TW202222912A - Resin composition, cured object, layered product, method for producing cured object, and semiconductor device - Google Patents

Abstract

A resin composition that comprises a precursor of a cyclization-product resin and compound B, which generates a base by the action of a base; a cured object obtained by curing the resin composition; a layered product including the cured object; a method for producing the cured object; and a semiconductor device including the cured object or the layered product.

Description

Resin composition, cured product, laminate, method for producing cured product, and semiconductor device

The present invention relates to a resin composition, a cured product, a laminate, a method for producing the cured product, and a semiconductor element.

Cyclized resins such as polyimide 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 element for actual mounting is mentioned as an example, the use as a material of an insulating film or a sealing material, or a protective film can be mentioned. Moreover, it can also be used as a base film, a cover film, etc. of a flexible substrate.

For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of a cyclized resin such as a polyimide precursor. Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and thereafter, as necessary, exposure, development, heating, and the like are performed to form a cured product on the substrate. The precursor of the cyclized resin such as the above-mentioned polyimide precursor is cyclized by heating, for example, and becomes a cyclized resin such as polyimide in the cured product. Since the resin composition can be applied by a known coating method or the like, it can be said that it is excellent in suitability for manufacturing, for example, the applied resin composition has a high degree of freedom in designing the shape, size, and application position at the time of application. In addition to the high performance possessed by cyclized resins such as polyimide, the industrial application development of the above-mentioned resin composition is increasingly expected from the viewpoint of excellent suitability for such production.

For example, Patent Document 1 describes a sensory energy ray base generator characterized by having a specific urethane structure.

[Patent Document 1] Japanese Patent Laid-Open No. 2007-241205

In such a resin composition, both the improvement of the storage stability of the composition and the improvement of the elongation at break of the obtained cured product are required.

An object of the present invention is to provide a resin composition excellent in the storage stability of the composition and the elongation at break of the obtained cured product, a cured product obtained by curing the resin composition, a laminate comprising the cured product, The manufacturing method of the said hardened|cured material, and the semiconductor element containing the said hardened|cured material or the said laminated body.

式（1-1）中，R ¹表示氫原子或可以經取代的烴基，R ²表示可以經取代的烴基，R ¹和R ²可以鍵結而形成環結構； 式（1-2）中，R ¹表示氫原子或可以經取代的烴基，R ²表示可以經取代的烴基，R ¹和R ²可以鍵結而形成環結構，R ³分別獨立地表示氫原子或可以經取代的烴基，R ⁴表示氰基、硝基、-C（=O）OR、-OC（=O）R、-C（=O）R、-S（=O） ₂R、氟化烷基或鹵素原子，R表示可以經取代的烴基； 式（1-3）中，R ¹表示氫原子或可以經取代的烴基，R ²表示可以經取代的烴基，R ¹和R ²可以鍵結而形成環結構，R ³分別獨立地表示氫原子或可以經取代的烴基，Ar表示經選自氰基、硝基、-C（=O）OR、-OC（=O）R、-C（=O）R、-S（=O） ₂R、氟化烷基、鹵素原子中的至少1個基團取代之芳香族基，R表示可以經取代的烴基。 ＜5＞如＜1＞至＜4＞之任一項所述之樹脂組成物，其係進一步包含熱鹼產生劑或光鹼產生劑。 ＜6＞如＜1＞至＜5＞之任一項所述之樹脂組成物，其係進一步包含熱鹼產生劑。 ＜7＞如＜1＞至＜6＞之任一項所述之樹脂組成物，其係進一步包含光聚合起始劑。 ＜8＞如＜1＞至＜7＞之任一項所述之樹脂組成物，其係進一步包含聚合性化合物。 ＜9＞一種硬化物，其係將＜1＞至＜8＞之任一項所述之樹脂組成物硬化而成。 ＜10＞一種積層體，其係包括2層以上的由＜9＞所述之硬化物形成之層，並且在由上述硬化物形成之層之間的任一個之間包括金屬層。 ＜11＞一種硬化物之製造方法，其係包括將＜1＞至＜8＞之任一項所述之樹脂組成物適用於基材上而形成膜之膜形成步驟。 ＜12＞如＜11＞所述之硬化物之製造方法，其係包括選擇性地曝光上述膜之曝光步驟及使用顯影液對上述膜進行顯影而形成圖案之顯影步驟。 ＜13＞如＜11＞或＜12＞所述之硬化物之製造方法，其係包括在50～450℃下對上述膜進行加熱之加熱步驟。 ＜14＞一種半導體元件，其係包含＜9＞所述之硬化物或＜10＞所述之積層體。 [發明效果] Examples of typical embodiments of the present invention are shown below. <1> A resin composition comprising a precursor of a cyclized resin and a compound B which generates a base by the action of a base. <2> The resin composition according to <1>, wherein the base generated from the compound B is an amine. <3> The resin composition according to <1> or <2>, wherein the compound B has an urethane bond. <4> The resin composition according to any one of <1> to <3>, wherein the compound B is represented by the following formula (1-1), formula (1-2) or formula (1-3) represented compound. [Chemical formula 1]

In formula (1-1), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, and R ¹ and R ² can be bonded to form a ring structure; In formula (1-2), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, R ¹ and R ² can be bonded to form a ring structure, R ³ each independently represents a hydrogen atom or a hydrocarbon group that can be substituted, R ⁴ represents cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) ₂ R, fluorinated alkyl group or halogen atom, R Represents a hydrocarbon group that can be substituted; in formula (1-3), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, R ¹ and R ² can be bonded to form a ring structure, R ³ respectively independently represent a hydrogen atom or a hydrocarbon group that can be substituted, Ar represents a cyano group, a nitro group, -C(=O)OR, -OC(=O)R, -C(=O)R, - S(=O) ₂ R, a fluorinated alkyl group, an aromatic group substituted with at least one of a halogen atom, and R represents an optionally substituted hydrocarbon group. <5> The resin composition according to any one of <1> to <4>, which further contains a thermal base generator or a photobase generator. <6> The resin composition according to any one of <1> to <5>, which further contains a thermal alkali generator. <7> The resin composition according to any one of <1> to <6>, which further contains a photopolymerization initiator. <8> The resin composition according to any one of <1> to <7>, which further contains a polymerizable compound. <9> A cured product obtained by curing the resin composition according to any one of <1> to <8>. <10> A layered body comprising two or more layers formed of the cured product described in <9>, and including a metal layer between any of the layers formed of the cured product. <11> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <8> on a substrate to form a film. <12> The manufacturing method of the hardened|cured material as described in <11> which comprises the exposure process of selectively exposing the said film, and the development process of developing the said film using a developing solution, and forming a pattern. <13> The manufacturing method of the hardened|cured material as described in <11> or <12> which comprises the heating process of heating the said film at 50-450 degreeC. <14> A semiconductor element comprising the cured product described in <9> or the laminated body described in <10>. [Inventive effect]

According to the present invention, there are provided a resin composition excellent in the storage stability of the composition and the elongation at break of the obtained cured product, a cured product obtained by curing the above resin composition, a laminate comprising the above cured product, and the above cured product A manufacturing method of the product, and a semiconductor element including the above-mentioned cured product or the above-mentioned laminated body.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range shown by "-" symbol shows the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively. In this specification, the term "step" not only refers to an independent step, but also refers to a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. With regard to the labels of groups (atomic groups) in this specification, the labels of unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) and substituted groups (atomic groups). 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 with light but also exposure with particle beams such as electron beams, ion beams, and the like. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, far ultraviolet rays represented 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 acid" means "acrylic acid" and "methacrylic acid" "Both or either, "(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 the present specification, the total solid content refers to the total mass of the components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage with respect to the total mass of a composition of other components except a solvent. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. 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 combining guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) were connected in series and used as a column to obtain the determination. Unless otherwise stated, the molecular weights are determined using THF (tetrahydrofuran) as the eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent such as when the solubility is low. In addition, unless otherwise specified, the detection in the GPC measurement was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). In this specification, when the positional relationship of each layer constituting the layered product is described as "upper" or "lower", other layers may be present on the upper side or lower side of the reference layer among the plurality of layers concerned. That is, a third layer or element may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference and the other layers described above do not need to be in contact. Also, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the base material is referred to as "up", or, in the case of a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "up" , and the opposite direction is called "down". Furthermore, the setting of the up-down direction is for the convenience of explaining this specification, and in an actual aspect, the "up" direction in this specification can also be different from the vertical upward direction. In this specification, unless otherwise stated, as each component contained in a composition, a composition may contain 2 or more types of compounds corresponding to this component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 air pressure), and the relative humidity is 50% RH. In this specification, the combination of the preferred aspects is the more preferred aspect.

(resin composition) The resin composition of the present invention includes a precursor of a cyclized resin (hereinafter, also referred to as "specific resin") and a compound B (hereinafter, also simply referred to as "compound B") which generates a base by the action of a base.

The 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 resin composition of this invention is used for forming the photosensitive film for negative development. In the present invention, negative-type development refers to development in which a non-exposed portion is removed by development during exposure and development, and positive-type development refers to development in which an exposed portion is removed by development. As the above-mentioned exposure method, the above-mentioned developer solution, and the above-mentioned development method, the exposure method described in the exposure step in the description of the manufacturing method of the cured product described later, the developer solution and the development method described in the development step are used, for example.

In the resin composition of the present invention, the storage stability of the composition and the elongation at break of the obtained cured product are excellent. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it is presumed as follows.

From the past, resin compositions comprising precursors of cyclized resins and thermal base generators have been studied. In a precursor of a cyclized resin such as a polyimide precursor, a cyclization reaction such as imidization proceeds by the action of a base. Taking advantage of this property, a film containing a resin composition having a cyclized resin precursor and an alkali generator is formed, followed by a high-temperature heat treatment, etc., whereby a cured product containing a cyclized resin having high heat resistance and high mechanical properties can be obtained . On the other hand, when such a composition is stored, it is found that a small amount of basic compound is generated in the composition liquid, and the cyclization reaction of the precursor of the cyclized resin may proceed in the composition. As a result, the solvent solubility of the precursor of the cyclized resin decreases, and problems such as precipitation of the above-mentioned resin in the composition occur. Precursors of these cyclized resins promote cyclization under basic conditions, so cyclization is sometimes suppressed by adjusting the composition to be acidic. However, when a large amount of alkali is generated during storage, even when the composition is prepared to be acidic, the cyclization is accelerated in the composition by the action of the alkali, so the composition may only be adjusted to be acidic. It is difficult to obtain the stability during storage (also referred to as the storage stability of the composition). In this invention, by using the compound B which produces|generates an alkali by the action of an alkali, the storage stability of a resin composition and the mechanical properties (elongation at break) of the obtained cured film can be made compatible at a high level. In the resin composition, the compound B has high stability and is unlikely to generate an alkali during storage, and therefore has high storage stability. On the other hand, when curing by heat treatment or the like, it is considered that the compound B is rapidly generated by the action of a base generated by thermal decomposition of a part of the compound B itself or a base generated from a base generator added to the resin composition. Decomposes and releases a sufficient amount of base. From this, it is considered that the cyclization reaction in the precursor of the cyclized resin proceeds sufficiently, and high mechanical properties (elongation at break) can be achieved.

Among them, Patent Document 1 does not describe a resin composition containing a precursor of a cyclized resin and compound B.

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

＜Specific resin＞ The resin composition of the present invention contains a precursor (specific resin) of a cyclized resin. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain represents the relatively longest bonding chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyimide, and the like. The precursor of the cyclized resin refers to the resin that changes its chemical structure due to external stimuli and becomes the cyclized resin. More preferably, a resin that forms a ring structure to become a cyclized resin. As a precursor of a cyclized resin, a polyimide precursor, a polybenzoxazole precursor, a polyimide imide precursor, etc. are mentioned. That is, the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor. Specific resins are preferred. The resin composition of the present invention preferably contains a polyimide precursor as the specific resin. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. When the specific resin has a radically polymerizable group, it is preferable that the resin composition of the present invention contains a radical polymerization initiator described later, and it is more preferable that it includes a radical polymerization initiator described later and a radical crosslinking agent described later. . Furthermore, the sensitizer mentioned later can be contained as needed. For example, a negative photosensitive film is formed from the resin composition of the present invention. 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 the resin composition of this invention contains the photoacid generator mentioned later. From the resin composition of the present invention, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed.

式（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價的有機基，R ¹¹⁵表示4價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基。 [Polyimide Precursor] The type and the like of the polyimide precursor used in the present invention are 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. Examples of the divalent organic group include linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, including linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The above-mentioned linear or branched aliphatic group may be substituted with a group in which the hydrocarbon group in the chain contains a heteroatom, and the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a group in which a ring-membered hydrocarbon group contains a heteroatom. As a preferable embodiment of this invention, the group represented by -Ar- and -Ar-L-Ar- can be illustrated, and the group represented by -Ar-L-Ar- is especially preferable. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms including a single bond and may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably 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, the group includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. The diamine is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The above-mentioned linear or branched aliphatic group may be substituted with a group in which the hydrocarbon group in the chain contains a heteroatom, and the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a group in which a ring-membered hydrocarbon group contains a heteroatom. As an example of the group containing an aromatic group, the following are mentioned.

式中，A表示單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO ₂-、-NHCO-或該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-中之基團為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） 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 represents a single bond or a divalent linking group, and is selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -C(=O)-, and -S- which may be substituted by a fluorine atom. , -SO ₂ -, -NHCO- or groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C (= The group in O)-, -S- or -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C ( CH ₃ ) ₂ - is further preferred. In the formula, * represents a bonding site with other structures.

Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4- Bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-di Methylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenylene and 3,3-diaminodiphenylene, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4 ,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 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-amine) phenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane 3-amino-4-hydroxyphenyl) bismuth, bis(4-amino-3-hydroxyphenyl) bismuth, 4,4'-diamino-terphenyl, 4,4'-bis(4-amine bis[4-(4-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(2 -Aminophenoxy)phenyl] bismuth, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene -Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamine diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 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 ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diamine Amino biphenyl, 9,9'-bis(4-amino) Phenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Phenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octa Methylpentasiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, bis Ester of aminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminobenzene) base) 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-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4- (4-Aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoropropane) Methyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) diphenyl bismuth, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl bismuth, 2,2-bis[4-(4-amino-3- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2 At least 1 of ,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl a diamine.

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

Moreover, the diamine which has two or more alkylene glycol units described in the paragraphs 0032 to 0034 of International Publication No. 2017/038598 in the main chain 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 combination of two or more of the above. Preferably, Ar is 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，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價的有機基，R ⁵⁰～R ⁵⁷中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R ⁵⁰～R ⁵⁷的1價的有機基，可以舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式5]

式（61）中，R ⁵⁸及R ⁵⁹分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為提供式（51）或式（61）的結構之二胺，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1種或組合使用2種以上。 In addition, from the viewpoint of i-ray transmittance, it is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61). 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, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents the bonding site to the nitrogen atom in the formula (2). Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 to 6), an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1-6) fluorinated alkyl groups, etc. [Chemical formula 5]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in the formula (2). As the diamine providing the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine can be mentioned Amino biphenyl, 2,2'-bis(fluoro)-4,4'-diamino biphenyl, 4,4'-diamino octafluorobiphenyl, etc. These can be used alone or in combination of two or more.

式（5）中，R ¹¹²為單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-以及該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-CO-、-S-及-SO ₂-中之基團為更佳，選自包括-CH ₂-、-C（CF ₃） ₂-、-C（CH ₃） ₂-、-O-、-CO-、-S-及-SO ₂-之群組中的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 6]

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

式（O）中，R ¹¹⁵表示4價的有機基。R ¹¹⁵的較佳範圍與式（2）中之R ¹¹⁵的含義相同，較佳範圍亦相同。 Specific examples of R ¹¹⁵ include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride. As a structure corresponding to R ¹¹⁵ , the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 7]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred 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-phenanthrene tetracarboxylic dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

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

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ can also have an OH group. More specifically, as R ¹¹¹ , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkoxy group. Moreover, 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. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. As the polymerizable group, a group capable of performing a crosslinking reaction by the action of heat, radicals, etc., is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoxyl group. azole group, blocked isocyanate group, amine group. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, 2-methallyl group, and a group having an aromatic ring directly bonded to the vinyl group (for example, vinylphenyl, etc.), (meth)acrylamido, (meth)acryloyloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.

[Chemical formula 8]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. 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 -, a cycloalkylene group or a polyalkeneoxy group. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecane and other alkylenes. base, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH) CH ₂ -, polyalkyleneoxy, ethylidene, propylidene and other alkylene groups, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, and polyalkeneoxy groups are more preferred, and alkylene groups such as ethylidene and propylidene groups or polyalkeneoxy groups are further preferred. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkeneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. In the case where 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 a block arrangement, Arrangements with alternating patterns are also possible. The number of carbon atoms in the alkylene group (in the case where the alkylene group has a substituent, the number of carbon atoms in the substituent group) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is the most preferable. 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. Moreover, it is preferable that the number of alkeneoxy groups (the number of repetitions of polyalkeneoxy groups) contained in the polyalkeneoxy group is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoints of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyvinyloxy group, polypropeneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of A group obtained by bonding two propeneoxy groups is preferred, polyvinyloxy or polypropeneoxy is more preferred, and polyvinyloxy is further preferred. In the above-mentioned groups obtained by bonding a plurality of vinyloxy groups and a plurality of propeneoxy groups, the vinyloxy groups and the propeneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged alternately, etc. patterned. Several preferred aspects such as vinyloxy in these groups are repeated as described above.

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.

In formula (2), 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 by 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 A group, a tertiary alkyl ester group, etc. are preferable, and an acetal group or a ketal 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 structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

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

式（2-A）中，A ¹及A ²表示氧原子，R ¹¹¹及R ¹¹²分別獨立地表示2價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基，R ¹¹³及R ¹¹⁴中的至少一者為包含聚合性基之基團，兩者為包含聚合性基之基團為較佳。 Preferably, the repeating unit represented by the formula (2) is the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 9]

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, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both are preferably a group containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same. R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by 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, it goes without saying that the polyimide precursor may contain other types of repeating 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 total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. Moreover, as for the number average molecular weight (Mn), 2,000-40,000 are preferable, 3,000-30,000 are more preferable, 4,000-20,000 are still more preferable. The dispersity of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the dispersion degree of molecular weight is a value calculated by weight average molecular weight/number average molecular weight. Furthermore, when the resin composition includes a plurality of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersity of at least one polyimide precursor are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polyimide precursors as one resin are respectively within the above-mentioned ranges.

式（3）中，R ¹²¹表示2價的有機基，R ¹²²表示4價的有機基，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價的有機基。 [Polybenzoxazole Precursor] The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (3). [Chemical formula 10]

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 have the same meanings as R ¹¹³ in formula (2), respectively, 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, including a linear or branched (preferably linear) aliphatic group and 2 -COOH dicarboxylic acids are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, more preferably 3 to 20, and even more 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. acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexanoic acid Fluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3- Methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoroic acid Suberic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid , hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tridecanedioic acid acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacosanedioic acid, Tridecanedioic acid, tridecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, and the like.

（式中，Z為碳數1～6的烴基，n為1～6的整數。） [Chemical formula 11]

(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 acid having an aromatic group is preferred, and the following dicarboxylic acid including only a group having an aromatic group and two -COOH is more preferred.

式中，A表示選自包括-CH ₂-、-O-、-S-、-SO ₂-、-CO-、-NHCO-、-C（CF ₃） ₂-及-C（CH ₃） ₂-之群組中的2價的基團，*分別獨立地表示與其他結構的鍵結部位。 [Chemical formula 12]

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 For 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 phthalic 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 preferred 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'-diaminophenol Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-diamine bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane 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，X ₁表示-O-、-S-、-C（CF ₃） ₂-、-CH ₂-、-SO ₂-、-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，R ¹²²為上述式所表示之結構亦較佳。在R ¹²²為上述式所表示之結構之情況下，在共計4個*及#中，任意2個為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且其他2個為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位，或者2個*為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位為進一步較佳。 [Chemical formula 13]

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. Moreover, it is also preferable that R ¹²² is a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, among the total of 4 * and #, any two are the bonding site to the nitrogen atom to which R ¹²² in the formula (3) is bonded, and the other two are Preferably, it is the bonding site of the oxygen atom bonded to R ¹²² in the formula (3), and two * are the bonding sites of the oxygen atom bonded to R ¹²² in the formula (3) and two # is the bonding site to the nitrogen atom bonded to R ¹²² in the formula (3), or two * are the bonding sites to the nitrogen atom bonded to R ¹²² in the formula (3) and two # More preferably, it is the bonding site of the oxygen atom bonded to R ¹²² in the formula (3), and 2 * are the bonding sites of the oxygen atom bonded to R ¹²² in the formula (3), and 2 It is more preferable that # is the bonding site to the nitrogen atom bonded to R ¹²² in the formula (3).

It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [Chemical formula 14]

In formula (As), R ₁ is selected from hydrogen atom, alkylene group, substituted alkylene group, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond or the following formula Organic groups in the group of (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，*表示與上述式（A-s）所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [Chemical formula 15]

(In the formula (A-sc), * represents a bond with the aromatic ring of 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, also on R ₃ makes the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it becomes higher when the curing at low temperature is further improved. It is particularly preferable in terms of the effect of the cyclization rate.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, the effect of maintaining high transparency to i-rays and high cyclization rate during curing at low temperature 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 alkylene group and the substituted alkylene group for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, which can maintain high transparency to i-ray and low temperature -CH 2 -, -CH(CH 3 )-, - -CH 2 -, -CH(CH 3 )-, - -CH ₂ -, -CH(CH ₃ )-, - C(CH ₃ ) ₂ - is better.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A No. 2013-256506, and these 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 Japanese Patent Laid-Open No. 2013-256506, which are incorporated into the present specification. middle. Of course, it is not limited to these, it goes without saying.

In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also contain other types of repeating units. It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit in terms of suppressing 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，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 16]

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 formula (SL), as a preferable Z, those in which R ^5s and R ^6s in the b structure are phenyl groups can be mentioned. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure 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 formula (SL) is included as another type of repeating unit, it is also preferable to further include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in the formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more 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 dispersity 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 more preferred. The following are still further preferred. Also, in the case where the resin composition contains a plurality of polybenzoxazole precursors as the specific resin, the weight average molecular weight, number average molecular weight and dispersion degree of at least one polybenzoxazole precursor are within the above-mentioned ranges. good. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight and the degree of dispersion calculated by using the above-mentioned plural types of polybenzoxazole precursors as one resin are respectively within the above-mentioned ranges.

式（PAI-2）中，R ¹¹⁷表示3價的有機基，R ¹¹¹表示2價的有機基，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價的有機基。 [Polyamide imide precursor] The polyamide imide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [Chemical formula 17]

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 and aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by linking two or more, such as 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, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. 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.

Further, 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 carboxyl groups among 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, a branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compound etc. are 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, A tricarboxylic acid compound of an aromatic group having 6 to 20 carbon atoms, a single bond, or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a single bond is preferable. A bond or a tricarboxylic acid compound of a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group is more preferable.

In addition, specific examples of the tricarboxylic acid compound include single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - Or phenylene to connect 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, phthalate Compounds of formic acid (or, phthalic anhydride) and benzoic acid, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (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 further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [Chemical formula 18]

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 linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by linking two or more groups, such as 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, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. 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 a hydrogen atom, 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.

Further, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. 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. The carboxyl group in the dicarboxylic acid dihalide may be halogenated, for example, it is preferably chlorinated. That is, it is preferable that the dicarboxylic acid dihalide is a dicarboxylic acid dichloride compound. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that may be halogenated to be used in the production of polyamide imide precursors include linear or branched aliphatic and cyclic aliphatic Or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides, etc. Only one type of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more types may be used.

Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a A cyclic aliphatic group, an aromatic group having 6 to 20 carbon atoms, a single bond, or a dicarboxylic acid compound or a dicarboxylic acid dihalide of a group obtained by combining two or more of these groups by a linking group is relatively Preferably, a dicarboxylic acid compound or dicarboxylic acid dihalogenation containing an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group Things are better.

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'-biphenylcarboxylic acid, 4,4'- Dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of a dicarboxylic acid dihalide, the compound of the structure formed by halogenating two carboxyl groups in the specific example of the said dicarboxylic acid compound is mentioned.

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

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

Moreover, in order to improve the adhesiveness with a board|substrate, the aliphatic group which has a siloxane structure may be copolymerized with a polyamide imide precursor. Specifically, as the diamine component, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

As one embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), and the repeating unit represented by the formula (2) can be mentioned. The total content of the indicated 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 above-mentioned total content is not particularly limited, and all repeating units in the polyamide imide precursor except the terminal may be repeating units represented by formula (PAI-2), and formula (PAI-1). Any one of the repeating unit and the repeating unit represented by formula (2). Moreover, 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 mentioned In the form of 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 above-mentioned total content is not particularly limited, and all the repeating units in the polyamide imide precursor except the terminal may be the repeating units represented by the formula (PAI-2) or 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 of the polyamide imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyamide imide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Moreover, in the case where the resin composition contains a plurality of polyamide imide precursors as a specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polyamide imide precursor are within the above-mentioned ranges is better. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight and the degree of dispersion calculated by using the above-mentioned plural types of polyamide imide precursors as one resin are respectively within the above ranges.

[Method for producing polyimide precursor, etc.] The polyimide precursor and the like can be obtained, for example, by a method of reacting tetracarboxylic dianhydride and diamine at low temperature, and by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide A method of esterifying an amine acid with a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of a diamine and a condensing agent, by A method in which tetracarboxylic dianhydride and alcohol are used to obtain a diester, and the remaining dicarboxylic acid is halogenated using a halogenating agent, followed by a method of reacting it with a diamine. In the above-mentioned production method, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated using a halogenating agent and reacted with a diamine is more preferable. As the above-mentioned condensing agent, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. As said alkylating agent, N,N- dimethylformamide dimethyl acetal, N,N- dimethylformamide diethyl acetal, N,N-dialkylformamide can be mentioned Amine dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. As said halogenating agent, thionyl chloride, oxalyl chloride, phosphorus oxychloride, 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 type or two or more types. The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate. , dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately set depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N- Dimethyl-4-aminopyridine and the like.

-Capping agent- In the production method of the polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative or amine group remaining at the resin end of the polyimide precursor or the like. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the resin end, examples of the blocking agent include monohydric alcohols, phenols, thiols, thiophenols, monoamines, and the like, from the viewpoint of reactivity and film stability. , it is better to use monohydric alcohols, phenols or monoamines. Preferable compounds of monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloroethanol Primary alcohols such as methanol and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantanol alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as preferable compound of monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 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-aminowater Sylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of terminal blocking agents. Moreover, when sealing the amine group of a resin terminal, it can seal with the compound which has a functional group which can react with an amine group. The preferred sealants for amine groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., carboxylic acid anhydrides, carboxylic acid chlorides are more preferred . Preferable compounds of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic acid anhydride, etc. In addition, as a preferable compound of the carboxylic acid chloride, acetyl chloride, acryl chloride, acryl chloride, methacryloyl chloride, trimethyl acetyl chloride, cyclohexane methyl chloride, 2-ethyl chloride can be mentioned. Hexyl chloride, cinnamon chloride, 1-adamantanecarboxy chloride, heptafluorobutane chloride, stearate chloride, benzyl chloride, etc.

-Solid Precipitation- When producing a polyimide precursor or the like, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixed solution thereof to make the polymer into a It is possible to obtain a polyimide precursor or the like by precipitation as a solid by analysis and drying. In order to improve the degree of purification, operations such as redissolving, reprecipitating, and drying the polyimide precursor and the like may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.

〔content〕 The content of the specific resin in the resin 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 % with respect to the total solid content of the resin composition. The above is further preferred. Moreover, the content of the resin in the resin 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 resin composition. % or less is still more preferable, and 95 mass % or less is still more preferable. The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.

Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resin. Specifically, the 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 resin composition of the present invention contains two or more kinds of specific resins, for example, it contains 2 different from the structure (R ¹¹⁵ described in the above formula (2)) derived from dianhydride which is a polyimide precursor. More than one polyimide precursor is preferred.

<Other resins> The resin composition of the present invention may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter, also simply referred to as “other resins”). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic acid amide resins, and urethane resins , Butyral resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (hardened product) excellent in solvent resistance can be obtained. For example, in place of or in addition to the polymerizable compound described later, a polymerizable group having a weight average molecular weight of 20,000 or less with a high value of polymerizable groups (for example, the molar content of the polymerizable group in 1 g of resin is 1×10 ^-3 ) molar/g or more) (meth)acrylic resin is added to the resin composition to improve the coatability of the resin composition, the solvent resistance of the pattern (hardened product), and the like.

When the resin 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 with respect to the total solid content of the resin composition. Preferably, 2 mass % or more is still more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still further preferable. In addition, the content of other resins in the resin 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 resin composition. It is still more preferable that it is not more than 50 mass %, and it is still more preferable that it is not more than 50 mass %. Moreover, as a preferable aspect of the resin composition of this invention, the aspect in which content of another resin is a low content can also be used. 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 with respect to the total solid content of the resin composition. It is still more preferable, and 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, as long as it is 0 mass % or more. The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.

<Compound B> The resin composition of this invention contains the compound B which produces|generates a base by the action of a base. As the compound B, for example, a compound having a base protected by an alkali-decomposable group can be mentioned. The base protected by the alkali-decomposable group is not particularly limited. For example, a known amine protecting group that can be deprotected with a base, for example, a group having a carbamate structure is preferable, and examples include 9-Fluorenylmethylcarbamate, 1,1-dimethyl-2-cyanomethylcarbamate, p-nitrobenzylcarbamate, 2,4-dichlorobenzyl carbamate, etc.

Moreover, it is preferable that compound B contains an urethane bond. It is preferable that the said amine ester bond is included in the base protected by the alkali-decomposable group, and it is more preferable that the said amine ester bond is decomposed by the action of a base to generate an amine.

The base generated from compound B by the action of the base is preferably an amine, more preferably a secondary amine or a tertiary amine. In addition, the conjugate acid of the base generated from the compound B by the action of the base is preferably a base having a pKa of 0 or more, more preferably a base of 3 or more, and more preferably a base of 6 or more. The lower limit of the pKa of the conjugate acid is not particularly limited, but 30 or less is preferable. The pKa is expressed by the negative logarithm pKa of the equilibrium constant Ka taking into account the dissociation reaction releasing hydrogen ions from the acid. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD/ChemSketch (registered trademark). When there are plural pKas of the above conjugated acids, at least one is preferably within the above range.

The base generated from the compound B by the action of the base may be a base having only one base, or a base having two or more bases. In addition, the base generated from the compound B by the action of the base may be one molecule or two or more molecules.

The molecular weight of the base generated from the compound B by the action of the base is preferably 50-300, more preferably 80-250.

Specific examples of the generated base are not particularly limited, but include piperidine, 4-hydroxyethylpiperidine, 4-(3-phenylpropylpiperidine), cyclohexylamine, diisopropylamine, diisopropylamine, and Cyclohexylamine, Dimethylpiperidine, 1,3-Di-4-piperidinylpropane, 2,6-Dimethylpiperidine, Methylcyclohexylamine, 4-Hydroxymethylpiperidine, Diisobutyl Amine, isopropylcyclohexylamine, di-tertiary isobutylamine, etc.

式（1-1）中，R ¹表示氫原子或可以經取代的烴基，R ²表示可以經取代的烴基，R ¹和R ²可以鍵結而形成環結構； 式（1-2）中，R ¹表示氫原子或可以經取代的烴基，R ²表示可以經取代的烴基，R ¹和R ²可以鍵結而形成環結構，R ³分別獨立地表示氫原子或可以經取代的烴基，R ⁴表示氰基、硝基、-C（=O）OR、-OC（=O）R、-C（=O）R、-S（=O） ₂R、氟化烷基或鹵素原子，R表示可以經取代的烴基； 式（1-3）中，R ¹表示氫原子或可以經取代的烴基，R ²表示可以經取代的烴基，R ¹和R ²可以鍵結而形成環結構，R ³分別獨立地表示氫原子或可以經取代的烴基，Ar表示經選自氰基、硝基、-C（=O）OR、-OC（=O）R、-C（=O）R、-S（=O） ₂R、氟化烷基、鹵素原子中的至少1個基團取代之芳香族基，R表示可以經取代的烴基。 Compound B is preferably a compound represented by the following formula (1-1), formula (1-2) or formula (1-3), and more preferably a compound represented by the following formula (1-1). [Chemical formula 19]

In formula (1-1), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, and R ¹ and R ² can be bonded to form a ring structure; In formula (1-2), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, R ¹ and R ² can be bonded to form a ring structure, R ³ each independently represents a hydrogen atom or a hydrocarbon group that can be substituted, R ⁴ represents cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) ₂ R, fluorinated alkyl group or halogen atom, R Represents a hydrocarbon group that can be substituted; in formula (1-3), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, R ¹ and R ² can be bonded to form a ring structure, R ³ respectively independently represent a hydrogen atom or a hydrocarbon group that can be substituted, Ar represents a cyano group, a nitro group, -C(=O)OR, -OC(=O)R, -C(=O)R, - S(=O) ₂ R, a fluorinated alkyl group, an aromatic group substituted with at least one of a halogen atom, and R represents an optionally substituted hydrocarbon group.

In formula (1-1), R ¹ represents a hydrogen atom or a hydrocarbon group which may be substituted, and a hydrocarbon group which may be substituted is preferable. As the above-mentioned hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group is preferable, and an alkyl group or an aryl group is more preferable. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 2 to 10 carbon atoms is more preferable. The above-mentioned alkyl group may be any of linear, branched, or cyclic, and may be a group represented by a combination of these. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 6 carbon atoms is more preferable. As said alkenyl group, any of linear, branched, or cyclic may be sufficient as it, and the group represented by these combinations may be sufficient as it. As the alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable. The above-mentioned alkynyl group may be any one of linear, branched, or cyclic, and may be a group represented by a combination of these. As the aryl group, an aryl group having 1 to 20 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is further preferable. Moreover, it is preferable that the said aryl group is an aromatic hydrocarbon group. As a substituent in the said hydrocarbon group, a well-known substituent can be used in the range which can obtain the effect of this invention, and a hydroxyl group etc. are mentioned. In formula (1-1), R ² represents an optionally substituted hydrocarbon group. The preferred aspect of R ² is the same as the preferred aspect of R ¹ in the above formula (1-1). In formula (1-1), R ¹ and R ² may be bonded to form a ring structure. As the formed ring structure, a 5-membered ring or a 6-membered ring is preferable, and a 6-membered ring is more preferable. Moreover, although the said ring structure may be an aliphatic ring structure or an aromatic ring structure, an aliphatic ring structure is preferable. Specifically, a piperidine ring which may have a substituent is exemplified as a ring structure formed by bonding R ¹ and R ² . As said substituent, an alkyl group, a hydroxyalkyl group, an aralkyl group, etc. are mentioned.

In the formula (1-2), the preferred aspects of R ¹ and R ² are the same as the preferred aspects of R ¹ and R ² in the formula (1-1), respectively. In formula (1-2), R ³ each independently represents a hydrogen atom or a hydrocarbon group which may be substituted. As the above-mentioned hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group is preferable, an alkyl group or an aryl group is more preferable, and an alkyl group is even more preferable. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is further preferable. The above-mentioned alkyl group may be any of linear, branched, or cyclic, and may be a group represented by a combination of these. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 6 carbon atoms is more preferable. As said alkenyl group, any of linear, branched, or cyclic may be sufficient as it, and the group represented by these combinations may be sufficient as it. As the alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable. The above-mentioned alkynyl group may be any one of linear, branched, or cyclic, and may be a group represented by a combination of these. As the aryl group, an aryl group having 1 to 10 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is further preferable. Moreover, it is preferable that the said aryl group is an aromatic hydrocarbon group. As a substituent in the said hydrocarbon group, a well-known substituent can be used in the range which can obtain the effect of this invention, and a hydroxyl group etc. are mentioned. In formula (1-2), R ⁴ represents a cyano group, a nitro group, -C(=O)OR, -OC(=O)R, _-C (=O)R, -S(=O)2R, As a fluorinated alkyl group or a halogen atom, a cyano group is preferable from the viewpoint of the generation efficiency of a base. R represents a hydrocarbon group that may be substituted, an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group or a group represented by a combination thereof is preferred, an alkyl group, an aromatic hydrocarbon group or a group represented by a combination thereof is more Preferably, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a naphthyl group or a group represented by a combination thereof is further preferred. As a substituent in R, a halogen atom, a hydroxyl group, an alkoxy group, etc. are mentioned.

In the formula (1-3), the preferred aspects of R ¹ and R ² are the same as the preferred aspects of R ¹ and R ² in the formula (1-1), respectively. In the formula (1-3), the preferred aspect of R ³ is the same as the preferred aspect of R ³ in the formula (1-2). In formula (1-3), Ar represents a group selected from the group consisting of cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) ₂ An aromatic group substituted with at least one of R, a fluorinated alkyl group, and a halogen atom. A preferable aspect of R is the same as R in the above formula (1-2). As the above-mentioned aromatic group, an aromatic group having 1 to 20 carbon atoms is preferable, an aromatic group having 6 to 10 carbon atoms is more preferable, and a phenyl group is further preferable. The above-mentioned aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred.

Moreover, as compound B, it is also preferable to use the compound which does not have an acid group. It is thought that migration of metals, such as copper, is also easily suppressed from the said aspect, and the cured film obtained is excellent in adhesiveness.

The molecular weight of compound B is preferably 100-700, preferably 100-500, more preferably 150-400.

[化學式21]

Specific examples of compound B include the following compounds. [Chemical formula 20]

[Chemical formula 21]

The content of Compound B is preferably 0.1 to 20.0 mass %, more preferably 0.1 to 10.0 mass %, and even more preferably 0.5 to 5.0 mass % with respect to the total mass of the resin composition of the present invention.

<Organometallic complex> From the viewpoint of chemical resistance, it is preferable that the resin composition of the present invention contains an organometallic complex. Organometallic complexes only need to be organic complexes containing metal atoms, but complexes containing metal atoms and organic groups are preferred, and compounds in which organic groups coordinate metal atoms are more preferred, and metallocene compounds are preferred. for further better. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. The above-mentioned organic group is not particularly limited, but a hydrocarbon group or a group formed by a combination of a hydrocarbon group and a hetero atom is preferable. As the 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 metal contained in the organometallic complex is not particularly limited, but a metal corresponding to a Group 4 element is preferred, and at least one metal selected from the group consisting of titanium, zirconium and hafnium is more preferred , at least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is 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 type of metal atom may be contained, or two or more types of metal atoms may be contained.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, and a titanocene compound, a zirconocene compound or a hafnocene compound is More preferably, titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are 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. In the present invention, having photoradical polymerization initiation energy means generating free radicals capable of initiating radical polymerization 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 in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, it can be determined by The presence or absence of the radical crosslinking agent disappears to confirm the presence or absence of photoradical polymerization initiation energy. When confirming the disappearance or not, an appropriate method can be selected according to the type of the radical crosslinking agent. For example, it may be confirmed by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography). In the case that the organometallic complex has the initiation energy of photo-radical polymerization, it is preferred that the organometallic complex is a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnium compound, and two Titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred. In the case where 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, titanium chelates, 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 preferably. [Chemical formula 22]

In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the above-mentioned 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. Examples of the aromatic group in R of the formula (P) include aromatic groups having 6 to 20 carbon atoms, and preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl, etc. As the alkyl group in R of 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 group, ethyl group, propyl group, and octyl group are mentioned. , isopropyl, tert-butyl, isoamyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. As the halogen atom in the above-mentioned R, F, Cl, Br and I can be 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, ethyl, and propyl groups are mentioned. base, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. The above R may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryl Oxycarbonyl, acyloxy, monoalkylamine, dialkylamine, monoarylamine and diarylamine, etc.

Specific examples of the organometallic complex are not particularly limited, but tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate) can be exemplified. Titanium, diisopropoxybis(acetoacetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl) base)phenyl)titanium, pentamethylcyclopentadienyltrimethoxide titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following said compound. [Chemical formula 23]

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 resin composition of the present invention. The lower limit is more preferably 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 3.0 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 using 2 or more types, it is preferable that the total amount is in the said range.

＜Solvent＞ The 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.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (for example, 2-alkane Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methyl propionate and 2-alkane Ethyl oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 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. are preferred.

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, and triethyl ether. Glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levodextran ketone, and dihydrodextran Sugar ketones and the like are preferred.

As cyclic hydrocarbons, aromatic hydrocarbons, such as toluene, xylene, and anisole, and cyclic terpenes, such as limonene, are mentioned as preferable ones, for example.

As the sulfites, for example, dimethyl sulfite can be mentioned as a preferable one.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexylester-2-pyrrolidone, N,N-dimethylethyl acetate amide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc. are preferred.

Preferable examples of the urea 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-methyl alcohol Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monodiethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol and diacetone alcohol, etc.

Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., it is also preferable to mix two or more types.

In the present invention, selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve 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 Alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucan ketone, dihydroglucan ketone, one kind of solvent or two or more kinds of solvents The mixed solvent is preferred. It is particularly preferred to use dimethylsulfoxide and γ-butyrolactone together or N-methyl-2-pyrrolidone and ethyl lactate together.

From the viewpoint of coatability, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass of the total solid concentration of the resin composition of the present invention , it is more preferable to set it as an amount of 10-70 mass %, and it is still more preferable to set it as 20-70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types. When two or more kinds of solvents are contained, the total is preferably within the above-mentioned range.

[Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of starting polymerization by light and/or heat. In particular, it is preferable to contain a photopolymerization initiator. Preferably, the photopolymerization initiator is 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 of photoexcitation.

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 wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbis Oxime compounds such as imidazoles and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl groups such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For such details, 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, and the contents are incorporated into the present specification. In addition, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in JP 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in JP 2019-044030 A, the peracid-based initiator described in JP 2019-167313 A, These contents are also incorporated into this manual.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 can be exemplified, and this content is incorporated in the present specification. Among the commercially available products, KAYACURE DETX-S (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, the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the This content is incorporated into this manual.

As the α-hydroxyketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE- 2959, IRGACURE 127 (product name: all made by BASF).

As the α-amino ketone-based starter, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all are BASF Corporation) can be used system).

As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption maximum wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used, and the contents are incorporated in the present specification.

As an acylphosphine oxide-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. are mentioned. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF Corporation) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF Corporation), Keycure VIS 813 (manufactured by King Brother Chem Corporation), and the like.

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 has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator, so it is particularly preferable.

Specific examples of the oxime compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, and compounds described in JP 2006-342166 A. Compounds, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP 2004-534797 A, JP 2017-019766 A Compounds described, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, JP 2017-198865 A The compounds described in WO 2017/164127, the compounds described in paragraphs 0025 to 0038 of WO 2017/164127, the compounds described in WO 2013/167515, and the like are incorporated herein by reference.

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 resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 24]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open 2012- The photoradical polymerization initiator 2) described in Gazette 014052. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used . In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 25]

As a photoradical polymerization 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 Japanese Patent Laid-Open No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, the contents of which are incorporated in the present specification.

As the photoradical polymerization 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. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 is mentioned, and the content is incorporated in this specification.

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 Unexamined Publication No. 2013-164471, and the contents thereof are incorporated into the present specification.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A. The compound is the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and the contents thereof are incorporated into the present specification. Moreover, ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION) is also mentioned as an oxime compound which has a nitro group.

As a photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. As such a photopolymerization initiator, the compound described in International Publication No. 2019/088055, etc. are mentioned, and the content is incorporated in this specification.

As the photopolymerization initiator, an oxime compound (hereinafter, also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 into which an electron withdrawing group is introduced can also be used. Examples of the electron withdrawing group possessed by the above-mentioned aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group and a nitro group are preferable, and an acyl group is more preferable, and a benzyl group is still more preferable from the viewpoint of easily forming a film having excellent light resistance. The benzyl group may have a substituent. As a substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkenyl group, an alkylthio group, an arylthio group , amide group or amine group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclicoxy group, alkylthio group, arylthio group or amine group are more preferred, alkoxy group, alkyl group A thio group or an amine group is further preferred.

式中，R ^X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、亞膦醯基、胺甲醯基或胺磺醯基， R ^X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R ^X3～R ^X14分別獨立地表示氫原子或取代基。 其中，R ^X10～R ^X14中的至少1個為拉電子基團。 The oxime compound OX is preferably at least one selected from the group consisting of the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). [Chemical formula 26]

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an aryl group sulfinyl group, alkylsulfonyl group, arylsulfonyl group, yl group, yloxy group, amino group, phosphonide group, carbamoyl group or sulfamoyl group, R ^X2 represents alkyl, alkene alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl group, arylsulfonyl group, aryloxy group or amine group, and R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent. Among them, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

In the above formula, R ^X12 is an electron withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated in the present specification.

As the optimum oxime compound, the oxime compound having a specific substituent shown in JP-A No. 2007-269779 or the oxime compound having a thioaryl group shown in JP-A No. 2009-191061 can be mentioned. , and incorporate it into this manual.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl groups Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl - Compounds in the group of benzene-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, metallocene compounds, oxime compounds, triarylimidazole dimers, dibenzoyl It is still more preferable to use at least one compound in the group of ketone compounds, and it is still more preferable to use a metallocene compound or an oxime compound.

In addition, as the photoradical polymerization initiator, N, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkyl anthraquinones and other quinones formed by condensed with aromatic rings, Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 27]

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 or a phenyl group or C1-20 alkyl, C1-12 alkoxy, halogen atom, cyclopentyl, cyclohexyl, C2-12 alkenyl, interrupted by one or more oxygen atoms A phenyl group or biphenyl group substituted with at least one of the alkyl group having 2 to 18 carbon atoms and the alkyl group having 1 to 4 carbon atoms, R ^I01 is a group represented by formula (II) or the same as R ^I00 R ^I02 to R ^I04 are each independently an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons or a halogen atom.

[Chemical formula 28]

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. WO 2015/125469 can also be used as the photo-radical polymerization initiator, and the contents are incorporated in the present specification.

As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation over time becomes difficult, so that the stability over time of the resin composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photo-radical polymerization initiators include JP 2010-527339 A, JP 2011-524436 A, WO 2015/004565, JP 2011-524436 Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E ) and compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester-based photoinitiators described in paragraph 0007 of JP 2017-523465 A, JP 2017- The photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, and Japanese Patent No. 6469669 The oxime ester photoinitiator and the like described, and the contents are incorporated into this specification.

When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 30 mass % with respect to the total solid content of the resin 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 types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range. In addition, since the photopolymerization initiator may function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further performed by heating in an oven, a hot plate, or the like.

[Sensitizer] The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with the thermal radical polymerization initiator, the photoradical polymerization initiator, etc., thereby producing electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator are decomposed by chemical change, and a radical, an acid, or a base is generated. As sensitizers that can be used, benzophenone-based, micheler's ketone-based, coumarin-based, pyrazoleazo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, and anthracene-based sensitizers can be used series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series and other compounds. Examples of the sensitizer 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)benzo Thiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4' -diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin , 3-ethoxycarbonyl-7-diethylamino coumarin (7-(diethylamino) coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Esters, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyazole) Methylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminostyryl) Styrene, diphenylacetanilide, benzalanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. In addition, other sensitizing dyes can be used. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present specification.

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

[Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Regarding the chain transfer agent, it is defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (edited by The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH, and GeH in the molecule, those having a compound used for RAFT (Reversible Addition Fragmentation chain Transfer: Reversible addition chain transfer polymerization) dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compound, etc. These can generate free radicals by supplying hydrogen to less reactive radicals or can be deprotonated to generate free radicals after being oxidized. In particular, a thiol compound can be preferably used.

In addition, as a chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. WO 2015/199219 can also be used, and the contents are incorporated in the present specification.

When the 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, preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention More preferably, 0.5-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more types of chain transfer agents, the total is preferably within the above range.

[Photoacid generator] It is preferable that the resin composition of this invention contains a photoacid generator. The photoacid generator represents a compound that generates at least one of a Brynster acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. When a photoacid generator is used alone or in combination with a sensitizer, a photoacid generator capable of generating an acid by exposure to light is preferred. Preferable examples of the acid to be generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivatives, and phosphorus derivatives. , Antimony derivatives, halogen peroxides, sulfonamides, etc.

Examples of the photoacid generator used in the resin composition of the present invention include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, onium salt compounds, and the like. . From the viewpoints of sensitivity and storage stability, organohalogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of mechanical properties of the formed film, oxime esters are preferred.

Examples of the quinonediazide compound include a sulfonic acid ester bond of quinonediazide to a monovalent or polyvalent hydroxy compound, and a sulfonic acid sulfonamide bond of quinonediazide to a monovalent or polyvalent amine compound. On the other hand, those obtained are those obtained by the sulfonate bond of quinonediazide and/or the sulfonamide bond to the polyhydroxypolyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinonediazide, but on average, more than 40 mol% of the total functional groups are substituted with quinonediazide as better. By containing such a quinonediazide compound, it is possible to obtain a resin composition that is sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of a mercury lamp, which are normal ultraviolet rays.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, cyclohexanol, naphthol, Bis-Z, and BisP. -EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P , BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF , TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the product name above, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are the product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethylacetate Oxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxydiol Benzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin, etc., but It is not limited to these.

Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc., but not limited on such.

In addition, specific examples of the polyhydroxypolyamine compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but It is not limited to these.

Among these, it is preferable to contain a phenol compound and an ester with a 4-naphthoquinonediazidesulfonyl group as the quinonediazide compound. Thereby, higher sensitivity and higher resolution to i-ray exposure can be obtained.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, the contrast between the exposed portion and the unexposed portion can be obtained, and thus higher sensitivity can be achieved, which is preferable. Furthermore, a sensitizer etc. can be added as needed.

The photoacid generator is preferably 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), the following formula (OS-103), the formula (OS-104), or the formula (OS-105) The represented oxime sulfonate compounds are preferred.

[Chemical formula 29]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When a plurality of X ³ exist, they may be the same or different. The alkyl group and the alkoxy group in the above X ³ may have a substituent. As the alkyl group in the above-mentioned X ³ , a straight-chain or branched-chain 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, and ^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 formula (OS-1) include those in paragraphs 0064 to 0068 of JP 2011-209692 A and 0158 to 0167 in JP 2015-194674 A. The following compounds are described, and these contents are incorporated into this specification.

[Chemical formula 30]

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 formula (OS-103) to formula (OS-105), the alkyl group represented by R ^s1 (preferably with 1 to 30 carbon atoms), aryl group (preferably with 6 to 30 carbon atoms) or heteroaryl ( It is preferable to have 4 to 30 carbon atoms) within a range in which the effects of the present invention can be obtained, and may have a known substituent.

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. There may be two or more R ^s2 in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, one is an alkyl group, an aryl group or a halogen atom, more preferably, one is an alkyl group, an aryl group or a halogen atom Alkyl groups and the remainder are hydrogen atoms are particularly preferred. The alkyl group or aryl group represented by R ^s2 may have a known substituent within a range in which the effects of the present invention can be obtained. 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 containing 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. good. In formula (OS-103) to formula (OS-105), the alkyl group (preferably carbon number 1-30) and alkoxy group (preferably carbon number 1-30) 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), and 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 31]

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 base, 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 formulae (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and a hydrogen atom is preferable.

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 the 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 paragraphs 0088 to 0095 of Japanese Patent Laid-Open No. 2011-209692 and Japanese Patent Laid-Open No. 2015-194674. Compounds described in paragraphs 0168 to 0194 of the gazette, and these contents are incorporated into 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 32]

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 sulfo group , cyano, aryl or heteroaryl. The aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and the aspect in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further 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, and an alkylcarbonyl group , 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.

作為市售品，可以舉出WPAG-336（FUJIFILM Wako Pure Chemical Corporation製）、WPAG-443（FUJIFILM Wako Pure Chemical Corporation製）、MBZ-101（Midori Kagaku Co.,Ltd.製）等。 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 the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195-0207 of JP-A No. 2015-194674, These contents are incorporated into this manual. Among the above-mentioned compounds, the following b-9, b-16, b-31, and b-33 are preferable. [Chemical formula 33]

As a commercial item, WPAG-336 (made by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (made by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (made by Midori Kagaku Co., Ltd.), etc. are mentioned.

Moreover, the compound represented by the following structural formula can also be mentioned as a preferable example. [Chemical formula 34]

Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), the specification of U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Laid-Open Japanese Patent Laid-Open No. 48-36281, Japanese Patent Laid-Open No. 55-32070, 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. 61-169837 Sho 62-58241, JP 62-212401, JP 63-70243, JP 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) and the like, and these contents are incorporated into the present specification. In particular, a trihalomethyl-substituted oxazole compound: S-triazole compound can be mentioned as a preferable example. More preferably, at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-tris-s-tris-s-s-s-s-s-s-s-s-s-s-s-s-s-s-s-derivatives, for example, 2,4,6 -Tris(monochloromethyl)-s-tris-tris, 2,4,6-tris(dichloromethyl)-s-tris-tris, 2,4,6-tris(trichloromethyl)-s-tris 𠯤, 2-methyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris𠯤, 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, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl) methyl)-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-s-tris, 2 -(p-Methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) base)-s-tris-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(4-naphthyloxynaphthyl)-4,6-bis (Trichloromethyl)-s-tris-tris, 2-phenylsulfanyl-4,6-bis(trichloromethyl)-s-tris-tris, 2-benzylsulfanyl-4,6-bis(trichloromethyl) base)-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-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-s-tris, etc.

As the organoborate compound, for example, 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, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, etc. and Kunz, Martin "Rad Tech'98" .Proceeding April 19-22, 1998, the organic borate described in "Chicago", etc., Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561 Organoboronium complexes or organoboroxonium complexes, Organoboronium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, Japanese Patent Laid-Open No. 9-188710 The organoboron phosphonium complexes described in Gazette No. 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP 7-306527 Organoboron transition metal complex complexes, such as Unexamined-Japanese-Patent No. 7-292014, etc. are taken as specific examples, and these content are incorporated in this specification.

As the dioxane compound, the compounds and the diazodioxane 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 the 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 Pat. No. 4,069,055, US Pat. No. 4,069,056, European Patent No. 104,143, US Pat. No., 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 No., 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, The permalate salts described in the respective specifications of US Patent 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), Selenium salts, C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct. (1988), arsenic salts, onium salts such as pyridinium salts, etc., and these contents are incorporated into the present specification.

式（RI-I）中，Ar ₁₁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2～12的烯基、碳數2～12的炔基、碳數6～12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2～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基的碳數為6～20的芳基醯胺基、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。Z ₁₁ ^-表示1價的陰離子，其為鹵素離子、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，從穩定性的方面考慮，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，Ar ₂₁、Ar ₂₂各自獨立地表示可以具有1～6個取代基的碳數1～20的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12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的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為碳數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，其為鹵素離子、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、反應性的方面考慮，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，R ₃₁、R ₃₂、R ₃₃各自獨立地表示可以具有1～6個取代基之碳數6～20的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面考慮，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2～12的烯基、碳數2～12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的單烷基胺基、烷基的碳數為碳數1～12的二烷基胺基、烷基的碳數為相互獨立的碳數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。Z ₃₁ ^-表示1價的陰離子，其為鹵素離子、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、反應性的方面考慮，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 35]

In formula (RI-I), Ar ₁₁ represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group with 1 to 12 carbons, an alkyl group with 2 carbons Alkenyl group of to 12, alkynyl of carbon number of 2 to 12, aryl group of carbon number of 6 to 12, alkoxy of carbon number of 1 to 12, aryloxy group of carbon number of 1 to 12, halogen atom, carbon number of 1 Alkylamine group of ~12, dialkylamine group of carbon number of 2 to 12, alkylamide of alkyl group of carbon number of 1 to 12, or arylamide of aryl group of carbon number of 6 to 20 group, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is halide ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability, perchloric acid ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferable substituents include 1 to 12 carbon atoms. alkyl, alkenyl with 2-12 carbons, alkynyl with 2-12 carbons, aryl with 1-12 carbons, alkoxy with 1-12 carbons, aryloxy with 1-12 carbons , halogen atom, monoalkylamine group with 1 to 12 carbon atoms, dialkylamine group with 1 to 12 carbon atoms in the alkyl group, and alkyl amide group with 1 to 12 carbon atoms in the alkyl group An amino group or an arylamide 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. Z21- represents a monovalent anion, which is halide ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, stable from stable From the viewpoint of properties and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group having 1 to 6 substituents having 6 to 20 carbon atoms, preferably , from the viewpoint of reactivity and stability, aryl groups are preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 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 to 12, halogen atom, monoalkylamine group of carbon number of 1 to 12, dialkylamine group of alkyl group of carbon number of 1 to 12, alkane The number of carbon atoms in the group is an alkyl amido group or an aryl amido group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group with 1 to 12 carbon atoms, and a carbon number 1-12 thioaryl groups. Z ₃₁ ^- represents a monovalent anion, which is halide ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable.

[化學式37]

[化學式38]

[化學式39]

Specific examples of preferable photoacid generators include the following. [Chemical formula 36]

[Chemical formula 37]

[Chemical formula 38]

[Chemical formula 39]

The photoacid generator is preferably used in 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, more preferably 0.5 to 10 mass %, and 0.5 to 3 mass % with respect to the total solid content of the resin composition. It is even more preferable to use 0.5 to 1.2 mass %. A photoacid generator may be used individually by 1 type, and may be used in combination of a plurality of types. When using a plurality of types in combination, it is preferable that these total amounts are within the above-mentioned range. Moreover, in order to provide photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.

<Alkali Generator> The resin composition of the present invention may contain an alkali generator. Among them, the base generator is a compound capable of generating a base by physical or chemical action. As a preferable alkali generator for the resin composition of this invention, a thermal alkali generator and a photobase generator are mentioned. It is assumed that the base generator does not contain the above-mentioned compound B. The resin composition of the present invention preferably contains an alkali generator, more preferably contains a thermal alkali generator or a photobase generator, and further preferably contains a thermal alkali generator. By including a thermal alkali generator in the resin composition, for example, the cyclization reaction of the precursor can be accelerated by heating, and the cured product has good mechanical properties and chemical resistance, for example, as a rewiring layer included in a semiconductor package The performance with the interlayer insulating film becomes good. As an alkali generator, an ionic alkali generator may be sufficient, and a nonionic alkali generator may be sufficient. Examples of the base generated from the base generator include secondary amines and tertiary amines. The alkali generator of the present invention is not particularly limited, and known alkali generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carbamoyl amine compounds, acetamide compounds, urethane compounds, and benzyl carbamic acid can be used. Ester Compounds, Nitrobenzyl Carbamate Compounds, Sulfonamide Compounds, Imidazole Derivative Compounds, Aminoimide Compounds, Pyridine Derivative Compounds, α-Aminoacetophenone Derivative Compounds, Quaternary Ammonium Salts Derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amide imide compounds, phthalimide derivative compounds, acyloxyimide-based compounds, and the like. As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned. [Chemical formula 40]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group, a halogen atom or a hydrogen atom which does not have a tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. In addition, none of Rb ¹ , Rb ² and Rb ³ has 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 forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited to this.

In formula (B1) and formula (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably contains a cyclic structure, and more preferably 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 is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The single ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.

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 preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred) or aralkyl A base (preferably with a carbon number of 7 to 25, more preferably 7 to 19, and further preferably 7 to 12) is preferable. 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. In particular, Rb ¹ and Rb ² are linear, branched or cyclic alkyl groups that may have substituents (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, and more preferably 3 to 12). Preferably, a cycloalkyl group that may have a substituent (preferably carbon number 3-24, more preferably 3-18, and further preferably 3-12) is more preferable, and a cyclohexyl group that may have a substituent is further preferable good.

Examples of Rb ³ include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and an aryl group (preferably having 6 to 22 carbon atoms, and having 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), aralkyl (carbon number 7-23) is better, 7-19 is better, 7-12 is further better), aralkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better), alkane Oxy group (preferably carbon number 1-24, more preferably 2-18, further preferred 3-12), aryloxy (preferably carbon number 6-22, more preferably 6-18, 6- 12 is more preferred) or aralkoxy (the number of carbon atoms is preferably 7-23, more preferably 7-19, and more preferably 7-12). Among them, cycloalkyl (preferably carbon number of 3 to 24, more preferably 3 to 18, and even more preferably 3 to 12), aralkenyl and aralkoxy are preferred. Rb ³ may 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 41]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² have the same meanings as Rb ¹ and Rb ² in 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), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, and 7-12 are more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb ¹³ is preferably an aralkyl group.

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 are more preferred, 2-3 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), aralkyl ( The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 11), and hydrogen atom is more preferred.

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

Moreover, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [Chemical formula 42]

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably carbon number 1-12, more preferably 1-6, further preferably 1-3), alkenyl (preferably carbon number 2-12, 2 ~6 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), aralkyl (carbon number 7 is preferred) ～23 is preferable, 7～19 is more preferable, 7～11 is further preferable), hydrogen atom or methyl group is preferable. Rb ¹⁷ 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 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are further preferable), among them, aryl group is preferable.

[Chemical formula 43]

In formula (B3), L represents a hydrocarbon group, which is a hydrocarbon group having a divalent valence of a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 more than one. In addition, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, the "connection chain" refers to the one that connects the connection objects in the shortest (minimum number of atoms) among the atomic chains on the path connecting the two atoms of the connection object or the group of connecting atoms. For example, in the compound represented by the following formula, L is composed of phenylene ethylidene, and has ethylidene as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain (that is, is The number of atoms constituting the connecting chain, hereinafter also referred to as "connecting chain length" or "connecting chain length") is four. [Chemical formula 44]

The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, it is preferable that the linking chain length of L is 4 or 5, and 4 is the most optimal. Specific preferred compounds of the base generator include, for example, compounds described in Paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in Paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.

Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1). [Chemical formula 45]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, and a divalent organic group is preferable. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is more preferable. The linking chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), hydrocarbon group (carbon number 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 10 are further preferred), and specifically, aliphatic hydrocarbon groups (1 to 24 carbon atoms are preferred, and 1 to 12 are preferred) More preferably, 1-10 is more preferable) or aromatic hydrocarbon group (carbon number is preferably 6-22, 6-18 is more preferable, 6-10 is further preferable), aliphatic hydrocarbon group is preferable. When an aliphatic hydrocarbon group is used as R ^N1 and R ^N2 , the basicity of the generated base is high, which is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, the aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

Examples of the aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to the combination of chain alkyl groups and cyclic alkyl groups, An alkyl group with an oxygen atom in it. The linear or branched chain alkyl group having 1 to 24 carbon atoms is preferable, 2 to 18 are more preferable, and 3 to 12 are further preferable. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like. The cyclic alkyl group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. The group related to the combination of a chain alkyl group and a cyclic alkyl group includes, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl Wait. The alkyl group having an oxygen atom in the chain is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, R ^N1 and R ^N2 are preferably an alkyl group having 5 to 12 carbon atoms, from the viewpoint of increasing the boiling point of the base that is decomposed and formed later. Among them, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable in a formulation that places importance on the adhesiveness at the time of lamination with a metal (for example, copper).

R ^N1 and R ^N2 may be connected to each other to form a ring structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. In addition, the cyclic structure formed by R ^N1 and R ^N2 may be a single ring or a condensed ring, but a single ring is preferable. The cyclic structure to be formed is preferably a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring. , an imidazoline ring, a pyrazolidine ring, a piperidine ring, a piperidine ring, a morpholine ring, and the like, preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperidine ring, and a morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes with an acid is preferably used.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl ( EE) base et al. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, and the like.

The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a bivalent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, and a bivalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a bivalent aromatic hydrocarbon group, or a bivalent aromatic hydrocarbon group which may have an oxygen atom in the chain. A group related to a combination of a divalent aliphatic hydrocarbon group having an oxygen atom and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. Preferably, these groups do not have oxygen atoms. The divalent hydrocarbon linking group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group is preferably one having 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an aryl-extended alkyl group) is preferably one having 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 for further better.

As the linking group L, specifically, a linear or branched chain-like alkylene group, a cyclic alkylene group, a group related to a combination of a chain-like alkylene group and a cyclic alkylene group, a group having in the chain An alkylene group of an oxygen atom, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylidene group, and an arylidene group are preferred. The linear or branched chain alkylene group having 1 to 12 carbon atoms is preferred, 2 to 6 are more preferred, and 2 to 4 are further preferred. The cyclic alkylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably one having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

The linear or branched chain alkenylene group is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl extended group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylidene alkylene group is preferably one having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain alkylene, cyclic alkylene, alkylene having oxygen atoms in the chain, chain alkenylene, aryl, aryl, and alkylene are preferred, 1,2 -ethylidene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylidene (especially cis-vinylidene), vinylidene Phenyl (1,2-phenylene), phenylmethylene (especially 1,2-phenylene), oxyethylidene (especially 1,2-vinyloxy-1,2- ethylidene) is better.

As the base generator, the following examples can be given, but the present invention is not limited to these.

[Chemical formula 46]

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.

Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these. [Chemical formula 47]

Specific examples of the imide salt include the following compounds, but the present invention is not limited to these. [Chemical formula 48]

When the resin composition of the present invention contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. Alkali generators can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that the total amount is in the said range.

<Polymerizable compound> It is preferable that the resin composition of this invention contains a polymerizable compound. As a polymerizable compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical crosslinking agent] The resin composition of the present invention preferably 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. Examples of the group containing the above-mentioned ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acryloyl. Groups with ethylenically unsaturated bonds such as amine groups. Among these, as the above-mentioned group containing an ethylenically unsaturated bond, a (meth)acrylamide group, a (meth)acrylamido group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, (Meth)acryloyl groups are more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 15 ethylenically unsaturated bonds is more preferable. The compound of 6 is more preferable. In addition, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention may also include a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. better.

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, the addition reaction products of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl groups, amine groups, and hydrogen thiol groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used, Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or Substitution reaction products of unsaturated carboxylic acid esters or amides with releasable substituents such as tosyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ether, and allyl ether can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated into the present specification.

Moreover, it is also preferable that the radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol Di( meth)acrylate, trimethylolpropane tris(acryloyloxypropyl) ether, tris(acryloyloxyethyl) isocyanurate, glycerol or trimethylolethane, etc. Compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols and then (meth)acrylated Amino (meth)acrylates described in each publication of Sho 51-037193, Japanese Patent Publication No. Sho 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. Sho 52-030490 Polyester 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, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making the 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.

Moreover, as preferable radical crosslinking agent substances other than the above, those 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 having a perylene ring and having two or more ethylenically unsaturated bond-containing groups or a cardo resin.

Furthermore, as other examples, the specific unsaturated compounds described in JP 46-043946 A, JP 01-040337 A, JP 01-040336 A, or JP 02 - Vinylphosphonic acid-based compounds and the like described in Gazette 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society 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, and the etc. are incorporated into this manual.

In addition, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds, which are described as formula (1) and formula (2) together with specific examples thereof, can also be used as a radical crosslinking agent in a polyfunctional alcohol. A compound obtained by adding ethylene oxide or propylene oxide and then (meth)acrylated.

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

As a radical crosslinking agent, dipeotaerythritol triacrylate (a commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipeotaerythritol tetraacrylate (a commercial product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipivaloerythritol penta(meth)acrylate (commercially available as KAYARAD D -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 oligomer types can also be used.

Commercially available products of the radical crosslinking agent include, for example, SR-494 produced by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy-extending chains, and SR-494 as a tetrafunctional acrylate having four vinyloxy chains Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as DPCA-60 having 3 TPA-330 of trifunctional acrylate of isobutyloxy chain, 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 the radical crosslinking agent, for example, the amine esters 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 Acrylates, those 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 having an ethylene oxide-based skeleton The amine ester compounds are also preferred. Furthermore, 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 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 preferred is a free-radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and the aliphatic polyhydroxy compound is neopentylerythritol or dipivostriol Alcohol compounds. 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 radical crosslinking agent having an acid group is 0.1-300 mgKOH/g, and particularly preferably 1-100 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and furthermore, the developability is excellent. In addition, the polymerizability was good. The said acid value is measured based on the description of JISK0070:1992.

From the viewpoints of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate for the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) can be used 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate Esters, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6hexanediol dimethacrylate , dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO of bisphenol A Adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2hydroxy-3-propenyloxypropane methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylate with other urethane bond, bifunctional methyl with urethane bond based acrylate. These can be mixed and used 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to a polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Regarding the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (hardened product). As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-Methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, alkenyl glycidyl ether, and the like. 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. In addition, as a bifunctional or more radical crosslinking agent, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned.

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 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 using 2 or more types simultaneously, it is preferable that the total amount is in the said range.

[Other cross-linking agents] It is also preferable that the resin composition of the present invention contains other cross-linking agents different from the above-mentioned radical cross-linking agents. 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 crosslinking agents in the molecule, which are promoted by the above-mentioned photoacid generator or photobase generator to facilitate interaction with the composition. The other compounds in the compound or the reaction products of the other compounds or the reaction products thereof are preferably the compounds of the group that form a covalent bond, and have a plurality of compounds in the molecule that are promoted by the action of acids or bases in the composition with the other compounds or their compounds. Compounds of reactive groups that form covalent bonds between the reaction products are preferred. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other cross-linking agents, compounds having at least one group selected from the group consisting of oxymethyl, methylol and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group of hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other cross-linking agents include compounds having an amine group-containing compound such as formaldehyde or formaldehyde and alcohols, such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, to be reacted with an oxymethyl group, A compound in which a hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine 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 which the hydroxymethyl group of these compounds self-condenses may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. The crosslinking agent using alkylene urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and contains a compound selected from the group consisting of glycoluril-based crosslinking agents described below. At least one compound in the group of the agent and the melamine-based crosslinking agent is more preferable.

As a compound containing at least one of the alkoxymethyl group and the alkoxymethyl group in the present invention, the alkoxymethyl group or the alkoxymethyl group directly in the aromatic group or the following urea structure can be mentioned. Compounds substituted on a nitrogen atom or on a trisium are taken as structural examples. Preferably, the alkoxymethyl or alkoxymethyl group of the above compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the alkoxymethyl group contained in the above-mentioned compound is preferably 1-10, more preferably 2-8, particularly preferably 3-6. The molecular weight of the above-mentioned compound is preferably 1500 or less, more preferably 180-1200.

[Chemical formula 49]

R ₁₀₀ represents an alkyl group or an acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include various compounds of the following general formula.

[Chemical formula 50]

In the formula, X represents a single bond or a 2-valent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an acid group. A group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, R ⁵ represents a group that can be removed by the action of an acid.)). R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1-3, d is 0-4, e is 0-3, f is 0-3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Examples of R ⁵ in the group represented by -C(R ⁴ ) ₂ COOR ⁵ include a group that is decomposed by the action of an acid to generate an alkali-soluble group, a group that is released by the action of an acid, and a group represented by -C(R 4 ) 2 COOR 5 . Out-C(R ₃₆ )(R ₃₇ )(R ₃₈ ),-C(R ₃₆ )(R ₃₇ )(OR ₃₉ ),-C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred aspects of the alkyl group and the aryl group are the same as the preferred aspects of the above-mentioned alkyl group and the aryl group. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may have a well-known substituent within the range which can obtain the effect of this invention.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As a group which is decomposed by the action of an acid to generate an alkali-soluble group or a group which is released by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, and an enol ester are preferred. Base et al. Further preferred are tertiary alkyl ester groups and acetal groups.

As a compound which has an alkoxymethyl group, the following structures are mentioned specifically,. As a compound which has an acyloxymethyl group, the compound which changed the alkoxymethyl group of the following compounds to an acyloxymethyl group is mentioned. As a compound which has an alkoxymethyl group or an acyloxymethyl group in a molecule|numerator, the following various compounds are mentioned, However, It is not limited to these.

[Chemical formula 51]

[Chemical formula 52]

As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an alkoxymethyl group is directly substituted on an aromatic ring or a tris-ring is 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 monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, and monomethoxyl glycoluril. Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethyl methylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethyl Glycoluril Glycoluril based cross-linking agents such as glycoluril; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, etc., Monomethylolated ethyl urea or dimethylolated 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, Monomethylolated Propylene Urea , 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, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, and tetramethylolated 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 direct bond on an aromatic ring (preferably a benzene ring) can also be preferably used A compound having at least one group selected from the group consisting of methylol and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethyl phenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(hydroxymethyl)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.

Commercially available products can also be used as other crosslinking agents, and preferred commercialized products 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 Sanwa Chemical Co., Ltd.) and the like.

Moreover, it is also preferable that the 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 compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has two or more epoxy groups in one molecule is preferable. The epoxy group undergoes a cross-linking reaction below 200°C, and does not produce a dehydration reaction caused by cross-linking, so it is difficult to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature hardening and warpage of the resin composition of the present invention.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further lowered, and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

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 epoxy 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) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S , EP-4088S, EP-3950S (product names above, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (product names above, 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, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[Chemical formula 53]

In the formula, n is an integer of 1-5, and m is an integer of 1-20.

Among the above-mentioned structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.

-Oxetane compounds (compounds with an oxetane group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxy oxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121 and OXT-221) 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)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzodiazepine compound is preferred without degassing during curing, thereby further reducing thermal shrinkage and suppressing warpage.

Preferable examples of benzodiazepine compounds include P-d-type benzodiazepines, F-a-type benzodiazepines, (the above are product names, manufactured by Shikoku Chemicals Corporation), and benzodiazepines of polyhydroxystyrene resins. Adducts, novolac-type dihydrobenzos 㗁𠯤 compounds. These can be used individually or in mixture of 2 or more types.

The content of other crosslinking agents is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and 1.0 to 10 mass % relative to the total solid content of the resin composition of the present invention. Mass % is particularly good. The other crosslinking agent may be contained only by one type, or may contain two or more types. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.

<Metal Adhesion Improver> It is preferable that the 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 alkoxysilyl-containing silane coupling agents, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having sulfonamide structures, compounds having thiourea, and phosphoric acid derivatives. Compounds, β-ketoester compounds, amine compounds, etc.

[Silane coupling agent] Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of JP-A No. 2018-173573 are incorporated herein by reference. Moreover, 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, Me represents a methyl group, and Et represents an ethyl group.

[Chemical formula 54]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 - Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based Adhesives] Examples of the aluminum-based adhesive adjuvant include aluminum tris(ethylacetate)aluminum, tris(acetoacetate)aluminum, aluminum ethylacetate diisopropoxide, and the like.

In addition, as other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the vulcanized compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used compounds, and these contents are incorporated into this specification.

The content of the metal adhesion improver is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass with respect 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 using 2 or more types, it is preferable that the sum total is in the said range.

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

The migration inhibitor is not particularly limited, but includes a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole 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) compounds, with Thiourea and hydrogen thio compounds, hindered phenolic compounds, salicylic acid derivatives, and hydrazine derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, and tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

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., and these contents are incorporated into this specification.

Specific examples of the migration inhibitor include the following compounds.

[Chemical formula 55]

When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass % with respect to the total solid content of the resin composition of the present invention , 0.1 to 1.0 mass % is more preferable.

Only one type of migration inhibitor may be used, or two or more types may be used. 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 resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, and the like .

As a specific compound of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, p- tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2' - Methylene bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N - Nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary Butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 -(N-Ethyl-N-sulfopropylamine)phenol, 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, 2,2,6,6-tetramethylpiperidine 1-oxygen Free radicals, phenothia, phenothia, 1,1-diphenyl-2-pyrrolehydrazine, copper(II) dibutyldithiocarbonate, nitrobenzene, N-nitroso-N-phenyl Hydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO 2015/125469 can also be used, and the contents are incorporated into the present specification. .

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0.02 to 15% by mass, more preferably 0.02 to 15% by mass relative to the total solid content of the resin composition of the present invention. 0.05-10 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.

＜Acid scavenger＞ It is preferable that the resin composition of this invention contains an acid scavenger in order to reduce the change in performance with time from exposure to heating. Among them, the acid scavenger refers to a compound that can capture and generate an acid by being present in the system, and a compound having a low acidity and a high pKa is preferable. As the acid scavenger, compounds with amine groups are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, primary amines, secondary amines, tertiary amines, ammonium salts More preferably, secondary amine, tertiary amine and ammonium salt are more preferable. As the acid scavenger, compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and alkylamine derivatives having a hydroxyl group and/or an ether bond can be preferably used. compounds, aniline derivatives with hydroxyl and/or ether bonds, etc. In the case of having an onium structure, the acid scavenger is an anion having a cation selected from the group consisting of ammonium, diazo, iodonium, perium, phosphonium, pyridinium and the like and an acid having a lower acidity than that generated by the acid generator. Salt is preferred.

As an acid scavenger having an imidazole structure, imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, etc. are mentioned. As an acid scavenger having a diazabicyclic structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonane- 5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triaryl perionium hydroxide, benzylmethyl perionium hydroxide, perium hydroxide having a 2-oxoalkyl group, and specifically Triphenyl perium hydroxide, tris(tert-butylphenyl) perium hydroxide, bis(tert-butylphenyl) iodonium hydroxide, benzalkonium methylthiophenium hydroxide, 2-oxopropane hydroxide base thiophenium, etc. Tri(n-butyl)amine, tri(n-octyl)amine, etc. are mentioned as an acid scavenger which has a trialkylamine structure. As an acid scavenger having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. are mentioned. As an acid scavenger having a pyridine structure, pyridine, 4-picoline, etc. are mentioned. Examples of alkylamine derivatives having a hydroxyl group and/or ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the like. N,N-bis(hydroxyethyl)aniline etc. are mentioned as an aniline derivative which has a hydroxyl group and/or an ether bond.

Specific examples of preferable acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, Cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine , DBU (diazabicyclo undecyl), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylene glycol Amine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine Amine, N,N,N',N'-Tetrabutyl-1,6-hexanediamine, Spermine, Diaminocyclohexane, Bis(2-methoxyethyl)amine, Piperidine , methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane (dianilinoethane), 2-aminoethanol, toluidine, aminophenol, hexylaniline, benzene diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrroleidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylamine, etc.

These acid scavengers may be used alone or in combination of two or more. The composition of the present invention may contain an acid scavenger or may not contain an acid scavenger, but when it does contain an acid scavenger, the content of the acid scavenger is usually 0.001 to 10% by mass based on the total solid content of the composition. Preferably it is 0.01-5 mass %.

The usage ratio of the acid generator and the acid scavenger is preferably acid generator/acid scavenger (molar ratio)=2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the reduction of the resolution caused by the increase in thickness of the relief pattern with time from exposure to heat treatment. , 300 or less is better. The acid generator/acid scavenger (molar ratio) is more preferably 5.0 to 200, further preferably 7.0 to 150.

＜Other additives＞ The resin composition of the present invention can contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium, as needed, within the range in which the effects of the present invention can be obtained. Compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (eg, defoaming agents, flame retardants, etc.), etc. By appropriately containing these components, properties such as film physical properties can be adjusted. For these components, for example, refer to the descriptions in paragraph 0183 and subsequent paragraphs of Japanese Patent Application Laid-Open No. 2012-003225 (paragraph 0237 of the corresponding specification of US Patent Application Publication No. 2013/0034812) and the descriptions in Japanese Patent Application Laid-Open No. 2008-250074 paragraphs 0101 to 0104, paragraphs 0107 to 0109, etc., and these contents are incorporated into this specification. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the resin composition of the present invention.

[Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially, fluidity) when prepared as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. . That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved, thereby improving the wettability of the surface to be coated. Improves coatability to the coated surface. Therefore, it is possible to more preferably form a film with a uniform thickness with little thickness unevenness.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1-068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (ASAHI GLASS CO above ., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and the compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A can also be used, and these The contents are incorporated into this manual. A block polymer can also be used as a fluorine-based surfactant, and specific examples thereof include compounds described in JP-A No. 2011-89090, and these contents are incorporated into the present specification. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, the fluorine-containing polymer compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a compound having two or more (preferably A repeating unit of a (meth)acrylate compound of an alkaneoxy group (preferably vinyloxy group, propyleneoxy group) having 5 or more), the following compounds can also be exemplified as the fluorine-based interface used in the present invention active agent. [Chemical formula 56]

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Fluorine-based Surfactant A fluoropolymer having an ethylenically unsaturated group on a side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, which are incorporated into the present specification. Moreover, as a commercial item, MEGAFACE RS-101 by DIC CORPORATION, RS-102, RS-718K etc. are mentioned, for example.

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 in terms of the uniformity of the thickness of the coating film and the liquid saving properties, 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.), KP-341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), and the like.

Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen 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.

As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) can be exemplified etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauric acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (TAKEMOTO OIL&FAT CO., LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

Specific examples of the cationic surfactant include organosiloxane polymer KP-341 (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.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI Co., Ltd.), and the like.

Only one type of surfactant may be used, or two or more types may be used in combination. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

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

In addition, the compound described in the paragraph 0155 of International Publication No. WO 2015/199219 can also be used as the higher fatty acid derivative, and the content is incorporated in the present specification.

When the 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 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 contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates a radical by thermal energy and initiates or promotes a polymerization reaction of a 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. In addition, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, which are incorporated herein by reference.

When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 30% 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 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. The said average particle diameter of an inorganic particle is a primary particle diameter, and is a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In the case where it is difficult to perform the above-mentioned measurement, the measurement can also be performed by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.

[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 salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. Examples of benzophenone-based ultraviolet absorbers 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 the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Furthermore, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-based 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 this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is 0.001% by mass or more and 1% by mass relative to the total solid mass of the composition of the present invention. Mass % 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. Since the resin composition contains an organotitanium compound, a resin layer excellent in chemical resistance can be formed even when it is cured at a low temperature.

As the 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 resin composition has excellent storage stability and can obtain a good hardened pattern, so the titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are diisopropoxide bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, Isopropanol bis (tetramethylheptanedione) titanium, diisopropanol bis (ethyl acetate) titanium, etc. II) Titanium tetraalkoxide compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium Tetramethoxypropoxide, Titanium Tetramethylphenoxide, Titanium Tetra(n-nonanol), Titanium Tetra(n-propoxide), Titanium Tetrastearyloxide, Tetrakis[bis{2,2-(allyloxy) Methyl) butanol}] titanium and so on. 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(dioctyl phosphate) titanium isopropoxide, tris(dodecylphenyl sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonic acid titanate and the like.

Among them, as the organotitanium compound, from the viewpoint of exhibiting better chemical resistance, those selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds and III) titanocene compounds At least one compound is preferred. In particular, bis(ethylacetate)titanium diisopropoxide, tetrakis(n-butoxide)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, with respect to 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance more effectively. On the other hand, when the compounding amount is 10 parts by mass or less, the The storage stability is more excellent.

〔Antioxidants〕 The composition of the present invention may contain antioxidants. By containing an antioxidant as an additive, the elongation 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 above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, 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] Dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]Dioxaphosphin-2-yl)oxy]ethyl]amine and phosphite ethylbis(2,4-di-tert-butyl-6-methyl) phenyl) etc. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO- 80 and Adekastab AO-330 (the above are made 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, and the contents are incorporated in the present specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As potential antioxidants, compounds in which the sites that act as antioxidants are protected by protective groups can be mentioned, and the compounds are prepared by heating at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst. A compound that acts as an antioxidant when heated to remove the protecting group. Examples of potential antioxidants include compounds described in International Publication No. WO 2014/021023, International Publication No. 2017/030005, and JP 2017-008219 A, the contents of which are incorporated into the present specification. As a commercial item of a potential 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 formula (3) the indicated compound.

[Chemical formula 57]

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably carbon number 2 to 10), and R ⁶ represents an extension having carbon number 2 or more (preferably carbon number 2 to 10). alkyl. R ⁷ represents an alkylene group having 2 or more carbon atoms (preferably, a carbon number of 2 to 10), and a 1- to 4-valent organic group containing at least any one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.

The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group contained in 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, it is more preferable that k is an integer of 2 to 4. 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 have a substituent. Among them, those having an alkyl ether group and -NH- are preferred from the viewpoints of solubility in a developer and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion at the time of metal complex formation Consider, -NH- is better.

The compounds represented by the general formula (3) include the following as examples, but are not limited to the following structures.

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

[Chemical formula 61]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, with respect to the resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials, and by setting the addition amount to 10 parts by mass or less, for example The sensitivity of the resin composition is improved by the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.

[Anti-agglomeration agent] The resin composition of this embodiment may contain an anti-agglomeration agent as needed. As an anti-agglomeration agent, sodium polyacrylate etc. are mentioned.

In this invention, an anti-agglomeration agent may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain an anti-agglomeration agent, but when included, the content of the anti-agglomeration agent is 0.01% by mass or more and 10% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.02 mass % or more and 5 mass % or less are more preferable.

[Phenolic compounds] The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (the product names above, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the above is the product name, manufactured by ASAHI YUKIZAI CORPORATION), etc.

In the present invention, the phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain the phenolic compound, but when included, the content of the phenolic compound is 0.01% by mass or more and 30% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

[Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. things etc. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, and an epoxy group is introduced.

In the present invention, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds, but when included, the content of the other polymer compounds is 0.01% by mass relative to the total solid mass of the composition of the present invention More than 30 mass % is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

<Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s is preferable, 2,000 mm ² /s to 10,000 mm ² /s is more preferable, and 3,000 mm ² /s to 8,000 mm ² /s for further better. As long as it is in the said range, it becomes easy to obtain the coating film with high uniformity. When it is 1,000 mm ² /s or less, for example, it is difficult to coat with a film thickness required as an insulating film for rewiring, and when it is 12,000 mm ² /s or more, the coating surface morphology may be deteriorated.

The amount of acid groups (also referred to as "resist acid value") contained in the composition is preferably 6.0 mgKOH/g or less, more preferably 5.0 mgKOH/g or less, relative to 1 g of the resin composition of the present invention. The lower limit of the amount of the above-mentioned acid group is not particularly limited, and may be 0 mgKOH/g. As said acid group, the acid group whose pKa is 15 or less is mentioned, and a carboxyl group, a phenolic hydroxyl group, etc. are mentioned. The acid value of the above-mentioned resist is measured by, for example, a titration method using potassium hydroxide. Since the resin composition of the present invention contains Compound B which is excellent in stability, even if the amount of acid groups is reduced, it is excellent in storage stability. That is, in order to improve the storage stability of a composition, it is not always necessary to adjust the composition to be acidic.

<Restrictions on Substances Contained in Resin Compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. When it is 2.0% or more, the storage stability of the resin composition may be impaired. As a method of maintaining the moisture content, adjustment of the humidity in the storage conditions, reduction of the porosity of the storage container during storage, and the like are exemplified.

From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm good. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, with the exception of metals included as complexes of organic compounds and metals. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.

Further, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, there can be mentioned a method of selecting a raw material having a small metal content as a raw material constituting the resin composition of the present invention; The raw material of the product is filtered through a filter; the polytetrafluoroethylene and the like are lined in the device to conduct distillation under the condition that the pollution is suppressed as much as possible.

Considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm good. Among them, it is preferable that it is less than 5 mass ppm in the state of halide ions, 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. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above ranges, respectively. As a method of adjusting the content of halogen atoms, ion exchange treatment and the like can be preferably used.

As a container of the resin composition of the present invention, a conventionally known container can be used. Further, as the container, in order to suppress the contamination of impurities into the raw material or the resin composition of the present invention, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<The cured product of the resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The hardening of the resin composition is preferably carried out by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and in the range of 170°C to 350°C Excellent inside. The form of the cured product of the resin composition is not particularly limited, and a film form, a rod form, a spherical form, a granular form, and the like can be selected according to the application. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the cured product can also be selected for purposes such as forming a protective film on the wall surface, forming a beer hall for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat release function. shape. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage ratio refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula. Shrinkage rate [%]=100-(volume after hardening÷volume before hardening)×100

<Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is less than 70%, the mechanical properties of the cured product may be poor. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

<Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method. For the mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating a tank itself, and the like can be employed. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

In addition, in order to remove foreign matter, such as dust and fine particles, in the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (High Density Polyethylene) is better. Filters can be pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of filters may be connected in series or in parallel and used. In the case of using a plurality of filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, an HDPE filter having a pore diameter of 1 μm as the first stage and an HDPE filter having a pore diameter of 0.2 μm as the second stage are connected in series. Also, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a loop filtering. Moreover, you may filter after pressurization. In the case of pressurizing and filtering, the pressurizing pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less Preferably, it is more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. 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. Furthermore, after the filtration using a filter, the step of leaving the resin composition filled in the bottle in a reduced pressure state and deaerating may be carried out.

(Manufacturing method of hardened product) It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material. Moreover, the manufacturing method of the hardened|cured material of this invention comprises the said film formation process, the exposure process of selectively exposing the film formed by the film formation process, and developing the film exposed by the exposure process using a developing solution to form a pattern The development step is better. The manufacturing method of the hardened|cured material of this invention includes the said film formation process, the said exposure process, the said development process, the heating process of heating the pattern obtained by the development process, and the exposure process of the pattern obtained by the development process. At least one of the post-development exposure steps is particularly preferred. Moreover, it is also preferable that the manufacturing method of this invention includes the said film formation step and the step of heating the said film. Hereinafter, the details of each step will be described.

<Film formation step> The resin composition of the present invention can be used in a film forming step for forming a film by applying it to a substrate. It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material.

[Substrate] The type of the base material can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and semiconductor materials. Metal substrates such as coating films, magnetic films, reflective films, Ni, Cu, Cr, Fe, etc. ), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates for plasma display panels (PDP), etc. In the present invention, especially semiconductor fabrication substrates are preferred, and silicon substrates, Cu substrates and mold substrates are even more preferred. In addition, layers such as an adhesion layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surfaces of these substrates. In addition, the shape of the base material is not particularly limited, and may be circular or rectangular. 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, as a base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) can be used.

Moreover, when a resin composition is applied to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.

As a method of applying the resin composition of the present invention to a substrate, coating is preferable.

Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. method, slit coating method, inkjet method, etc. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray method or inkjet method are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and The slit coating method is preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration or coating conditions of the resin composition 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, spin coating, spray coating, inkjet method, etc. are preferred, and in the case of a rectangular substrate, slit A coating method, a spraying method, an inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transcribe|transferring the coating film formed by the said application method to a dummy support beforehand is also applicable to a base material. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention. . Also, a step of removing excess film in the end portion of the base material may be performed. Examples of such a step include edge bead rinse (EBR), back rinse (Back rinse), and the like. In addition, a pre-wetting step may be employed, in which the resin composition is applied after various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate.

<Drying step> After the film forming step (layer forming step), the above-mentioned film may be used in a step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the manufacturing method of the hardened|cured material of this invention may include the drying process which dries the film formed by the film formation process. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the film in the drying step is preferably 50-150°C, more preferably 70-130°C, and further preferably 90-110°C. Moreover, drying can also be performed by reducing pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure step> The said film can be used for the exposure step of selectively exposing the film. That is, the manufacturing method of the hardened|cured material of this invention may include the exposure process which selectively exposes the film formed by the film formation process. Selectively exposing means exposing a portion of the film. Moreover, by selectively exposing, the exposed area (exposed part) and the unexposed area (non-exposed part) are formed on the film. The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured. For example, the exposure energy at a wavelength of 365 nm is preferably 50 to 10,000 mJ/cm ² , and 200 to 8,000 mJ/cm ² for better.

The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

Regarding the exposure wavelength, if the relationship with the light source is explained, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) ) High pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of the radiation is 532nm and the third harmonic is 355nm, etc. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as it is a method of exposing at least a part of the film formed of the resin composition of the present invention, and exposure using a photomask, exposure by direct laser imaging, etc. are exemplified .

<Heating step after exposure> The above-mentioned film may be used in a step of heating after exposure (post-exposure heating step). That is, the manufacturing method of the hardened|cured material of this invention may include the post-exposure heating process which heats the film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, the temperature from the start of heating to the maximum heating temperature is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min good. In addition, the temperature increase rate can be appropriately changed during the heating process. It does not specifically limit as a heating means in a post-exposure heating process, A well-known hot plate, oven, infrared heater, etc. can be used. Moreover, it is also preferable to carry out in the environment of a low oxygen concentration by flowing inert gas, such as nitrogen gas, helium gas, and argon gas, etc. at the time of heating.

<Development step> The above-mentioned film after exposure can be used in the developing step of forming a pattern by developing with a developing solution. That is, the manufacturing method of the hardened|cured material of this invention may include the developing process which develops the film exposed by the exposure process using a developing solution, and forms a pattern. By performing development, one of the exposed part and the non-exposed part of the film is removed, and a pattern is formed. Among them, the development of removing the non-exposed portion of the film by the development step is called negative development, and the development of removing the exposed portion of the film by the development step is called positive development.

[Developer] As the developing solution used in the developing step, an alkaline aqueous solution or a developing solution containing an organic solvent can be exemplified.

When the developing solution is an alkaline aqueous solution, examples of the alkaline compounds that the alkaline aqueous solution can contain include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH ( Tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl Diethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Hydrogen Tetraoctylammonium oxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis(hydroxide) 2-hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole and piperidine are preferred, and TMAH is more preferred. For example, in the case of using TMAH, 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 even more preferably 0.3 to 3% by mass in the total mass of the developer. good.

When the developing solution contains an organic solvent, the organic solvent includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid, etc., for example. Butyl, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetate alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methoxyacetate) Methyl oxyacetate, ethyl ethoxyacetate, 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 propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 2-methoxypropionic acid) methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy -Methyl 2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2- ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutane Ethyl acid, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethylene glycol Cellosolve 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 can be preferably used ketone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Preferable examples of the sulfites include dimethylsulfoxide, and as the alcohols, preferred examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, and diethylenediol. Alcohol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide are preferably used. Wait.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, development of at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly included The solution is preferred, and the developing solution containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferred, and the developing solution including cyclopentanone is the most preferred.

When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more relative to the total mass of the developer solution. The above are excellent. Moreover, the said content may be 100 mass %.

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

[How to supply developer] The method for supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle In order to carry out spin-on immersion development or continuous supply of developer. 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 production efficiency, the method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferable. From the viewpoint of the permeability of the part, the method of supplying using a spray nozzle is more preferable. Also, after the developer is continuously supplied using the straight nozzle, the substrate is rotated to remove the developer from the substrate, and after the continuous supply using the straight nozzle again after spin drying, the substrate is rotated to remove the developer from the substrate. The step of liquid solution can also be repeated several times. In addition, as a method of supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, and developing the substrate by ultrasonic waves or the like can be employed The steps of liquid vibration and the steps combining these, etc.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it can be preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.

In the developing step, after the treatment with the developing solution, cleaning (rinsing) of the pattern using the rinsing solution may be further performed. In addition, a method of supplying a rinsing liquid or the like may be employed before the developing liquid in contact with the pattern is completely dried.

[Rinse fluid] When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. In the case where the developing solution is a developing solution containing an organic solvent, as the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used ).

As the organic solvent when the rinsing liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve can be preferably mentioned. Agent 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 cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, and propylene glycol. , methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone , dimethyl sulfoxide, PGMEA, PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinsing liquid contains an organic solvent, preferably 50% by mass or more of the rinsing liquid is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. Moreover, 100 mass % of the rinse liquid 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 rinse liquid is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate through a liquid pan, and a method of spraying The method of supplying the rinsing liquid to the substrate in the form of a shower, and the method of continuously supplying the rinsing liquid to the substrate through a mechanism such as a straight nozzle. From the viewpoints of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it using 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 step is preferably a step of supplying or continuously supplying a rinsing liquid to the above-mentioned exposed film through a straight nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, and rinsing the substrate with ultrasonic waves or the like can be used. The steps of liquid vibration and the steps combining these, etc.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it can be performed preferably at 10 to 45°C, and more preferably at 18 to 30°C.

<Heating step> The pattern obtained by the development step (the rinsed pattern in the case of the rinse step) may be used in the heating step of heating the pattern obtained by the above development. That is, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by the developing process. Moreover, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by another method or the film obtained by the film formation process in the state which did not carry out the developing process. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. Moreover, the crosslinking etc. of the unreacted crosslinkable group in a specific resin or a crosslinking agent other than a specific resin are also performed. As the heating temperature (maximum heating temperature) in the heating step, 50-450°C is preferable, 150-350°C is more preferable, 150-250°C is further preferable, 160-250°C is further preferable, 160- 230°C is particularly preferred.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and utilizing the action of the base generated from the base generator, the base generated from the compound B, or the like.

The heating in the heating step is preferably performed at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The above-mentioned temperature increase rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of the acid or solvent can be prevented while maintaining productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured product can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out a heating rate of 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. 3 to 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 the start of the step of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after drying is, for example, higher than the temperature of the solvent contained in the resin composition of the present invention. It is preferable to start the temperature rise at a temperature that is 30 to 200°C lower in the boiling point.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, more preferably 100°C or higher, and particularly 120°C or higher. good. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating can be performed in stages. As an example, the following steps may be performed: ramp from 25°C to 120°C at 3°C/min and hold at 120°C for 60 minutes, and ramp from 120°C to 180°C at 2°C/min and hold at 180°C for 120 minutes . Moreover, as described in the specification of US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. By such a pretreatment step, the characteristics of the film can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be two or more steps, for example, the pretreatment step of the first step may be performed in the range of 100 to 150°C, and then the pretreatment step of the second step may be performed in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, 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 conduct the heating step in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon under a reduced pressure state. . 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 in a heating process, For example, a hot plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven etc. are mentioned.

<Exposure step after development> Instead of or in addition to the above heating step, the pattern obtained by the development step (in the case of performing the rinse step, the rinsed pattern) can also be used after the development of the pattern after the exposure and development step. in the exposure step. That is, the manufacturing method of the cured product of the present invention may include a post-development exposure step that exposes the pattern obtained by the development step. The manufacturing method of the cured product of the present invention may include a heating step and an exposure step after development, or may include only one of a heating step and an exposure step after development. In the post-development exposure step, for example, a reaction of cyclization of a polyimide precursor or the like by exposure to a photobase generator or a reaction of detachment of an acid-decomposable group by exposure to a photoacid generator can be accelerated. reaction etc. In the post-development exposure step, it is sufficient to expose at least a part of the pattern obtained in the development step, but it is preferable to expose all of the above-mentioned patterns. The exposure amount in the post-development exposure step is preferably 50-20,000 mJ/cm ² , more preferably 100-15,000 mJ/cm ² , when the exposure energy at the wavelength at which the photosensitive compound has sensitivity is converted. The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, preferably broadband light.

<Metal layer formation step> The pattern obtained by the developing step (preferably the pattern for at least one of the heating step and the post-exposure developing step) can be used in the metal layer forming step of forming the metal layer on the pattern. That is, it is preferable that the manufacturing method of the cured product of the present invention includes a metal layer forming step in the pattern obtained by the developing step (for at least one of the heating step and the post-development exposure step). pattern is preferably formed on the metal layer.

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

The formation method of the metal layer is not particularly limited, and conventional methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, Japanese Patent Application Laid-Open No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electrolytic plating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. As a preferable aspect of electroplating, electrolytic electroplating using a copper sulfate or copper cyanide electroplating solution can be mentioned.

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

＜Use＞ As the field to which the cured product of the present invention can be produced, or the cured product of the present invention, an insulating film of an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like can be mentioned. In addition, sealing films, substrate materials (base films or cover films of flexible printed wiring boards, interlayer insulating films), and patterns formed by etching insulating films for practical mounting as described above can also be used. For such uses, for example, you can refer to Science&Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Application of Polyimide Materials" "Development" published in November 2011, Japan Polyimide/Aromatic Polymer Research Association/Edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

In addition, the manufacturing method of the cured product of the present invention or the cured product of the present invention can also be used for the manufacture of layouts such as offset printing plates or screen plates, the use of etching forming components, and the protection of protective paint and dielectric layers in electronics, especially in microelectronics. manufacturing etc.

(Laminated body and method for manufacturing the laminated body) The layered product of the present invention refers to a structure having a plurality of layers formed of the cured product of the present invention. The layered body of the present invention is a layered body including two or more layers formed of a cured product, and may be a layered body formed by stacking three or more layers. At least one of the two or more layers formed of the above-mentioned cured product included in the above-mentioned layered body is a layer formed of the cured product of the present invention, and suppresses the shrinkage of the cured product or the deformation of the cured product accompanying the shrinkage, etc. From a viewpoint, it is also preferable that all the layers formed of the cured product included in the above-mentioned laminate are layers formed of the cured product of the present invention.

That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened|cured material of this invention, and it is more preferable to include the steps of repeating the manufacturing method of the hardened|cured material of this invention several times.

The layered product of the present invention includes two or more layers formed of a cured product, and an aspect in which a metal layer is included between any of the layers formed of the cured product is preferred. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step. That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer forming step of forming a metal layer on the layer formed of the hardened|cured material between the manufacturing methods of the hardened|cured material performed a plurality of times. The preferred aspect of the metal layer forming step is as described above. As the above-mentioned layered product, for example, a layered product having a layer structure in which at least three layers of a first layer made of a cured product, a metal layer, and a second layer of a cured product are laminated in this order can be mentioned as a preferred one. . It is preferable that the above-mentioned first layer formed from the hardened product and the above-mentioned second layer formed from the hardened product are both layers formed from the hardened product of the present invention. The resin composition of the present invention for forming the above-mentioned first layer formed of the hardened material and the resin composition of the present invention for forming the above-mentioned second layer formed of the hardened material may be compositions of the same composition, or Compositions with different compositions may be used. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

<Lamination step> It is preferable that the manufacturing method of the laminated body of this invention includes a lamination|stacking step. The lamination step includes again sequentially performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step, on the surface of the pattern (resin layer) or metal layer. A series of steps of at least one of the post-development exposure steps. However, at least one of the film formation step of (a) and the (d) heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, the (e) metal layer forming step may be further included. It goes without saying that the above-mentioned drying step and the like may be further appropriately included in the lamination step.

When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned heating step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified. Details of the surface activation treatment will be described later.

Preferably, the above-mentioned layering step is performed 2 to 20 times, more preferably 2 to 9 times. For example, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferable to set the resin layer to 2 or more and 20 or less layers, and to set it to 2 or more and 9 layers or less. The constitution is further preferable. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after the metal layer is provided. Specifically, at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, and (e) metal layer are repeated in this order. In the form of the formation step, at least one of (a) the film forming step, (d) the heating step, and the post-development exposure step, and (e) the metal layer forming step are sequentially repeated. The resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step.

(Surface activation treatment step) It is preferable that the manufacturing method of the layered product of the present invention includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step for the resin composition layer after the above-described development step. 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 resin composition layer, or may be performed on both the metal layer and the exposed resin composition layer, respectively. at least in part. It is preferable to perform surface activation treatment on at least a part of the metal layer, and it is preferable to perform surface activation treatment on a part or the whole of the region of the metal layer where the 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 composition layer (film) provided on the surface can be improved. Moreover, it is preferable to also perform surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to the surface activation treatment, the adhesiveness with the metal layer and the resin layer provided on the surface activated by the surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as in the case of performing negative development, it is difficult to be damaged by the surface treatment, and it is easy to improve the adhesiveness. Specifically, the surface activation treatment is selected from plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, Etching treatment of CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, and then immersion in Immersion treatment in organic surface treatment agents containing at least one amine group and thiol group compound, mechanical roughening treatment using a brush, plasma treatment is preferred, especially oxygen plasma using oxygen as a raw material gas Handling is better. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m ² , more preferably 1000-100,000 J/m ² , and most preferably 10,000-50,000 J/m ² .

(Manufacturing method of semiconductor element) Furthermore, the present invention discloses a semiconductor element including the cured product of the present invention or the laminate of the present invention. Moreover, this invention also discloses the manufacturing method of the semiconductor element which includes the manufacturing method of the hardened|cured material of this invention or the manufacturing method of the laminated body of this invention. As a specific example of a semiconductor element in which the resin composition of the present invention is used in 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. These contents are incorporated into this manual. [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. Unless otherwise specified, "parts" and "%" are based on mass.

<Manufacturing method of precursor of cyclized resin> [Synthesis Example 1: Synthesis of Cyclized Resin Precursor A-1 (Polymer A-1)] Mix 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diglyme, ethylene glycol dimethyl ether) and stirred at a temperature of 60°C for 4 hours, thereby synthesizing a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 17.0 g of thionium chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution obtained by dissolving 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was at -10 It was added dropwise to the reaction mixture at ±5°C over 60 minutes, and the mixture was stirred at room temperature for 2 hours. Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was collected by filtration, and dissolved in 500 g of tetrahydrofuran. To the obtained solution, 6000 g of water (poor solvent) was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was filtered again and dried at 45° C. for 3 days under reduced pressure. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added, and the mixture was stirred at room temperature for 35 minutes. Then, this was added to 3000 g of ethanol, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. To this, 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by Ambertec Ltd.) were added, followed by stirring for 4 hours. After that, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried at 45° C. for 24 hours under reduced pressure to obtain 45.1 g of polymer A-1. The molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000. The structure of the polymer A-1 is presumed to be a structure represented by the following formula (A-1).

[Synthesis Example 2: Synthesis of Cyclized Resin Precursor A-2 (Polymer A-2)] 23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of diphthalic dianhydride (BPDA) were added to the separable flask, and 2-hydroxyethyl methacrylate ( HEMA) 39.69g and tetrahydrofuran 136.83g, stirring at room temperature (25 degreeC), pyridine 24.66g was added, stirring, and the reaction mixture was obtained. After the heat generation based on the reaction was completed, it was cooled to room temperature and allowed to stand for 16 hours. Next, under ice-cooling, a solution obtained by dissolving 62.46 g of dicyclohexylcarbodiimide (DCC) in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring. -Diaminodiphenyl ether (DADPE) 27.42g was added over 60 minutes while suspending in 119.73g of tetrahydrofuran. Furthermore, after 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 tetrahydrofuran was added. A reaction liquid was obtained by removing the precipitate generated in the reaction mixture by filtration. The obtained reaction liquid was added to 716.21 g of ethanol, whereby a precipitate formed of a crude polymer was generated. The resulting crude polymer was filtered off and 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 out and then vacuum-dried, thereby obtaining 80.3 g of powdery polymer A-2. The molecular weight of the polymer A-2 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000. The structure of the polymer A-2 is presumed to be a structure represented by the following formula (A-2).

[Synthesis Examples 3 to 7: Synthesis of Cyclized Resin Precursors A-3 to A-7 (Polymers A-3 to A-7)] A polymer A- having a structure represented by any one of the following formulae (A-3) to (A-7) was synthesized by the same method as in Synthesis Example 1, except that the compounds used were appropriately changed. 3 to A-7. The Mw of polymer A-3 was 20500, the Mw of polymer A-4 was 20000, the Mw of polymer A-5 was 21000, the Mw of polymer A-6 was 19000, and the Mw of polymer A-7 was 22000.

[化學式63]

[Chemical formula 62]

[Chemical formula 63]

<Examples and Comparative Examples> In each Example, each 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, the content of each component described in the table is the amount (parts by mass) described in parentheses in each column of the table. The obtained 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 the table|surface, the description of "-" shows that a composition does not contain the corresponding component. In addition, the description in the column of "resist acid value" in a table|surface shows the quantity of the acid group contained in the composition with respect to 1 g of composition, and the unit is mgKOH/g.

[Table 1] Precursors of Cyclized Resins Sensitizer Organometallic complexes polymeric compound Polymerization Inhibitor / Migration Inhibitor additive Metal Adhesion Improver Other alkali generators Compound B solvent Resist acid value type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass Example 1 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 2 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-2 2.0 GBL 40 DMSO 10 3.7 3 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-3 2.0 GBL 40 DMSO 10 3.7 4 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-4 2.0 GBL 40 DMSO 10 3.7 5 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-5 2.0 GBL 40 DMSO 10 3.7 6 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-6 2.0 GBL 40 DMSO 10 3.7 7 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-7 2.0 GBL 40 DMSO 10 3.7 8 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-8 2.0 GBL 40 DMSO 10 3.7 9 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-9 2.0 GBL 40 DMSO 10 3.7 10 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-10 2.0 GBL 40 DMSO 10 3.7 11 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 4.0 GBL 40 DMSO 10 3.7 12 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 8.0 GBL 40 DMSO 10 3.5 13 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-2 4.0 GBL 40 DMSO 10 3.7 14 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-2 8.0 GBL 40 DMSO 10 3.5 15 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-2 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 16 A-2 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 17 A-3 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 18 A-4 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 19 A-5 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 I-1 0.8 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 20 A-6 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 I-2 0.8 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.2 twenty one A-7 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 2.8 twenty two A-1 35.0 B-2 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 twenty three A-1 35.0 B-3 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 twenty four A-1 35.0 B-1 1.1 - 0 C-2 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 25 A-1 35.0 B-1 1.1 - 0 C-1 6 D-2 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7

[Table 2] Precursors of Cyclized Resins Sensitizer Organometallic complexes polymeric compound Polymerization Inhibitor / Migration Inhibitor additive Metal Adhesion Improver Other alkali generators Compound B solvent Resist acid value type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass Example 26 A-1 35.0 B-1 1.1 - 0 C-1 6 D-3 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 27 A-1 35.0 B-1 1.1 - 0 C-1 6 D-4 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 28 A-1 35.0 B-1 1.1 X-1 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 29 A-1 35.0 B-1 1.1 X-2 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 30 A-1 35.0 B-1 1.1 X-3 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 31 A-1 35.0 B-1 1.1 X-4 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 32 A-1 35.0 B-1 1.1 X-5 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 33 A-1 35.0 B-1 1.1 X-6 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 34 A-1 35.0 B-1 1.1 X-7 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 35 A-1 35.0 B-1 1.1 X-8 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 36 A-1 35.0 B-1 1.1 - 0 C-1 6 - 0 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.8 37 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 - 0.0 H-1 2.0 GBL 40 DMSO 10 3.8 38 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 - 0.0 H-1 8.0 GBL 40 DMSO 10 3.6 39 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-2 2.0 GBL 40 DMSO 10 3.7 40 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-2 2.0 GBL 40 DMSO 10 3.7 41 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 42 A-1 35.0 B-1 1.1 X-1 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 43 A-2 35.0 B-2 1.1 - 0 C-1 6 D-4 0.1 - 0 E-2 2.4 E-3 0.9 F-2 1 G-1 2.0 H-1 2.0 NMP 45 EL 10 3.3 44 A-2 35.0 B-2 1.1 - 0 C-1 6 D-4 0.1 - 0 E-2 2.4 E-3 0.9 F-2 1 G-1 2.0 H-2 2.0 NMP 45 EL 10 3.3 45 A-2 35.0 B-2 1.1 - 0 C-1 6 D-4 0.1 - 0 E-2 2.4 E-3 0.9 F-2 1 G-1 2.0 H-4 2.0 NMP 45 EL 10 3.3 46 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 3.0 H-1 2.0 GBL 40 DMSO 10 3.7 47 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 4.0 H-1 2.0 GBL 40 DMSO 10 3.7 48 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-12 2.0 GBL 40 DMSO 10 3.7 49 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-13 2.0 GBL 40 DMSO 10 3.7 50 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-14 2.0 GBL 40 DMSO 10 3.7

[table 3] Precursors of Cyclized Resins Sensitizer Organometallic complexes polymeric compound Polymerization Inhibitor / Migration Inhibitor additive Metal Adhesion Improver Other alkali generators Compound B solvent Resist acid value type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass Example 51 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-15 2.0 GBL 40 DMSO 10 3.7 52 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-16 2.0 GBL 40 DMSO 10 3.7 53 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-17 2.0 GBL 40 DMSO 10 3.7 54 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-18 2.0 GBL 40 DMSO 10 3.7 55 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-19 2.0 GBL 40 DMSO 10 3.7 56 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-20 2.0 GBL 40 DMSO 10 3.7 57 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-21 2.0 GBL 40 DMSO 10 3.7 58 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-22 2.0 GBL 40 DMSO 10 3.7 59 A-1 35.0 B-1 1.1 X-1 1.1 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-1 2.0 GBL 40 DMSO 10 3.7 60 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-23 4.0 GBL 40 DMSO 10 3.7 61 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-24 4.0 GBL 40 DMSO 10 3.7 62 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-25 4.0 GBL 40 DMSO 10 3.7 63 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-26 4.0 GBL 40 DMSO 10 3.7 64 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-26 4.0 GBL 40 DMSO 10 3.7 65 A-1 35.0 B-1 1.1 - 0 C-1 6 D-1 0.1 D-5 2.0 - 0 - 0 F-1 1 G-1 2.0 H-26 4.0 GBL 40 DMSO 10 3.7 Comparative example 1 A-2 35.0 B-2 1.1 - 0 C-1 6 D-4 0.1 - 0 E-2 2.4 E-3 0.9 F-2 1 H-11 2.0 - 0.0 NMP 45 EL 10 6.5 2 A-2 35.0 B-2 1.1 - 0 C-1 6 D-4 0.1 - 0 E-2 2.4 E-3 0.9 F-2 1 H-11 1.0 - 0.0 NMP 45 EL 10 4.9

The details of each component described in the table are as follows.

[Precursors of cyclized resins] · A-1 to A-7: Polymers A-1 to A-7 obtained by the above synthesis example

[Photosensitizer (photopolymerization initiator)] ·B-1 to B-3: Compounds of the following structures [Chemical formula 64]

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: Pentamethylcyclopentadienyltrimethoxide 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 65]

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

[Polymerizable compound (radical crosslinking agent)] C-1 to C-2: compounds of the following structures [Chemical formula 66]

[Polymerization inhibitor/migration inhibitor] D-1 to D-5: compounds of the following structures [Chemical formula 67]

[Additives] · E-2 to E-3: Compounds of the following structures · I-1 to I-2: Compounds of the following structures [Chemical formula 68]

在上述結構式中，Et表示乙基。 [Metal Adhesion Improver] F-1 to F-2: Compounds of the following structures [Chemical Formula 69]

In the above structural formula, Et represents an ethyl group.

[Other base generators] G-1 to G-2: Compounds of the following structures H-11: Compounds of the following structures [Chemical formula 70]

[化學式72]

[Compound B] H-1 to H-10, H-12 to H-26: compounds of the following structures [Chemical formula 71]

[Chemical formula 72]

[Solvent] · NMP: N-methyl-2-pyrrolidone EL: ethyl lactate DMSO: dimethyl sulfoxide GBL: gamma-butyrolactone

＜Evaluation＞ [Evaluation of storage stability] The viscosity (0 day) of the resin composition prepared in each Example and the comparative example and the composition for comparison were measured using an E-type viscometer, respectively. After the composition was allowed to stand at 25° C. for 14 days in a light-shielding and airtight container, the viscosity was measured again using an E-type viscometer (14 days). The viscosity change rate (%) was calculated according to the following formula. Based on the obtained viscosity change rate (%), evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "Storage stability" in the following table. The lower the viscosity change rate, the higher the storage stability. Viscosity change rate (%)=|100×{1-(viscosity (14 days)/viscosity (0 days))}| The measurement of viscosity was performed at 25 degreeC, and others were based on JIS Z 8803:2011. -Evaluation criteria- A: The viscosity change rate is 5% or less. B: The viscosity change rate exceeds 5% and is 10% or less. C: The viscosity change rate exceeds 10% and is 15% or less. D: The viscosity change rate exceeds 15% and is 20% or less. E: The viscosity change rate exceeded 20%.

[Evaluation of Elongation at Break] The resin compositions or compositions for comparison prepared in each of the Examples and Comparative Examples were 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, thereby obtaining a resin composition layer having a uniform thickness of about 15 μm on the silicon wafer. In the example described as "negative" in the column of development conditions in the following table, the entire surface of the resin composition layer on the silicon wafer was exposed at an 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. In the example described as "M" in the column of exposure conditions, exposure was performed using a stepper as a light source. In the example described as "D" in the column of exposure conditions, exposure was performed using a direct exposure apparatus (ADTEC DE-6UH III) as a light source. In the example described as "A" in the column of "Curing method", the temperature of the resin composition layer after the exposure was heated at a temperature increase rate of 10°C/min under a nitrogen atmosphere using a hot plate, and the temperature reached the After the temperature described in the column of "hardening temperature (°C)", the above temperature was maintained for 3 hours. In the example described as "B" in the column of "hardening method", an infrared lamp heating device (manufactured by ADVANCE RIKO, Inc., RTP-6) was used, and in a nitrogen atmosphere, the heating rate was 10°C/min. The resin film obtained in each Example was heated up, and after reaching the temperature described in "hardening temperature (degreeC)", the said temperature was maintained for 3 hours. The cured resin composition layer (cured product) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled hardened material was punched out using a punching machine to produce a test piece having a sample width of 3 mm and a sample length of 30 mm. The elongation in the longitudinal direction of the obtained test piece was measured in accordance with JIS-K6251 at a crosshead speed of 300 mm/min in an environment of 25° C. and 65% RH (relative humidity) using a tensile tester (Tensilon). measured. The measurement was performed five times, 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 are described in the column of "elongation at break" in the table. It can be said that the larger the index value, the more excellent the film strength of the cured product. -Evaluation Criteria- A: The above-mentioned index value is 65% or more. B: The above index value is more than 60% and less than 65%. C: The above-mentioned index value is 55% or more and less than 60%. D: The above-mentioned index value is 50% or more and less than 55%. E: The above index value is less than 50%.

[Evaluation of Adhesion] The resin compositions or the comparative compositions prepared in the respective Examples and Comparative Examples were applied in layers on a copper substrate by spin coating, thereby forming a resin composition layer or a comparative composition. layer with composition. The copper substrate on which the obtained resin composition layer or the comparative composition layer was formed was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer or comparative composition layer with a uniform thickness of 20 μm on the copper substrate material layer. In the example described as "negative" in the column of "development conditions" in the table, a mask in which a square-shaped non-mask portion of 100 μm square was formed was used and described as “positive” in the column of “development conditions” in the table In this example, a photomask with a 100 μm square square mask portion formed thereon was used, and the exposure energy was 500 mJ/cm ² with the light of the exposure wavelength (nm) described in the column of “Exposure wavelength nm” in the table. The resin composition layer or the comparative composition layer on the copper substrate was exposed. In the example described as "M" in the column of exposure conditions, exposure was performed using a stepper as a light source. In the example described as "D" in the column of exposure conditions, a direct exposure device (ADTEC DE-6UH III) was used as a light source without using a mask, and laser direct imaging exposure was performed in the range of 100 μm square. Then, it developed with cyclopentanone for 60 seconds, and the square-shaped resin layer of 100 micrometers square was obtained. In the example described as "A" in the column of "Curing method", the temperature of the resin composition layer after the exposure was heated at a temperature increase rate of 10°C/min under a nitrogen atmosphere using a hot plate, and the temperature reached the After the temperature described in the column of "hardening temperature (°C)", the above temperature was maintained for 3 hours. In the example described as "B" in the column of "hardening method", an infrared lamp heating device (manufactured by ADVANCE RIKO, Inc., RTP-6) was used, and in a nitrogen atmosphere, the heating rate was 10°C/min. The resin film obtained in each Example was heated up, and after reaching the temperature described in "hardening temperature (degreeC)", the said temperature was maintained for 3 hours. In an environment of 25°C and 65% relative humidity (RH), using an adhesive strength tester (manufactured by XYZTEC, CondorSigma), the shear force of the 100 μm square resin layer on the copper substrate was measured and evaluated as follows benchmarks were evaluated. The evaluation results are described in the "adhesion" column of the table. It can be said that the greater the shearing force, the better the metal adhesion (copper adhesion) of the cured film. - Evaluation Criteria - A: The shear force exceeded 30 gf. B: The shear force exceeds 25 gf and is 30 gf or less. C: The shear force exceeds 20 gf and is 25 gf or less. D: The shear force is 20 gf or less. In addition, 1gf is 0.00980665N.

[Table 4] Exposure conditions Exposure wavelength nm Development conditions Hardening temperature [℃] Hardening method storage stability Elongation at break tightness Example 1 M 365 burden 230 A A C A 2 M 365 burden 230 A A B A 3 M 365 burden 230 A A C A 4 M 365 burden 230 A A B A 5 M 365 burden 230 A A C A 6 M 365 burden 230 A A B A 7 M 365 burden 230 A A B A 8 M 365 burden 230 A A C A 9 M 365 burden 230 A A C A 10 M 365 burden 230 A A C A 11 M 365 burden 230 A A C A 12 M 365 burden 230 A B B B 13 M 365 burden 230 A A A A 14 M 365 burden 230 A B A B 15 M 365 burden 230 A B A B 16 M 365 burden 230 A A C A 17 M 365 burden 230 A A C A 18 M 365 burden 230 A A C A 19 M 365 just 230 A A C A 20 M 365 just 230 A A C A twenty one M 365 burden 230 A A C A twenty two M 365 burden 230 A A C A twenty three M 365 burden 230 A A C A twenty four M 365 burden 230 A A C A 25 M 365 burden 230 A A C B

[table 5] Exposure conditions Exposure wavelength nm Development conditions Hardening temperature [℃] Hardening method storage stability Elongation at break tightness Example 26 M 365 burden 230 A A C B 27 M 365 burden 230 A A C B 28 M 365 burden 230 A A C A 29 M 365 burden 230 A A C A 30 M 365 burden 230 A A C A 31 M 365 burden 230 A A C A 32 M 365 burden 230 A A C A 33 M 365 burden 230 A A C A 34 M 365 burden 230 A A C A 35 M 365 burden 230 A A C A 36 M 365 burden 230 A A C B 37 M 365 burden 230 A A D A 38 M 365 burden 230 A B B B 39 M 365 burden 200 A A C A 40 M 365 burden 180 A A D A 41 M 365 burden 230 B A C A 42 M 405 burden 230 A A C A 43 M 365 burden 230 A A C A 44 M 365 burden 230 A A B A 45 M 365 burden 230 A A B A 46 M 365 burden 230 A C B A 47 M 365 burden 230 A D B B 48 M 365 burden 230 A A C A 49 M 365 burden 230 A A B A 50 M 365 burden 230 A A C A

[Table 6] Exposure conditions Exposure wavelength nm Development conditions Hardening temperature [℃] Hardening method Stability over time Elongation at break tightness Example 51 M 365 burden 230 A A B A 52 M 365 burden 230 A A B A 53 M 365 burden 230 A B B A 54 M 365 burden 230 A B B A 55 M 365 burden 230 A A C A 56 M 365 burden 230 A A C A 57 M 365 burden 230 A A B A 58 M 365 burden 230 A A B A 59 D 405 burden 230 A A C A 60 M 365 burden 230 A A A A 61 M 365 burden 230 A A A A 62 M 365 burden 230 A A A A 63 M 365 burden 230 A A A A 64 M 365 burden 200 A A B A 65 M 365 burden 180 A A C A Comparative example 1 M 365 burden 230 A E C D 2 M 365 burden 230 A B E C

From the above results, it was found that by using the resin composition of the present invention, a resin composition excellent in the storage stability of the composition and the elongation at break of the obtained cured product can be obtained. The composition for comparison in Comparative Example 1 did not contain Compound B but contained a large amount of "H-11" as another alkali generator. In this aspect, it can be seen that the storage stability of the composition is poor. The composition for comparison in Comparative Example 2 contained no compound B but a small amount of "H-11" as another base generator. In this aspect, it was found that the obtained cured product was inferior in elongation at break.

<Example 101> The resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed in a layer form by spin coating, and dried at 100° C. for 4 minutes. After forming a photosensitive film with a film thickness of 20 μm, exposure was performed using a stepper (Nikon Co., Ltd., NSR1505 i6). For exposure, via a mask (a binary mask with a pattern of 1:1 line-to-space, line width 10 μm) at a wavelength of 365 nm. After exposure, it was heated at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes, and rinsed with PGMEA for 30 seconds, thereby obtaining a layer pattern. 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 to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, a semiconductor element was manufactured using these interlayer insulating films for rewiring layers, and as a result, normal operation was confirmed.

Claims (14)

A resin composition comprising a precursor of a cyclized resin and Compound B which produces a base by the action of a base. The resin composition according to claim 1, wherein The base produced from compound B is an amine. The resin composition according to claim 1 or claim 2, wherein Compound B has an urethane bond. The resin composition according to claim 1 or claim 2, wherein compound B is a compound represented by the following formula (1-1), formula (1-2) or formula (1-3), [Chemical formula 1]

In formula (1-1), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, and R ¹ and R ² can be bonded to form a ring structure; In formula (1-2), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, R ¹ and R ² can be bonded to form a ring structure, R ³ each independently represents a hydrogen atom or a hydrocarbon group that can be substituted, R ⁴ represents cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) ₂ R, fluorinated alkyl group or halogen atom, R Represents a hydrocarbon group that can be substituted; in formula (1-3), R ¹ represents a hydrogen atom or a hydrocarbon group that can be substituted, R ² represents a hydrocarbon group that can be substituted, R ¹ and R ² can be bonded to form a ring structure, R ³ respectively independently represent a hydrogen atom or a hydrocarbon group that can be substituted, and Ar represents a group selected from the group consisting of cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, - S(=O) ₂ R, a fluorinated alkyl group, an aromatic group substituted with at least one of a halogen atom, and R represents an optionally substituted hydrocarbon group. The resin composition according to claim 1 or claim 2, further comprising a thermal base generator or a photobase generator. The resin composition according to claim 1 or claim 2, further comprising a thermal alkali generator. The resin composition according to claim 1 or claim 2, further comprising a photopolymerization initiator. The resin composition according to claim 1 or claim 2, further comprising a polymerizable compound. A hardened product obtained by hardening the resin composition according to any one of claim 1 to claim 8. A layered body comprising two or more layers formed of the hardened product described in claim 9, and including a metal layer between any of the layers formed of the hardened product. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of Claims 1 to 8 on a substrate to form a film. The method for producing a cured product according to claim 11, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern. The manufacturing method of the hardened|cured material of Claim 11 which comprises the heating process of heating the said film at 50-450 degreeC. A semiconductor element comprising the cured product of claim 9.