides described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 The urethane compounds of the backbone are also preferred. In addition, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amino group in the molecule can also be used. Compounds of structure or sulfide structure.

The free-radical cross-linking agent may also be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. The free-radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Particularly preferably, in a radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is neopentylerythritol or dipivale. Compounds of tetraols. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., LTD., for example.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. When the acid value of the radical crosslinking agent is within the above-mentioned range, workability in production is excellent, and furthermore, developability is excellent. In addition, the polymerizability was good. On the other hand, the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g, from the viewpoint of the development speed during alkali development. The said acid value is measured based on the description of JISK0070:1992.

It is preferable to use bifunctional methacrylate or acrylate as the curable resin composition of this invention from the viewpoint of the resolution of a pattern and the stretchability of a film. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 diacrylate can be used Methacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Diacrylate methacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-triacrylate Cyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, bisphenol PO adduct diacrylate of A, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO modified diacrylic acid of isocyanurate Esters, isocyanuric acid-modified dimethacrylates, and bifunctional acrylates with urethane bonds, and bifunctional methacrylates with urethane bonds. Two or more of these can be mixed and used as needed. Moreover, as a radical crosslinking agent, a monofunctional radical crosslinking agent can be used suitably from a viewpoint of suppressing the warpage accompanying the elastic modulus control of a pattern. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate can be preferably used Butoxyethyl acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (Meth)acrylic acid derivatives such as (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-ethylene N-vinyl compounds such as pyrrolidone and N-vinyl caprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. class etc. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable.

When a radical crosslinking agent is contained, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the curable resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When two or more types are used in combination, it is preferable that the total amount is in the above-mentioned range.

<Other crosslinking agents> It is preferable that the curable resin composition of this invention contains other crosslinking agent different from the said radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and has a plurality of compounds in the molecule which are promoted by the sensitivity of the above-mentioned photosensitizer and other compounds in the composition or their reaction products The compound of the reaction group that forms covalent bonds between them is preferably, and has a plurality of compounds in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. Compounds of the reactive groups are preferred. The above acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator as a photosensitive agent in the exposure process. As other cross-linking agents, compounds having at least one group selected from the group consisting of methylol and alkoxymethyl are preferred, and compounds having at least one group selected from the group including methylol and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group is directly bonded to a nitrogen atom is more preferable. As another crosslinking agent, for example, a compound having an amine group such as formaldehyde or formaldehyde and alcohol reacted with melamine, acetylene urea, urea, alkylene urea, benzoguanamine, etc., and a methylol or alkoxyl group can be used. A compound in which the hydrogen atom of the above-mentioned amine group is substituted with a methyl group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, the oligomer in which the methylol groups of these compounds are self-condensed may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea or alkylene urea is called urea-based cross-linking agent. The crosslinking agent of alkylene urea is called alkylene urea type crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine type crosslinking agent. Among these, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and preferably includes a compound selected from the group consisting of glycoluril described later At least one compound in the group of a crosslinking agent and a melamine-based crosslinking agent is more preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

Specific examples of the urea-based crosslinking agent include, for example, monohydroxymethylated acetylene carbamide, dihydroxymethylated acetylene carbamide, trihydroxymethylated acetylene carbamide, tetrahydroxymethylated acetylene carbamide, and monomethoxy methoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxy Methylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide Methylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide Acetylene carbamide cross-linking agents such as methylated acetylene carbamide; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea and bisbutoxymethyl urea; Monohydroxymethylated ethyl urea or dihydroxymethylated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea Ethyl urea and other ethyl urea crosslinking agents; Monohydroxymethylated propylene glycol, dihydroxymethylated propylene glycol, monomethoxymethylated propylene glycol, dimethoxymethylated propylene glycol , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethyl propylene urea Propylene urea based crosslinking agent such as propylene propylene urea; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of the benzoguanamine-based crosslinking agent include, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, and tetrahydroxymethylated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene guanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as a compound having at least one group selected from the group consisting of methylol and alkoxymethyl, a compound selected from the group consisting of methylol and alkoxymethyl can also be preferably used. A compound in which at least one group in the group is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, and bis(hydroxymethyl) base) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)biphenyl (Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyl oxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene yltris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl -1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products can also be used, and preferable ones include 46DMOC, 46DMOEP (the above are manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML- OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML- BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, the same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (the above are manufactured by Sanwa Chemical Co., Ltd.), etc.

Moreover, it is also preferable that the curable resin composition of this invention contains at least 1 compound chosen from the group which consists of an epoxy compound, an oxetane compound, and a benzodiazepine compound as another crosslinking agent.

[Epoxy compound (a compound having an epoxy group)] As an epoxy compound, the compound which has two or more epoxy groups in 1 molecule is preferable. The epoxy group undergoes a cross-linking reaction at 200° C. or lower, and does not generate a dehydration reaction derived from the cross-linking, so film shrinkage is unlikely to occur. Therefore, containing an epoxy compound is effective for low-temperature curing and warpage suppression of the curable resin composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. The polyethylene oxide group refers to those having 2 or more repeating units of ethylene oxide, and preferably 2 to 15 repeating units.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl Polyalkylene glycol type epoxy resins such as glycerol ethers; epoxy-containing silicones such as polymethyl(glycidoxypropyl)siloxane, etc., but not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) ) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, Rika Resin (registered trademark) ) BEO-20E (the above are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) ) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (the above are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000- H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, B REN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxetane compounds (compounds having oxetanyl groups)] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzene Dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more .

[Benzoxazole compounds (compounds with a benzoxazolyl group)] The benzodiazepine compound is preferable because the crosslinking reaction originating from the ring-opening addition reaction does not cause outgassing during curing, and further reduces thermal shrinkage and suppresses warpage.

Preferable examples of benzodiazepine compounds include B-a-type benzodiazepines, B-m-type benzodiazepines, P-d-type benzodiazepines, and F-a-type benzodiazepines (the above are trade names, SHIKOKU CHEMICALS CORPORATION Manufacture), benzos adducts of polyhydroxy styrene resins, and phenol novolac-type dihydrobenzos. These may be used alone or in combination of two or more.

The content of other crosslinking agents is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 0.5 to 15 mass % with respect to the total solid content of the curable resin composition of the present invention, 1.0-10 mass % is especially preferable. The other crosslinking agents may be contained only by one, or two or more of them may be contained. When two or more types of other crosslinking agents are contained, it is preferable that the total is within the above-mentioned range.

<Compounds with Sulfonamide Structure and Compounds with Thiourea Structure> The curable resin composition of the present invention further contains a compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure from the viewpoint of improving the adhesiveness to the base material of the obtained pattern. At least one compound is preferred.

在式（S-1）中，R表示氫原子或有機基團，R可以與其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。 上述R係與下述式（S-2）中的R² 相同的基團為較佳。 具有磺醯胺結構之化合物可以為具有2個以上磺醯胺結構之化合物，具有1個以上磺醯胺結構之化合物為較佳。[Compound having a sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical formula 74]

In formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to other structures to form a ring structure, and * each independently represents a bonding site to other structures. The above R is preferably the same group as R ² in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and a compound having one or more sulfonamide structures is preferred.

在式（S-2）中，R¹ 、R² 及R³ 分別獨立地表示氫原子或1價有機基團，R¹ 、R² 及R³ 中的2個以上可以相互鍵結而形成環結構。 R¹ 、R² 及R³ 分別獨立地表示1價有機基團為較佳。 作為R¹ 、R² 及R³ 的例子，可以舉出氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、或者將該等組合2個以上之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如，可以舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為上述環烷基，例如，可以舉出環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可以舉出甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基甲矽烷基，碳數1～10的烷氧基甲矽烷基為較佳，碳數1～4的烷氧基甲矽烷基為更佳。作為上述烷氧基甲矽烷基，可以舉出甲氧基甲矽烷基、乙氧基甲矽烷基、丙氧基甲矽烷基及丁氧基甲矽烷基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。上述芳基可具有烷基等取代基。作為上述芳基，可以舉出苯基、甲苯基、二甲苯基及萘基等。 作為上述雜環基，可以舉出從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、嗎啉環、二氫哌喃環、四氫哌喃環、三𠯤環等雜環結構去除1個氫原子之基團等。The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical formula 75]

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure. It is preferable that R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, An aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group combining two or more of these, and the like. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. As said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc. are mentioned. As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above-mentioned heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, One hydrogen atom is removed from heterocyclic structures such as pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, dihydropyran ring, tetrahydropyran ring, and trihydropyran ring group, etc.

Among these, compounds in which R ¹ is an aryl group and R ² and R ³ are each independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, Hydroxynaphthylsulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-di Methylmethanesulphonamide, N,N-Dimethylethanesulphonamide, N,N-Diethylmethanesulphonamide, N-Methoxymethanesulphonamide, N-Dodecylmethanesulphonamide amine, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.

在式（T-1）中，R⁴ 及R⁵ 分別獨立地表示氫原子或1價有機基團，R⁴ 及R⁵ 可以鍵結而形成環結構，R⁴ 可以與*所鍵結之其他結構鍵結而形成環結構，R⁵ 可以與*所鍵結之其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。[Compound having a thiourea structure] The thiourea structure is a structure represented by the following formula (T-1). [Chemical formula 76]

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ may be bonded to form a ring structure, and R ⁴ may be bonded to other * The structure is bonded to form a ring structure, and R ⁵ may be bonded to other structures to which * is bonded to form a ring structure, and * each independently represents a bonding site with other structures.

Preferably, R ⁴ and R ⁵ are each independently a hydrogen atom. Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, and an aryl ether group. group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, or a combination of two or more of these. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. As said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc. are mentioned. As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above-mentioned heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, One hydrogen atom is removed from heterocyclic structures such as pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, dihydropyran ring, tetrahydropyran ring, triscal ring, etc. group, etc. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

在式（T-2）中，R⁴ ～R⁷ 分別獨立地表示氫原子或1價有機基團，R⁴ ～R⁷ 中的至少2個可以相互鍵結而形成環結構。The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical formula 77]

In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), R ⁴ and R ⁵ are synonymous with R ⁴ and R ⁵ in formula (T-1), and the preferred embodiments are also the same. In formula (T-2), it is preferable that R ⁶ and R ⁷ are each independently a monovalent organic group. In the formula (T-2), the preferred aspect of the monovalent organic group in R ⁶ and R ⁷ is the same as the preferred aspect of the monovalent organic group in R ⁴ and R ⁵ in the formula (T-1) Same pattern.

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1- Adamantyl thiourea, N-benzylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diiso Propylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea , N,N-diphenylthiourea, ethylenethiourea (2-imidazoline thione), Carbimazole, 1,3-dimethyl-2-thiohydantoin, etc.

〔content〕 With respect to the total mass of the curable resin composition of the present invention, the total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10 mass %, more preferably 0.1 to 5 mass % , 0.2 to 3 mass % is more preferable. The curable resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more types. When only one compound is contained, the content of the compound is preferably within the above-mentioned range, and when two or more kinds are contained, the total amount thereof is preferably within the above-mentioned range.

<Migration inhibitor> It is preferable that the curable resin composition of the present invention further contains a migration inhibitor. By including the migration inhibitor, the movement of metal ions originating from the metal layer (metal wiring) into the photosensitive film can be effectively suppressed.

The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring) compound of ring, tetrazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) , thioureas and compounds with hydrogen thio groups, hindered phenol compounds, salicylic acid derivatives, and hydrazine derivatives. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion scavenger that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, and JP 2011 A can be used. - Compounds described in paragraph 0052 of Japanese Patent Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015/199219 compounds, etc.

Specific examples of the migration inhibitor include the following compounds.

[Chemical formula 78]

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass relative to the total solid content of the curable resin composition. 0.1-1.0 mass % is more preferable.

The migration inhibitor may be only one type or two or more types. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned range.

<Polymerization inhibitor> The curable resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, p-tert-butyl can be preferably used. Catechol (tert-butylcatechol), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butyl) phenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitroso diphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl- 4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N -Ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis( 4-Hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 ,5-Tris𠯤-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, phenothiazine , 1,1-diphenyl-2-pyrrolehydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso Alkyl-N-phenylhydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-tert-butylhydroxytoluene, 1, 4-Naphthoquinone, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP-A 2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used.

In addition, the following compounds can be used.

[Chemical formula 79]

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0 mass % and 0.01 to 5 mass % relative to the total solid content of the curable resin composition of the present invention. % is preferable, 0.02-3 mass % is more preferable, and 0.05-2.5 mass % is more preferable.

Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

<Metal Adhesion Improver> It is preferable that the curable resin composition of this invention contains the metal adhesion improver for improving the adhesion with the metal material used for electrodes, wiring, etc.. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, and beta keto acids. Ester (β keto ester) compounds, amine compounds, etc.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002 A, and compounds described in International Publication No. 2011/ Compounds described in paragraphs 0063 to 0071 of No. 080992, compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, and compounds described in paragraphs 0045 to 0052 of JP 2014-041264 , the compound described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Et represents an ethyl group.

作為其他矽烷偶合劑，例如可以舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-（三甲氧基矽基丙基）異氰脲酸酯、3-脲基丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基矽基丙基丁二酸酐。該等能夠單獨使用一種或者組合使用兩種以上。[Chemical formula 80]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. Propylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxy Silane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyl Acrylooxypropylmethyldiethoxysilane, 3-methacrylooxypropyltriethoxysilane, 3-acrylooxypropyltrimethoxysilane, N-2-(aminoethyl) group)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, Tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based Adhesives] As an aluminum-based adhesive agent, for example, tris(acetoacetate ethyl)aluminum, tris(acetoacetone)aluminum, acetoacetate ethyl diisopropoxide aluminum, etc. are mentioned.

In addition, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032-0043 of JP-A 2013-072935 can also be used compound.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above-mentioned range.

<Metal Adhesion Improver> It is preferable that the curable resin composition of this invention contains the metal adhesion improver for improving the adhesion with the metal material used for electrodes, wiring, etc.. As the metal adhesion improving agent, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032-0043 of JP-A 2013-072935 can also be used .

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 100 parts by mass of the heterocycle-containing polymer precursor. within the range of 5 parts by mass. By setting it as the said lower limit or more, the adhesiveness of the pattern and a metal layer after a heating process becomes favorable, and by setting it as below the said upper limit value, the heat resistance and mechanical properties of the cured product after a heating process become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above-mentioned range.

＜Other additives＞ The curable resin composition of the present invention can contain various additives such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardening agents, hardening catalysts, fillers, antioxidants, UV absorbers, anti-agglomeration agents, etc. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the curable resin composition.

[Sensitizer] The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal hardening accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc. to produce electron transfer, energy transfer, and heat generation. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane Alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-diethylamine Methylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole , 2-(p-dimethylaminophenylvinylidene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-bis ethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy carbonylcarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3 -Ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4 -Morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2- mercaptobenzothiazole, 2-(p-dimethylaminostyrene) benzoxazole, 2-(p-dimethylaminostyrene) benzothiazole, 2-(p-dimethylaminostyryl) ) naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzalaniline, N-methylacetaniline, 3 ',4'-Dimethylacetaniline, etc. As a sensitizer, a sensitizing dye can also be used. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A, which are incorporated in the present specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass relative to the total solid content of the curable resin composition of the present invention. The mass % is more preferable, and 0.5 to 10 mass % is further preferable. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain transfer agent] The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, 3rd Edition (ed. by the Society for Polymer Science, 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These can generate free radicals by supplying hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, a thiol compound can be preferably used.

Moreover, as a chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention, 1-10 mass parts is more preferable, and 1-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, it is preferable that the total is within the above-mentioned range.

又，界面活性劑亦能夠使用國際公開第2015/199219號的0159～0165段中所記載之化合物。 關於氟系界面活性劑，亦能夠將在側鏈中具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可以舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中所記載之化合物，例如DIC Corporation製造之MEGAFACE RS-101、RS-102、RS-718K等。[Surfactant] From the viewpoint of further improving coatability, a surfactant may be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Moreover, the following surfactant is also preferable. In the following formula, the parentheses representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating units of the side chains represent the repeating number of each repeating unit. [Chemical formula 81]

Moreover, the compound described in the paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used as the surfactant. Regarding the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective from the viewpoint of the uniformity of the thickness of the coating film or the liquid saving property, and the solubility in the composition is also good.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co. ., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

Examples of hydrocarbon-based surfactants include PIONIN A-76, New Kalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (the above are manufactured by Takemoto Oil & Fat Co., Ltd.), etc.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) base, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diethyl ether Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701 , 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112 , D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

As an anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.), SANDET BL (made by SANYO KASEI CO., LTD.) etc. are mentioned specifically,.

When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % with respect to the total solid content of the curable resin composition of the present invention, more preferably 0.005 to 1.0 mass %. Only one type of surfactant may be used, or two or more types may be used. When two or more types of surfactants are used, it is preferable that the total is within the above-mentioned range.

[Higher fatty acid derivatives] In order to prevent polymerization inhibition by oxygen, the curable resin composition of the present invention may be made non-uniform in the drying process after coating by adding a higher fatty acid derivative such as behenic acid or behenamide. distributed on the surface of the curable resin composition.

Moreover, the compound described in the paragraph 0155 of International Publication No. 2015/199219 can also be used as a higher fatty acid derivative.

When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.

[Thermal polymerization initiator] The resin composition of the present invention may also contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or promote the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5% by mass relative to the total solid content of the resin composition of the present invention. ~15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount thereof is preferably within the above range.

[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. When the average particle diameter of the said inorganic particle is less than 0.01 micrometer, the mechanical properties of the said cured film may deteriorate. Moreover, when the average particle diameter of the said inorganic particle exceeds 2.0 micrometers, the resolution may fall by the scattering of exposure light.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like, and examples of the benzophenone-based ultraviolet absorber include Examples of the agent include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl ketone etc. Moreover, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2- -(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetrakis Methyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate esters, etc. Moreover, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-type ultraviolet absorber -Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris-tris(hydroxyphenyl)tris-compounds, etc.

In the present invention, the aforementioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber, but when an ultraviolet absorber is contained, the content of the ultraviolet absorber is 0.001 mass % or more and 1 mass % relative to the total solid content mass of the composition of the present invention % or less is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.

[Organo-titanium compound] The resin composition of the present embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, even when it is cured at a low temperature, a resin layer excellent in chemical resistance can be formed.

As an organotitanium compound that can be used, an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, the titanium chelate compound having two or more alkoxy groups is more preferable from the viewpoint that the storage stability of the negative photosensitive resin composition is good and a good hardened pattern can be obtained. . Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium bis(2,4-glutarate) bis(n-butoxy), titanium diisopropoxide bis(2,4-glutarate) ), diisopropoxytitanium bis (tetramethyl pimelic acid ester), diisopropoxytitanium bis (ethyl acetate), etc. II) Tetraalkoxytitanium compounds: for example, tetrakis(n-butoxy)titanium, tetraethoxytitanium, tetrakis(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium Titanium, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetrakis (n-nonyloxide), titanium tetrakis (n-propoxide), titanium tetrastearyloxide, tetrakis[bis] {2,2-(allyloxymethyl) butoxy}] titanium, etc. III) Titanocene compounds: for example, titanium pentamethylcyclopentadienyltrimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxytitanium compounds: for example, tris(dioctylphosphate)isopropoxytitanium, tris(dodecylbenzenesulfonate)isopropoxytitanium, and the like. V) Titanium oxide compounds: for example, bis(glutarate) titanium oxide, bis(tetramethylpimelate) titanium oxide, phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

Among them, the organotitanium compound is selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound and III) titanocene compound from the viewpoint of exhibiting better chemical resistance At least one compound is preferred. In particular, bis(ethylacetate)diisopropoxytitanium, tetrakis(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6 -Difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the compounding amount is 0.05 parts by mass or more, favorable heat resistance and chemical resistance are exhibited in the obtained cured pattern, and on the other hand, when it is 10 parts by mass or less, the storage stability of the composition is excellent .

〔Antioxidants〕 The composition of the present invention may contain antioxidants. By containing an antioxidant as an additive, the ductility property of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. In addition, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]Diethylphosphine-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenol)ethyl phosphite, etc. . Examples of commercially available antioxidants include ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO- 80. ADKSTAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants. Moreover, the composition of this invention may contain a latent antioxidant as needed. As the latent antioxidant, the site that functions as an antioxidant is protected by a protective group, and the protective group is removed by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst. Compounds that thus act as antioxidants. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP 2017-008219 A. As a commercial item of a latent antioxidant, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. Examples of preferable antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and general formula (3 ) represented by the compound.

[Chemical formula 82]

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ⁶ represents an alkylene group having 2 or more carbon atoms. R ⁷ represents an alkylene group having 2 or more carbon atoms, and a 1- to 4-valent organic group containing at least any one of an O atom and a N atom. k represents an integer of 1-4.

The compound represented by the general formula (3) suppresses the oxidative deterioration of the aliphatic group or the phenolic hydroxyl group of the resin. Moreover, metal oxidation can be suppressed by the rust preventive effect on the metal material.

Since it can act on a resin and a metal material at the same time, k is an integer of 2 to 4 more preferably. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. group, vinyl group, heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may further have a substituent. Among them, alkyl ethers and -NH- are preferred from the viewpoints of solubility in developing solutions and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion by metal complex formation For example, -NH- is better.

Examples of the compound represented by the following general formula (3) include the following, but are not limited to the following structures.

[Chemical formula 83]

[Chemical formula 84]

[Chemical formula 85]

[Chemical formula 86]

The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. When the addition amount is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the ductility after hardening or the adhesion to the metal material, and when it is more than 10 parts by mass, there is a possibility that the The interaction leads to a decrease in the sensitivity of the resin composition. As for the antioxidant, only one type may be used, or two or more types may be used. When two or more types are used, the total amount of these is preferably within the above-mentioned range.

＜Restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass. As a method of maintaining the moisture content, adjustment of the humidity under storage conditions, reduction of the porosity of the storage container, and the like are exemplified.

From the viewpoint of insulating properties, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm Further preferred. As a metal, sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. are mentioned. When a plurality of metals are contained, the sum of these metals is preferably within the above range.

In addition, as a method for reducing the metal impurities unintentionally contained in the curable resin composition of the present invention, methods such as selecting a raw material with a small metal content as a raw material constituting the curable resin composition of the present invention; The raw material of the curable resin composition of the present invention is filtered through a filter, and the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible.

In the curable resin composition of the present invention, considering the use as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm is more preferable. Among them, it is preferable that it is less than 5 mass ppm in the state of a halogen ion, and it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromide ion is each in the said range. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like can be preferably used.

As the storage container of the curable resin composition of the present invention, a conventionally known storage container can be used. In addition, as the container, for the purpose of suppressing the contamination of impurities into the raw material or the curable resin composition, a multilayer bottle in which the inner wall of the container is made of six kinds of resins with six layers or a bottle with a seven-layer structure made of six kinds of resins can also be used. is better. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Application of curable resin composition> The curable resin composition of the present invention is preferably used for formation of an interlayer insulating film for rewiring layers. In addition, it can also be used for formation of an insulating film of a semiconductor device, formation of a stress buffer film, and the like.

<Preparation of curable resin composition> The curable resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and particles in the curable resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be previously washed with an organic solvent. In the filter filtration process, a plurality of filters can be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it can be loop filtering. Moreover, filtration can be performed by pressurization. When filtration is performed by pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, and even more preferably 0.05 MPa or more and 0.7 MPa or less. In addition to filtration using a filter, removal of impurities using an adsorbent material can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent material. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned.

(Cured film, laminated body, semiconductor device, and their manufacturing method) Next, a cured film, a laminated body, a semiconductor device, and the manufacturing method of these are demonstrated.

The cured film of the present invention is a cured film obtained by curing the curable resin composition of the present invention. The cured film is preferably a patterned cured film. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, or 1 μm or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

The cured film of the present invention may be laminated in two or more layers, and further 3 to 7 layers may be laminated to form a laminated body. It is preferable that the laminated system of this invention contains the cured film of two or more layers, and contains the metal layer between arbitrary said cured films. For example, as a preferable thing, the laminated body which consists of the layer structure which laminated|stacked at least 3 layers of a 1st cured film, a metal layer, and a 2nd cured film in this order is mentioned. Both the said 1st cured film and the said 2nd cured film are the cured film of this invention, As a preferable example, the said 1st cured film and the said 2nd cured film are both the curable resin composition of this invention, for example, can be mentioned. The state of the hardened film. The curable resin composition of this invention used for formation of the said 1st cured film and the curable resin composition of this invention used for formation of the said 2nd cured film may be a composition of the same composition, and may have a different composition. composition. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

As a field|area to which the cured film of this invention can be applied, the insulating film of a semiconductor device, the interlayer insulating film for rewiring layers, a stress buffer film, etc. are mentioned. Other examples include patterning of sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), and insulating films for encapsulation as described above by etching. For such applications, see, for example, SCIENCE AND TECHNOLOGY CO., LTD. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical library "Polyimide Materials "Basics and Development" published in November 2011, Japan Polyimide and Aromatic Polymer Research Association/Edited "Latest Polyimide Fundamentals and Applications" NTS Inc., August 2010, etc.

Moreover, the cured film in the present invention can also be used for the manufacture of printing plates such as offset printing plates and screen printing plates, the use in etching of forming components, and the protective paint and media in electronics, especially microelectronics. Manufacture of electrical layers, etc.

The manufacturing method of the cured film of the present invention (hereinafter, also simply referred to as "the manufacturing method of the present invention".) includes a film forming process for forming a film (resin film) by applying the curable resin composition of the present invention to a substrate. is better. Preferably, the manufacturing method of the cured film of the present invention includes the above-mentioned film formation process, an exposure process of exposing the above-mentioned film, and a development process of developing the above-mentioned film. Through the above-mentioned exposure process and development process, the pattern of the cured film can be obtained. Moreover, it is more preferable that the manufacturing method of the cured film of the present invention includes the above-mentioned film formation process and the above-mentioned development process as required, and also includes a heating process of heating the above-mentioned film at 50-450°C. Specifically, processes including the following (a) to (d) are also preferred. (a) Film forming process for forming a film (resin composition layer) by applying a curable resin composition to a substrate (b) Exposure process for exposing the film after the film formation process (c) Development process for developing the exposed film above (d) Heating process of heating the developed film at 50-450°C By heating in the above-mentioned heating process, the resin layer hardened by exposure can be further hardened. In this heating process, for example, the above-mentioned thermal alkali generator is decomposed to obtain sufficient hardenability.

The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. In the manufacturing method of the laminated body of this embodiment, after forming a cured film according to the manufacturing method of the said cured film, the process of (a), the process of (a)-(c), or the process of (a)-(d) are performed again. In particular, it is preferable that each of the above-mentioned processes is sequentially performed a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating a cured film in this way, a laminated body can be produced. In this invention, it is preferable to provide a metal layer especially on the part provided with the cured film or between the cured films, or on the part provided with the cured film and between the cured films. In addition, when manufacturing a laminated body, it is not necessary to repeat all the processes (a) to (d), as described above, by performing (a) at least a plurality of times, preferably (a) to (c) or (a) The process of -(d) can obtain the laminated body of a cured film.

<Film formation process (layer formation process)> The production method of the preferred embodiment of the present invention includes a film formation process (layer formation process) in which a curable resin composition is applied to a substrate to form a film (layer).

The type of base material can be appropriately specified according to the application, and can be made of semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection Film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrates, electrode plates for plasma display panels (PDP), etc., It is not particularly limited. Moreover, these base materials may be provided with layers, such as an adhesive layer and an oxide layer, on the surface. In the present invention, especially semiconductor fabrication substrates are preferred, and silicon substrates, Cu substrates and mold substrates are more preferred. Moreover, these base materials may be provided with layers, such as an adhesive layer and an oxide layer, which consist of hexamethyldisilazane (HMDS) etc. on the surface. Moreover, as a base material, a plate-shaped base material (substrate) can be used, for example. The shape of the base material is not particularly limited, and may be circular or rectangular, but a rectangular shape is preferred. As a size of a base material, if it is a circle, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

Moreover, when a curable resin composition layer is formed on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a base material.

As a method for applying the curable resin composition to a substrate, coating is preferable.

Specifically, as a method to be applied, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating can be exemplified. coating method, slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferred. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can also be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and a rectangular substrate is narrowly applied. Slit coating method, spray method, ink jet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Moreover, depending on the viscosity of the resin composition or the film thickness to be set, it is also preferable to apply it for 10 to 180 seconds at a rotational speed of 300 to 3,500 rpm. In addition, in order to obtain the uniformity of the film thickness, it is also possible to apply a combination of a plurality of rotation speeds. Moreover, the method of transcribe|transferring the coating film previously provided by the said application method and formed on the temporary support body to a base material can also be applied. Regarding the transfer method, in the present invention, those described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Laid-Open No. 2006-047592 can be preferably used. method. Also, a process of removing excess film at the end of the base material can be performed. Examples of such processes include edge bead residue rinse (EBR), air knife, back rinse, and the like. In addition, the following pre-wetting process can also be used: before the resin composition is applied to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

＜Drying process＞ The manufacturing method of the present invention may include a drying process for removing the solvent after the film forming process (layer forming process). The preferred drying temperature is 50 to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure process> The manufacturing method of this invention may include the exposure process which exposes the said film (resin composition layer). The exposure amount is not particularly limited as long as the curable resin composition can be cured. For example, the exposure energy at a wavelength of 365 nm is preferably 100 to 10,000 mJ/cm ² , and more preferably 200 to 8,000 mJ/cm ² . .

The exposure wavelength can be appropriately defined in the range of 190 to 1,000 nm, and is preferably 240 to 550 nm. In addition, it is preferable that the exposure light contains light with a wavelength of 365 nm or 405 nm, and it is more preferable to contain light with a wavelength of 405 nm.

If the exposure wavelength is described in relation to the light source, (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays ( Wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) second harmonic of YAG laser 532nm and third harmonic 355nm etc. For the curable resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. Thereby, in particular, high exposure sensitivity can be obtained. Also, from the viewpoint of handling and productivity, a wide (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp or a semiconductor laser of 405 nm is preferable.

In addition, the method of exposure is not particularly limited, as long as at least a part of the film (photosensitive film) composed of the curable resin composition is exposed to light, and exposure using a mask, laser-based exposure can be exemplified Exposure of direct imaging method, etc. In the present invention, the aspect in which the exposure in the exposure process is based on the exposure of the laser direct imaging method is also one of the preferred aspects.

＜Development process＞ The production method of the present invention may include a development process of developing the exposed film (resin composition layer) (developing the above-mentioned film). Unexposed parts (non-exposed parts) are removed by developing. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include discharging of the developer from a nozzle, spray spray, and immersion of the substrate in the developer, and the discharge from the nozzle can be preferably used. In the developing process, a process of continuously continuously supplying the developer to the substrate, a process of holding the developer in a substantially static state on the substrate, a process of vibrating the developer with ultrasonic waves or the like, and a combination of these can be used. process, etc.

The development system is performed using a developer. The developer can be used without any particular limitation as long as it can remove the unexposed portion (non-exposed portion). As the developer, a developer containing an organic solvent or an aqueous alkali solution can be used.

In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula in ChemBioDraw.

When the developing solution is a developing solution containing an organic solvent, as the organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate can be preferably mentioned. ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkane Alkyl oxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, methoxyacetate) butyl ester, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy propionate acid ethyl ester, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), Alkyl 2-alkoxypropanoates (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, 2-methylpropionate) methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2 -Methyl alkoxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (for example, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy ethyl 2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2 - Ethyl oxobutyrate, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl seleux Acetate, Ethyl Siloxane, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptane can be preferably used Ketones, N-methyl-2-pyrrolidone, etc., and, as cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably mentioned, and as the sulfites, for example, Preferably, dimethyl sulfoxide is used, and a mixture of these organic solvents can also be preferably used.

When the developing solution is a developing solution containing an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. Moreover, when a developing solution contains an organic solvent, one type of organic solvent can be used or two or more types of organic solvents can be mixed and used.

When the developing solution is a developing solution containing an organic solvent, it is preferable that 50 mass % or more of the developing solution is an organic solvent, 70 mass % or more is an organic solvent, and 90 mass % or more is an organic solvent. good. Moreover, in a developing solution, 100 mass % may be an organic solvent.

The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

When the developing solution is an alkaline aqueous solution, examples of the alkaline compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, and the like, and TMAH is preferred. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.3 to 3% by mass, based on the total mass of the developer. better.

[How to supply developer] The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate in the developer, spin-over immersion development in which the developer is supplied to the substrate using a nozzle, or continuous supply of the developer. method. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the efficiency in manufacturing, the method of supplying the developer with a straight nozzle or the method of continuously supplying it with a spray nozzle is preferable. From the viewpoint of the permeability of the image area, the method of supplying with a spray nozzle is more preferable. In addition, after the developer is continuously supplied with the straight nozzle, the substrate can be rotated to remove the developer from the substrate, and after spin drying, the developer can be continuously supplied again with the straight nozzle, and then the substrate can be rotated and removed from the substrate. The process of developing solution, and the process can be repeated several times. In addition, as a method of supplying the developer in the developing process, a process of continuously supplying the developer to the substrate, a process of holding the developer on the substrate in a substantially stationary state, and using an ultrasonic wave to supply the developer to the substrate can be adopted. The process of vibrating on the substrate and the process of combining these, etc.

The development time is preferably 5 seconds to 10 minutes, and more preferably 10 seconds to 5 minutes. The temperature of the developer at the time of development is not particularly limited, but it is usually 10 to 45°C, preferably 20 to 40°C.

After the treatment with the developer, further rinsing may be performed. In addition, a method such as supplying a rinsing liquid may be employed while the developer contacting the pattern is not completely dried. Rinse is preferably carried out in a solvent different from the developer. For example, rinsing can be performed using a solvent contained in the curable resin composition. When the developing solution is a developing solution containing an organic solvent, the rinse solution includes PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol), and the like, and PGMEA is preferred. In addition, as a rinse solution for development by a developer containing an aqueous alkaline solution, water is preferable. The flushing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it is preferably 10 to 45°C, more preferably 18 to 30°C.

Regarding the organic solvent in the case where the rinse liquid contains an organic solvent, the esters include, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and butyl propionate. Esters, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate Esters (eg: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate) methyl ethyl acetate, ethyl ethoxy acetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc. ( For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy Alkyl propionates (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate) ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy- Methyl 2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutyric acid Ethyl esters, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrus acetate, ethyl acetate, etc. Gysellus Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3- Heptanone, N-methyl-2-pyrrolidone, etc., and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably mentioned, and as the sulfites, for example, Preferable examples include dimethylsulfoxide, and examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, propylene glycol, and methyl isobutyl alcohol. Base carbitol, triethylene glycol, etc., and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are mentioned as amides.

When the rinsing liquid contains an organic solvent, one type of organic solvent can be used or two or more types of organic solvents can be used in combination. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferred, and cyclopentanone, γ-butyrolactone are preferred. Esters, dimethylsulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are further preferable.

When the rinse liquid contains an organic solvent, more than 50 mass % of the rinse liquid is preferably an organic solvent, more preferably 70 mass % or more of an organic solvent, and more preferably 90 mass % or more of an organic solvent. Moreover, in a rinse liquid, 100 mass % may be an organic solvent.

The rinse fluid may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[How to supply the rinse solution] The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate in the rinsing liquid, forming a liquid film of the rinsing liquid on the substrate, and applying a shower to the substrate. The method of supplying the rinsing liquid, and the method of continuously supplying the rinsing liquid to the substrate using a mechanism such as a straight nozzle. From the viewpoint of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, the method of supplying the rinse liquid by a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying it by a spray nozzle are: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it with a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing process is preferably a process in which a straight nozzle is used to supply or continuously supply a rinsing liquid to the above-mentioned exposed film, and a process in which the rinsing liquid is supplied by a spray nozzle is more preferable. Further, as a method of supplying the developer in the rinsing process, a process of continuously supplying the rinsing solution to the substrate, a process of holding the rinsing solution in a substantially stationary state on the substrate, and using an ultrasonic wave etc. The process of vibrating on the substrate and the process of combining these, etc.

＜Heating process＞ The manufacturing method of the present invention preferably includes a process (heating process) in which the developed film is heated at 50-450°C. It is preferable to include the heating process after the film forming process (layer forming process), drying process and developing process. In the heating process, for example, a cyclization reaction as a precursor of a specific resin is performed by decomposing the above-mentioned thermal alkali generator to generate a base. In addition, the curable resin composition of the present invention may contain a radically polymerizable compound other than the specific resin precursor, and curing of the unreacted radically polymerizable compound other than the specific resin precursor can also be performed during the process. conduct. As the heating temperature (maximum heating temperature) of the layer in the heating process, 50°C or higher is preferable, 80°C or higher is more preferable, 140°C or higher is further preferable, 150°C or higher is further preferable, and 160°C or higher is even more preferable More preferably, 170°C or higher is still more preferable. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, still more preferably 350°C or lower, still more preferably 250°C or lower, and still more preferably 220°C or lower.

The heating system is preferably carried out at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature. By setting the temperature increase rate to 1°C/min or more, while ensuring productivity, excessive volatilization of the amine can be prevented, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured film can be reduced. Furthermore, in the case of an oven capable of rapid heating, the heating rate is preferably 1 to 8°C/sec, more preferably 2 to 7°C/sec, from the temperature at the start of heating to the maximum heating temperature, and 3 to 3°C/sec. 6°C/sec is more preferable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started. For example, when the curable resin composition is applied to a substrate and then dried, the temperature of the dried film (layer) is, for example, higher than the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually increase the temperature at a lower temperature of 30 to 200°C.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

In particular, in the case of forming a multilayered laminate, from the viewpoint of the adhesiveness between layers of the cured film, the heating temperature is preferably 180°C to 320°C, and 180°C to 260°C is preferred. Heating is better. Although the reason for this is not clear, it is considered that the acetylene groups of the specific resins between the layers undergo a crosslinking reaction by setting the temperature to this temperature.

Heating can be performed in stages. As an example, the following pretreatment process can be performed: from 25°C to 180°C at 3°C/min, hold at 180°C for 60 minutes, from 180°C to 200°C at 2°C/min, at 200°C Hold for 120 minutes. The heating temperature of the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In the pretreatment process, as described in the specification of US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. The characteristics of the film can be improved by such a pretreatment process. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can also be performed in two or more steps. For example, the pretreatment process 1 can be performed in the range of 100 to 150°C, and then the pretreatment process 2 can be performed in the range of 150 to 200°C.

Cooling after heating may be further performed, and the cooling rate at this time is preferably 1 to 5°C/min.

From the viewpoint of preventing the decomposition of the specific resin, it is preferable to perform the heating process in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. Although it does not specifically limit as a heating means, For example, a hotplate, an infrared furnace, an electric heating oven, a hot air oven, etc. are mentioned.

<Metal layer formation process> The manufacturing method of the present invention preferably includes a metal layer forming process in which a metal layer is formed on the surface of the developed film (resin composition layer).

The metal layer is not particularly limited, and existing metal types can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are more preferred. , copper is further preferred.

The method of forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be applied. For example, photolithography, lift off, electrolytic plating, electroless plating, etching, printing, methods of combining the same, and the like are contemplated. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm in the thickest portion.

＜Lamination process＞ Preferably, the manufacturing method of the present invention further includes a lamination process.

The lamination process refers to the process of performing (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process on the surface of the cured film (resin layer) or metal layer in sequence. A series of processes. However, only the film formation process of (a) may be repeatedly performed. In addition, it is also possible to carry out the (d) heating process collectively at the end or in the middle of the build-up. That is, the processes (a) to (c) can be repeated a predetermined number of times, and then the (d) heating can be performed, whereby the laminated resin composition layer can be collectively cured. In addition, the (e) metal layer forming process may be included after the (c) development process. In this case, the (d) heating may be performed each time, or the (d) heating may be performed collectively after lamination for a predetermined number of times. Of course, the above-mentioned drying process or heating process, etc. may be further appropriately included in the lamination process.

When the build-up process is further performed after the build-up process, the surface activation treatment process may be further performed after the above-mentioned heating process, after the above-mentioned exposure process, or after the above-mentioned metal layer formation process. As the surface activation treatment, plasma treatment can be exemplified.

Preferably, the above lamination process is performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. In addition, each layer in the lamination process may be a layer with the same composition, shape, film thickness, etc., or may be a different layer.

For example, as in resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, the structure of resin layers is preferably two or more layers and 20 layers or less, and the structure of three or more layers and seven layers or less is more preferable. Preferably, 3 or more layers and 5 or less layers are more preferable.

In this invention, the aspect which forms the cured film (resin layer) of the said curable resin composition further so that the said metal layer may be covered especially after providing a metal layer is preferable. Specifically, it is possible to repeat the order of (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process, or The sequence of (a) film formation process, (b) exposure process, (c) development process, and (e) metal layer formation process is repeated, and the (d) heating process is arranged at the end or in the middle. The resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the lamination process of laminating the resin composition layer (resin layer) and the metal layer forming process.

(Surface activation treatment process) The manufacturing method of the layered product of the present invention may include a surface activation treatment process of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment process is usually performed after the metal layer formation process, but the metal layer formation process can also be performed after the above-mentioned exposure and development process, and after the surface activation treatment process for the photosensitive resin composition layer. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed photosensitive resin composition layer, or may be performed on both the metal layer and the exposed photosensitive resin composition layer, respectively. at least part of it. Surface activation treatment is preferably performed on at least a part of the metal layer, and surface activation treatment is preferably performed on a part or all of a region of the metal layer where the photosensitive resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesiveness with the resin layer provided on the surface can be improved. Moreover, it is preferable to also perform a surface activation process with respect to a part or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the photosensitive resin composition layer to the surface activation treatment, the adhesiveness with the metal layer or resin layer provided on the surface activation treatment can be improved. The surface activation treatment is specifically selected from plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF4 _- based treatment /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ etching treatment, surface treatment based on ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, and then immersion in amine containing amine The treatment in the organic surface treatment agent of the compound of at least one of the base and the thiol group, the mechanical roughening treatment using a brush, the plasma treatment is preferred, especially the oxygen plasma treatment using oxygen in the raw material gas is preferred. good. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used for the formation of the interlayer insulating film for rewiring layers, the descriptions in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to. described, and these contents are incorporated into this specification. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. As long as there is no special description, "parts" and "%" are quality standards.

<Synthesis Example 1: Synthesis of Polymer A-1> Put 23.48g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27g of 4,4'-biphenyltetracarboxylic dianhydride (BPDA) into a separate flask, and put methacrylic acid 39.69 g of 2-hydroxyethyl ester (HEMA) and 136.83 g of γ-butyrolactone were stirred at room temperature, and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction was completed, it was left to cool to room temperature and left to stand for 16 hours. Next, a solution obtained by dissolving 62.46 g of dicyclohexylcarbodiimide (DCC) in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice-cooling. For 60 minutes, what was prepared by suspending 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of γ-butyrolactone was added. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added, followed by stirring for 1 hour, and then, 136.83 g of γ-butyrolactone was added. The reaction liquid was obtained by removing the precipitate which generate|occur|produced in the reaction mixture by filtration. The obtained reaction liquid was added to 716.21 g of ethanol, and a precipitate consisting of a crude polymer was formed. The produced crude polymer was filtered off, and was dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum-dried to obtain a powdery polymer (polyimide precursor) A-1 . The molecular weight of the polyimide precursor A-1 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000.

<Synthesis Example 2: Synthesis of Polymer A-2> Polymer A-2 was synthesized by the same method as in Synthesis Example 1, except that ODPA 23.48 g and BPDA 22.27 g were changed to ODPA 46.96 g.

<Synthesis Example 3: Synthesis of Polymer A-3> In the same manner as in Synthesis Example 1, except that ODPA 23.48 g and BPDA 22.27 g were changed to ODPA 46.96 g, and HEMA 39.69 g was changed to HEMA 19.85 g and diethylene glycol monomethyl ether 18.32 g Polymer A-3.

<Synthesis Example 4: Synthesis of Polymer A-4> In a drying reactor equipped with a stirrer, a condenser, and a flat-bottomed joint equipped with an internal thermometer, 10.65 g (50 mM dihydrochloride) of 4,6-dihydroxy-1,3-phenylenediamine dihydrochloride was prepared while removing water. ear) was dissolved in N-methylpyrrolidone (NMP) 85.8 g. Next, 9.74 g (48 mmol) of terephthalic acid chlorides were dissolved in 55.0 g of NMP, and were added dropwise over 1 hour, followed by stirring at 25° C. for 2 hours. After stirring, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio), and stirred at 2,000 rpm for 30 minutes. The precipitated polybenzoxazole precursor resin was filtered and removed, and rinsed with 1.5 liters of water. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain A-4.

<Synthesis Example 5: Synthesis of Polymer A-5> 29.08 g of trimellitic anhydride was placed in a separate flask, 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone were added, and the mixture was stirred at room temperature, and 24.66 g of pyridine was added while stirring. A reaction mixture was obtained. After the end of the heat generation based on the reaction, it was naturally cooled to room temperature and left at room temperature for 16 hours. Next, a solution obtained by dissolving 62.46 g of dicyclohexylcarbodiimide (DCC) in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice-cooling. For 60 minutes, what was prepared by suspending 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of γ-butyrolactone was added. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added, followed by stirring for 1 hour, and then, 136.83 g of γ-butyrolactone was added. The reaction liquid was obtained by removing the precipitate which generate|occur|produced in the reaction mixture by filtration. The obtained reaction liquid was added to 716.21 g of ethanol, and a precipitate consisting of a crude polymer was formed. The produced crude polymer was filtered off, and was dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum-dried to obtain a powdery polymer (polyamide imide precursor) A -5.

<Synthesis Example 6: Synthesis of Polymer A-6> Polymer A-6 was synthesized by the same method as in Synthesis Example 1, except that ODPA 23.48 g and BPDA 22.27 g were changed to BPDA 44.54 g.

<Synthesis Example 7: Synthesis of Polymer A-7> Except that ODPA 23.48 g and BPDA 22.27 g were changed to ODPA 46.96 g, and HEMA 39.69 g was changed to 52.52 g of the compound represented by the following formula (7-1) Other than that, by the same method as in Synthesis Example 1, polymer A-7 was synthesized. [Chemical formula 87]

<Synthesis Example 8: Synthesis of Polymer A-8> 44.42g of 4,4'-(hexafluoroisopropyl)diphthalic anhydride and 20.02g of 4,4'-diaminodiphenyl ether were put into a separate flask, and 322.20g of γ-butyrolactone was added , and stirred at 130 °C for 6 hours. The obtained reaction was added dropwise to 2706.48 g of methanol to precipitate a polymer, and the obtained precipitate was filtered out, followed by vacuum drying to obtain a powdery polymer A-8.

<Synthesis Example 9: Synthesis of Polymer A-9> 29.51 g of 4,4'-oxybis(benzyl chloride) was placed in a separate flask, 220.47 g of γ-butyrolactone was added, and the mixture was stirred at -5°C. After adding 17.40 g of pyridines to this, a mixed solution of 36.63 g of 2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 110.23 g of γ-butyrolactone was added dropwise. After the dropwise addition, the mixture was stirred at -5°C for 1 hour, then heated to room temperature and stirred for 2 hours. Then, the reaction liquid was stirred at 130 degreeC for 6 hours. The obtained reaction was added dropwise to 2899.68 g of methanol to precipitate a polymer, and the obtained precipitate was filtered out, followed by vacuum drying to obtain a powdery polymer A-9.

<Synthesis Example 10: Synthesis of Polymer A-10> 4-(2-(1,3-dioxo-1,3-dihydroisobenzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl ) 41.82g of benzenecarboxylic acid and 20.02g of 4,4'- diaminodiphenyl ether were put into a separable flask, 310.30g of γ-butyrolactone was added, and the mixture was stirred at 130° C. for 6 hours. The obtained reaction was added dropwise to 2604.98 g of methanol to precipitate a polymer, and the obtained precipitate was filtered out, followed by vacuum drying to obtain a powdery polymer A-10.

<Examples and Comparative Examples> In each Example, each curable resin composition was obtained by mixing the components described in the following table, respectively. In addition, in each comparative example, each composition for comparison was obtained by mixing the components described in the following table, respectively. Specifically, let the content of each component described in Tables 1 to 7 be the amounts (parts by mass) described in parentheses in each column of Tables 1 to 7. However, content of a specific compound is made into the quantity (mass part) described in the column of "content (mass part)" of "specific compound". In addition, the description in the column of "mmol" of "organometallic complex" and "specific compound" in the table indicates the molar part (mmol part) of each compound. The description in the column of "amount (mol %) with respect to organometallic complex" of "specific compound" in the table indicates the ratio of the molar content of the specific compound to the molar content of the organometallic complex. (%). The obtained curable resin composition and the composition for comparison were subjected to pressure filtration using a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in Tables 1 to 5, the description of "-" means that the composition does not contain the component.

[Table 1] resin sensitizer Organometallic complexes cross-linking agent Polymerization inhibitors, etc. additive Metal Adhesion Improver specific compound solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity elongation at break drug resistance Type (parts by mass) mmol type Content (mass parts) mmol Relative to the amount of organometallic complex (mol%) Example 1 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.01 0.07 4 NMP (45.1) EL (11.3) M 405 burden C A A B 2 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.08 0.59 32 NMP (45.1) EL (11.3) M 405 burden B A A B 3 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.25 1.85 99 NMP (45.1) EL (11.3) M 405 burden A A A B 4 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.50 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 5 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 1.00 7.40 396 NMP (45.1) EL (11.3) M 405 burden A A A B 6 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 1.25 9.25 494 NMP (45.1) EL (11.3) M 405 burden A A A B 7 A-1 C35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 5.00 37.00 1978 NMP (45.1) EL (11.3) M 405 burden B A B B 8 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 10.00 74.00 3955 NMP (45.1) EL (11.3) M 405 burden C A B B 9 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-2 0.5 3.67 196 NMP (45.1) EL (11.3) M 405 burden A A A B 10 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-3 0.5 3.06 164 NMP (45.1) EL (11.3) M 405 burden A A A B 11 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-4 0.5 4.50 241 NMP (45.1) EL (11.3) M 405 burden A A A B 12 A-1 (135) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 0.5 3.52 188 NMP (45.1) EL (11.3) M 405 burden A A A B 13 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-6 0.5 3.07 164 NMP (45.1) EL (11.3) M 405 burden B A A A 14 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-7 0.5 4.34 232 NMP (45.1) EL (11.3) M 405 burden B A A A 15 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-8 0.5 5.61 300 NMP (45.1) EL (11.3) M 405 burden A A A B 16 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-9 0.5 6.66 356 NMP (45.1) EL (11.3) M 405 burden A A A B 17 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-10 0.5 5.74 307 NMP (45.1) EL (11.3) M 405 burden A A A B 18 A-1 (35) B-1 (1.4) - X-2 (1.0) 3.62 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 102 NMP (45.1) EL (11.3) M 405 burden B B A B 19 A-1 (35) B-1 (1.4) - X-3 (1.0) 2.47 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 150 NMP (45.1) EL (11.3) M 405 burden A A A B

[Table 2] resin sensitizer Organometallic complexes cross-linking agent Polymerization inhibitors, etc. additive Metal Adhesion Improver specific compound solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity elongation at break drug resistance Type (parts by mass) mmol type Content (mass parts) mmol Relative to the amount of organometallic complex (mol%) Example 20 A-1 (35) B-1 (1.4) - X-4 (1.0) 3.52 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 105 NMP (45.1) EL (11.3) M 405 burden B B A B twenty one A-1 (35) B-1 (1.4) - X-5 (1.0) 2.75 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 135 NMP (45.1) EL (11.3) M 405 burden B B A B twenty two A-1 (35) B-1 (1.4) - X-6 (1.0) 4.80 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 77 NMP (45.1) EL (11.3) M 405 burden A A A B twenty three A-1 (35) B-1 (1.4) - X-7 (1.0) 3.98 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 93 NMP (45.1) EL (11.3) M 405 burden A A A B twenty four A-1 (35) B-1 (1.4) X-8 (1.0) 2.95 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) F-1 (0.7) G-1 0.5 3.70 125 NMP (45.1) EL (11.3) M 405 burden A A A B 25 A-2 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 26 A-3 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 27 A-4 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 28 A-5 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 29 A-6 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 30 A-8 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 31 A-9 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 32 A-10 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 33 A-1 (35) B-2 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 34 A-1 (35} B-3 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 35 A-1 (35) B-1 (0.7) B-2 (0.7) X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 36 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-2 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 37 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 38 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B

[table 3] resin sensitizer Organometallic complexes cross-linking agent Polymerization inhibitors, etc. additive Metal Adhesion Improver specific compound solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity elongation at break drug resistance Type (parts by mass) mmol type Content (mass parts) mmol Relative to the amount of organometallic complex (mol%) Example 39 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 40 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 41 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 42 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) - - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 43 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) - E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 44 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-2 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 45 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-3 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 46 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-4 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 47 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-5 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 48 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-6 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 49 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 DMSO (11.3) γBL (45.1) M 405 burden A A A B 50 A-1 (50) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 51 A-1 (35) B-1 (3.0) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 52 A-1 (35) B-1 (1.4) - X-1 (2.0) 3.74 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 99 NMP (45.1) EL (11.3) M 405 burden A A A B 53 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (6.8) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 54 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.4) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 55 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (4.8) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 56 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (1.8) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 57 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (2.0) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B

[Table 4] resin sensitizer Organometallic complexes cross-linking agent Polymerization inhibitors, etc. additive Metal Adhesion Improver specific compound solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity elongation at break drug resistance Type (parts by mass) mmol type Content (mass parts) mmol Relative to the amount of organometallic complex (mol%) Example 58 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (11.3) EL (45.1) M 405 burden A A A B 59 A-1 (35) - - X-1 (2.4) 4.49 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 82 NMP (45.1) EL (11.3) M 405 burden A A A B 60 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) D 405 burden A A A B 61 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) D 405 burden A A A B 62 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.25 1.85 99 NMP (45.1) EL (11.3) M 405 burden A A A B G-2 0.25 1.84 98 63 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.25 1.85 99 NMP (45.1) EL (11.3) M 405 burden A A A A G-6 0.25 1.53 82 G-7 0.25 2.17 116 64 A-1 (35) B-1 (1.4) - X-1/X-2 (1.0/1.0) 5.49 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 67 NMP (45.1) EL (11.3) M 405 burden A A A B 65 A-2/A-6 (18/18) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL 11.31 M 405 burden A A A B 66 A-2 (35) B-2 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) G-1 0.5 3.70 198 DMSO (11.3) γBL (45.1) M 405 burden A A A B 67 A-7 (35) - - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-4 (2.4) E-5 (0.5) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 just B B A B 68 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-2 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 69 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-3 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 70 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-4 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 71 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 72 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-6 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden B A A A 73 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-7 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden B A A A 74 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-8 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 75 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-9 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B

[table 5] resin sensitizer Organometallic complexes cross-linking agent Polymerization inhibitors, etc. additive Metal Adhesion Improver specific compound solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity elongation at break drug resistance Type (parts by mass) mmol type Content (mass parts) mmol Relative to the amount of organometallic complex (mol%) Example 76 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-10 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 77 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-7 (0.1) F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 78 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-8 (0.1) F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 79 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-9 (0.1) F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 80 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-10 (0.1) F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A B 81 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 365 burden A A A B 82 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 365 burden A A A B 83 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 365 burden A A A B 84 A-7 (35) - - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-4 (2.4) E-5 (0.5) - F-1 (0.7) G-1 0.5 3.70 198 NMP (45.1) EL (11.3) M 365 just A A A B 85 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-7 (0.1) F-1 (0.7) G-6 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A 86 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-8 (0.1) F-1 (0.7) G-6 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A 87 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-9 (0.1) F-1 (0.7) G-6 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A 88 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-10 (0.1) F-1 (0.7) G-6 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A 89 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-7 (0.1) F-1 (0.7) G-7 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A 90 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-8 (0.1) F-1 (0.7) G-7 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A 91 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-9 (0.1) F-1 (0.7) G-7 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A 92 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-10 (0.1) F-1 (0.7) G-7 0.5 3.70 198 NMP (45.1) EL (11.3) M 405 burden A A A A Comparative example 1 A-1 (35) B-1 (1.4) - X-1 (1.0) 1.87 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) - - - - NMP (45.1) EL (11.3) M 405 burden D B C B 2 A-1 (35) B-1 (1.4) - - 0 C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 0.5 3.70 - NMP (45.1) EL (11.3) M 405 burden E C A C

The details of each component described in Tables 1 to 5 are as follows.

[resin] • A-1 to A-10: Polymers A-1 to A-10 obtained by the above synthesis example

[Photosensitive agent (photo-radical polymerization initiator)] • B-1 to B-3: compounds of the following structures [Chemical formula 88]

上述X-1及X-3為具有光自由基聚合起始能之化合物。[Organometallic complex] •X-1: bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)benzene base) titanium • X-2: pentamethylcyclopentadienyl trimethylol titanium • X-3: bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorobenzene) Base) Titanium • X-4: Tetraisopropoxytitanium (manufactured by Matsumoto Fine Chemical Co. Ltd.) • X-5: Diisopropoxybis(acetylacetone) titanium (manufactured by Matsumoto Fine Chemical Co. Ltd. ) •X-6 to X-8: Compounds of the following structures. [Chemical formula 89]

The above-mentioned X-1 and X-3 are compounds having photoradical polymerization initiation energy.

[Crosslinking agent (radical crosslinking agent)] • C-1 to C-2: compounds of the following structures [Chemical formula 90]

[Polymerization inhibitors, etc.] • D-1 to D-7: Compounds D-1 of the following structures correspond to the above-mentioned migration inhibitors. D-2 to D-7 are compounds corresponding to the above-mentioned polymerization inhibitors. [Chemical formula 91]

[Additives] • E-1 to E-10: Compounds of the following structures [Chemical formula 92]

上述結構式中，Me表示甲基，Et表示乙基。<Metal Adhesion Improver> •F-1 to F-6: Compounds of the following structures [Chemical formula 93]

In the above structural formula, Me represents a methyl group, and Et represents an ethyl group.

[Specific Compounds] • G-1 to G-10: Compounds of the following structures [Chemical formula 94]

[Solvent (solvent)] • NMP: N-methyl-2-pyrrolidone • EL: ethyl lactate • DMSO: dimethyl sulfoxide

＜Evaluation＞ [Resolution evaluation] In each Example or Comparative Example, the prepared curable resin composition or the composition for comparison was coated on a silicon wafer by spin coating. The above-mentioned silicon wafer was dried on a hot plate at 100° C. for 5 minutes, and a curable resin composition layer with a uniform thickness of 20 μm was formed on the silicon wafer. In the example described as "M" in the exposure conditions, the curable resin composition layer on the silicon wafer was exposed using a stepper. Exposure was performed using the light of the wavelength described in "Exposure wavelength nm" in the table|surface, using the mask of the fuse box of 1 micrometer scale from 5 micrometers to 25 micrometers. The exposure amount is set to the minimum line width described later as the minimum exposure amount. In the example described as "D" in the exposure conditions, exposure was performed using a direct exposure apparatus (AdTech DE-6UH III). Regarding exposure, laser direct imaging exposure was performed at a wavelength of 405 nm so that the exposed portion became a line portion in a line and space pattern of 1 μm scale from 5 μm to 25 μm. The exposure amount is set to the minimum line width described later as the minimum exposure amount. The exposed curable resin composition layer was developed with cyclopentanone for 60 seconds, and then rinsed with PGMEA (propylene glycol monomethyl ether acetate). Among the patterns obtained after development, the line width of the line pattern with the smallest line width among the line patterns exposed on the silicon wafer between the line patterns was used as the "minimum line width", and the evaluation was performed according to the following evaluation criteria. It can be said that the smaller the line width, the better the resolution. For example, it means that the width of the metal wiring to be formed in the subsequent plating process can be made finer, which is a better result. The limit of determination is 5 μm. The evaluation result is described in the column of "resolution" in the table. -evaluation standard- A: The minimum line width is 5 μm or more and less than 8 μm. B: The minimum line width is 8 μm or more and less than 10 μm. C: The minimum line width is 10 μm or more and less than 12 μm. D: The minimum line width is 12 μm or more and less than 15 μm. E: The minimum line width is 15 μm or more.

[Exposure Sensitivity Evaluation] A curable resin composition layer having a uniform thickness of 20 μm was formed on a silicon wafer by the same method as the above-mentioned resolution evaluation. In the example described as “M” in the exposure conditions, a stepper was used to use a mask portion having a diameter of 15.0 μm (the example described as “negative” in the column of the development conditions in the table) or a non-mask portion (The example described as "positive" in the column of developing conditions in the table) exposed the curable resin composition layer on the silicon wafer. The exposure wavelength is described in "Exposure wavelength nm" in the table. The exposure amount is in the range of 50 to 500 mJ/cm ² and is changed in 50 mJ/cm ² increments. In the example described as "D" in the exposure conditions, laser direct imaging exposure was performed using a direct exposure apparatus (AdTech DE-6UH III). The exposure wavelength was set to 405 nm, and exposure was performed so as to form a non-exposed portion having a diameter of 15.0 μm. The exposure amount is in the range of 50 to 500 mJ/cm ² and is changed in 50 mJ/cm ² increments. The sensitivity was evaluated according to the following evaluation criteria according to the minimum exposure amount for forming a hole pattern with a lower bottom diameter of 15.0 μm. It can be said that the smaller the above-mentioned minimum exposure amount (the higher the sensitivity), the better, and the exposure sensitivity is excellent. The evaluation result is described in the column of "sensitivity" in the table. -Evaluation Criteria- A: The above-mentioned minimum exposure amount is less than 100 mJ/cm ² . B: The above-mentioned minimum exposure amount is 100 mJ/cm ² or more and less than 150 mJ/cm ² . C: The above-mentioned minimum exposure amount is 150 mJ/cm ² or more.

[Evaluation of Elongation at Break] The curable resin composition or the composition for comparison prepared in each Example and each Comparative Example was applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer on which the obtained resin layer was formed was dried on a hot plate at 100° C. for 5 minutes to obtain a curable resin composition layer with a uniform thickness of about 15 μm on the silicon wafer. In the example described as "negative" in the column of the developing conditions in the table, the entire surface of the curable resin composition layer on the silicon wafer was exposed with exposure energy of 500 mJ/cm ² . The exposure wavelength is described in "Exposure wavelength nm" in the table. In the example described as "positive" in the column of developing conditions in the table, exposure was not performed. The curable resin composition layer after the exposure was heated at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., it was maintained at 230° C. for 3 hours. The cured curable resin composition layer (cured film) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched with a punch, and a test piece having a sample width of 3 mm and a sample length of 30 mm was produced. Using a tensile tester (Tensilon), the elongation in the longitudinal direction of the obtained test piece was measured in accordance with JIS-K6251 in an environment of a crosshead speed of 300 mm/min, 25°C, and 65% RH (relative humidity). Determination. The measurement was performed five times each, and the arithmetic mean value of the elongation at break (elongation at break) of the test piece in the five measurements was used as an index value. The evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "elongation at break" in the table. It can be said that the larger the index value is, the more excellent the film strength of the cured film is. -Evaluation Criteria- A: The above-mentioned index value is 60% or more. B: The above-mentioned index value is 55% or more and less than 60%. C: The above index value is less than 55%.

[Evaluation of chemical resistance] -Calculation of dissolution rate- In each Example or Comparative Example, the curable resin composition layer was formed on the silicon wafer by the same method as the formation of the curable resin composition layer in the above-mentioned resolution evaluation. After that, in each Example or Comparative Example, for the example described as "M" in the column of "Exposure Condition", the entire surface of the curable resin composition layer was exposed without using a mask. In the example described as "D" in the column of "Condition", except that the entire surface of the curable resin composition layer was exposed by laser, it was carried out by the same method as the exposure method in the evaluation of the above-mentioned pattern formability. Exposure was performed to obtain a resin film. Next, the resin film obtained in each Example or Comparative Example was heated at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained for 3 hours to form a cured film. The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Drug: A 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and a 25 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) Evaluation conditions: The said cured film was immersed in the said chemical|medical agent at 75 degreeC for 15 minutes, the film thickness of the cured film before and after immersion was compared, and the dissolution rate (nm/min) was calculated. The obtained value of the dissolution rate was evaluated according to the following evaluation criteria, and described in the column of "chemical resistance". It can be said that the lower the dissolution rate, the better the chemical resistance. -evaluation standard- A: The dissolution rate is less than 250 nm/min. B: The dissolution rate is 250 nm/min or more and less than 500 nm/min. C: The dissolution rate is 500 nm/min or more.

From the above results, it can be seen that the curable resin composition of the present invention is excellent in resolution. The composition for comparison of Comparative Example 1 did not contain the specific compound. In addition, the composition for comparison of Comparative Example 2 did not contain an organometallic complex. It turned out that when these compositions for comparison were used, the resolution was inferior.

<Example 101> The curable resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate with the copper thin layer formed on the surface in a layer form by spin coating, and dried at 100°C for 4 days. After forming a photosensitive film with a film thickness of 20 μm in minutes, exposure was performed using a stepper (Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a 1:1 line-to-space pattern and a line width of 10 μm). After exposure, it heated at 100 degreeC for 4 minutes. After the above heating, the layer pattern was obtained by developing with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds. Next, the temperature was increased at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 120 minutes, thereby forming an interlayer insulating film for a rewiring layer. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, and as a result, it was confirmed that there was no problem in the operation.

without.

Claims (19)

A curable resin composition comprising: At least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide precursor 1 resin; Compound B having at least one group selected from the group consisting of N-hydroxyamino, N-hydroxyimino, N-hydroxyimino, and N-hydroxyimino; and Organometallic complexes. The curable resin composition according to claim 1, further comprising a photopolymerization initiator. The curable resin composition according to claim 1 or claim 2, further comprising a crosslinking agent. The curable resin composition according to claim 1 or claim 2, wherein The aforementioned organometallic complex is a metallocene compound. The curable resin composition according to claim 1 or claim 2, wherein The aforementioned organometallic complex is a titanium compound. The curable resin composition according to claim 1 or claim 2, wherein The aforementioned organometallic complex has photoradical polymerization initiation energy. The curable resin composition according to claim 1 or claim 2, wherein The aforementioned compound B is a compound having at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, and an N-hydroxyamide group. The curable resin composition according to claim 1 or claim 2, wherein the compound B includes a compound having an N-hydroxyimide group and a compound selected from the group consisting of compounds represented by formula (1-1). , a compound represented by formula (1-2), and at least one compound in the group of compounds represented by formula (1-3),

In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and have an optional substituent as a substituent. Carbon number 1-7 of at least one substituent selected from the group consisting of primary amine salt structure, secondary amine salt structure, tertiary amine group, tertiary amine salt structure, quaternary ammonium group and aliphatic heterocyclic group aliphatic hydrocarbon group, or an aliphatic hydrocarbon group with carbon number of 2 to 7 having at least one substituent selected from the group consisting of hydroxyl, alkoxy, thiol and alkylthio groups, R ²¹ and R ²² are respectively Each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, R ³¹ and R ³² each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and R ³³ represents an optionally substituted aliphatic hydrocarbon group. Aliphatic hydrocarbon group having 1 to 7 carbon atoms. The curable resin composition according to claim 1 or claim 2, wherein The ratio of the molar content of the compound B to the molar content of the organometallic complex is 30% to 500%. The curable resin composition according to claim 1 or claim 2, which is used for forming a photosensitive film for negative development. The curable resin composition according to claim 1 or claim 2, which is used for forming an interlayer insulating film for a rewiring layer. A cured film obtained by curing the curable resin composition according to any one of claim 1 to claim 11. A laminate comprising two or more layers of the cured film according to claim 12, and including a metal layer between any of the cured films. A method for manufacturing a hardened film, comprising: In the film forming process, the curable resin composition according to any one of Claims 1 to 11 is applied to a substrate to form a film. The method for manufacturing a cured film according to claim 14, comprising: an exposure process, which exposes the film; and a development process, which develops the film. The method for producing a cured film as claimed in claim 15, wherein The exposure light used in the aforementioned exposure includes light with a wavelength of 405 nm. The method for producing a cured film as claimed in claim 15, wherein The aforementioned exposure is based on the direct laser imaging method. The method for manufacturing a cured film as claimed in claim 14, comprising: In the heating process, the aforementioned film is heated at 50°C to 450°C. A semiconductor device comprising the cured film according to claim 12 or the laminate according to claim 13.