TW202140621A - Photosensitive resin composition, cured film, layered product, method for producing cured film, and semiconductor device - Google Patents

Abstract

A photosensitive resin composition which comprises at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazole, an organometal complex having a photopolymerization-initiating ability, and a hindered phenol compound, and which, when having been formed into a 15-[mu]m-thick film through 5-minute heating at 100 DEG C, has an absorbance at 405-nm wavelength of 0.2-0.6; a cured film obtained by curing the photosensitive resin composition; a layered product including the cured film; a method for producing the cured film; and a semiconductor device including the cured film or the layered product.

Description

Photosensitive resin composition, cured film, laminate, cured film manufacturing method, and semiconductor device

The present invention relates to a method for manufacturing a photosensitive resin composition, a cured film, a laminate, a cured film, and a semiconductor device.

Resins such as polyimide and polybenzoxazole have excellent heat resistance and insulation properties, and are therefore suitable for various applications. The above-mentioned use is not particularly limited. If a semiconductor device for packaging is exemplified, the use of a material as an insulating film or a sealing material, or a protective film can be cited. In addition, it is also used as a base film or coverlay film of a flexible substrate.

For example, in the above applications, resins such as polyimines and polybenzoxazoles are used in the form of photosensitive resin compositions containing polyimines, polybenzoxazoles, and the like, or photosensitive resin compositions containing these precursors. . Such a photosensitive resin composition is applied to a substrate by coating, for example, to form a photosensitive film, and then exposed, developed, heated, etc. as necessary, whereby a cured product can be formed on the substrate. The aforementioned polyimide precursor and polybenzoxazole precursor are cyclized, for example, by heating, and in the cured product, they become polyimide and polybenzoxazole, respectively. The photosensitive resin composition can be applied by a well-known coating method. Therefore, it can be said that, for example, the shape, size, and application position of the applied photosensitive resin composition during application have a high degree of freedom in design and other manufacturing flexibility. Excellent. In addition to the high performance possessed by polyimines, polybenzoxazoles, etc., from the viewpoint of excellent manufacturing adaptability, the industrial application of the above-mentioned photosensitive resin composition is increasingly expected.

For example, Patent Document 1 describes a negative photosensitive resin composition containing a polyimide precursor of a specific structure: 100 parts by mass, a photopolymerization initiator: 1-20 parts by mass, and More than one monocarboxylic acid compound with 2 to 30 carbons selected from the functional group in the group including a hydroxyl group, an ether group and an ester group: 0.01 to 10 parts by mass.

[Patent Document 1] JP 2011-191749 A

When forming a pattern composed of a photosensitive resin composition, it is required to increase the shape of the pattern.

The object of the present invention is to provide a photosensitive resin composition having an excellent pattern shape of the obtained pattern, a cured film obtained by curing the photosensitive resin composition, a laminate including the cured film, and a method for producing the cured film And a semiconductor device including the above-mentioned cured film or the above-mentioned laminate.

Examples of representative embodiments of the present invention are shown below. <1> A photosensitive resin composition comprising: at least one selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole Resin Organometallic complexes with photopolymerization initiation ability; and Hindered phenol compounds, When a film made of the photosensitive resin composition with a thickness of 15 μm is formed by heating at 100° C. for 5 minutes, the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6. <2> A photosensitive resin composition comprising: at least one selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole Resin Organometallic complexes with photo-radical polymerization initiation ability; and Hindered phenol compounds, For forming a film composed of the above-mentioned photosensitive resin composition, The film thickness of the film is 15 μm or more, and the absorbance at a wavelength of 405 nm of the film is 0.2 to 0.6. <3> The photosensitive resin composition as described in <1> or <2>, wherein the organometallic complex compound has photoradical polymerization initiation ability. <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the metal in the organic metal complex compound is titanium. <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the organic metal complex compound is a metallocene compound. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the content of the organic metal complex compound is 0.5 to 5.0 mass relative to the total solid content of the photosensitive resin composition %. <7> The photosensitive resin composition according to any one of <1> to <6>, which further contains a sensitizer. <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the resin is a polyimide containing at least one of a cyclic isoimide structure and a cyclic isoimide structure. The amide precursor, and the total molar amount of the cyclic amide structure and the cyclic isoimine structure in 1 g of the polyimide precursor is 0.08 to 1.68 mmol/g. <9> The photosensitive resin composition according to any one of <1> to <8>, which is used to form a photosensitive film for negative development. <10> The photosensitive resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer. <11> A cured film obtained by curing the photosensitive resin composition described in any one of <1> to <10>. <12> A laminate comprising two or more layers of the cured film described in <11>, and a metal layer is included between any of the cured films. <13> A method for manufacturing a cured film, which includes a film forming process, applying the photosensitive resin composition described in any one of <1> to <10> to a substrate to form a film. <14> The method for producing a cured film as described in <13>, which includes: an exposure process for exposing the film; and a developing process for developing the film. <15> The method for producing a cured film as described in <13> or <14>, wherein the above-mentioned exposure is exposure by a laser direct imaging method. <16> The method for producing a cured film according to any one of <13> to <15>, which includes a heating process in which the film is heated at 50 to 450°C. <17> A semiconductor device comprising the cured film described in <11> or the laminated body described in <12>. [Effects of the invention]

According to the present invention, there is provided a photosensitive resin composition having an excellent pattern shape of the obtained pattern, a cured film formed by curing the photosensitive resin composition, a laminate including the cured film, a method for manufacturing the cured film, and A semiconductor device including the above-mentioned cured film or the above-mentioned laminate.

Hereinafter, the main embodiment of the present invention will be described. However, the present invention is not limited to the specified embodiment. In this specification, the numerical range indicated by the symbol "～" refers to the range that includes the numerical values described before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only includes independent processes, but also includes processes that cannot be clearly distinguished from other processes as long as the process can achieve the expected effect of the process. In the label of the group (atomic group) in this specification, the label not marked with substituted and unsubstituted includes a group (atomic group) without a substituent, and also includes a group (atomic group) with a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. In addition, as the light used in the exposure, active rays or radiation such as the bright-ray spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, “(meth)acrylate” refers to both or either of “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to “acrylic acid” and “methacrylate”. Both or either of "acrylic acid" and "(meth)acryloyl" refer to both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, in this specification, the solid content concentration means the mass percentage of components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values based on gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be used, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and protecting columns HZ-L and TSKgel Super HZM-M as the columns. , TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, these molecular weights shall be those obtained by measurement using THF (tetrahydrofuran) as an eluent. In addition, as long as there is no special description, the detection in the GPC measurement is obtained by using a UV ray (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is only necessary to have another layer on the upper side or the lower side of the layer that becomes the reference among the plurality of layers of interest. That is, a third layer or element may be further interposed between the layer serving as the reference and the other layer described above, and the layer serving as the reference need not be in contact with the other layer described above. In addition, unless otherwise specified, the direction of the stacked layers on the substrate is referred to as "up", or when the photosensitive film is present, the direction from the substrate to the photosensitive film is referred to as "up", and the opposite direction is referred to as "up" Down". In addition, the setting of this vertical direction is for the convenience of this manual. In the actual situation, the "up" direction in this manual may be different from the vertical direction. In this specification, unless otherwise stated, the composition may include two or more compounds corresponding to the components as each component included in the composition. In addition, unless otherwise stated, the content of each component in the composition means the total content of all the compounds corresponding to the component. In this specification, unless otherwise stated, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred aspects is a better aspect.

(Photosensitive resin composition) The first aspect of the photosensitive resin composition of the present invention is as follows: A photosensitive resin composition comprising: selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and At least one resin in the group of polybenzoxazoles; organometallic complex compounds with photopolymerization initiation ability; and hindered phenol compounds formed by heating at 100°C for 5 minutes with a film thickness of 15 μm. In the case of a film composed of a resin composition, the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6. The second aspect of the photosensitive resin composition of the present invention is as follows: a photosensitive resin composition comprising: selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and At least one resin in the group of polybenzoxazoles; organometallic complex compounds having photo-radical polymerization initiation ability; and hindered phenol compounds for forming a film composed of the above-mentioned photosensitive resin composition, and the film of the above-mentioned film The thickness is 15 μm or more, and the absorbance at a wavelength of 405 nm of the film is 0.2 to 0.6. Hereinafter, when it is simply described as "photosensitive resin composition", "photosensitive resin composition of the present invention", etc., it means both the above-mentioned first aspect and the above-mentioned second aspect. In particular, when only the photosensitive resin composition of the first aspect (second aspect) is described, it is described as "the photosensitive resin composition of the first aspect" and "the photosensitive resin of the second aspect" Composition" etc.

The photosensitive 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. In addition, the photosensitive resin composition of the present invention is preferably used to form a photosensitive film for negative development. In the present invention, negative development refers to development in which the non-exposed part is removed by development during exposure and development, and positive development refers to development in which the exposed part is removed by development. As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method, for example, the exposure method explained in the exposure process in the explanation of the production method of the cured film described later, the developer explained in the development process, and Development method.

The photosensitive resin composition of the present invention is excellent in the exposure sensitivity and the pattern shape of the obtained pattern. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it can be presumed as follows.

For example, as described in Patent Document 1, the addition of an organic titanium compound having polymerization initiation ability and the like to the photosensitive resin composition is performed. However, when a photosensitive film is formed from a photosensitive resin composition containing an organometallic complex, and exposure and development are performed, a pattern with an excellent pattern shape may not be obtained in some cases. In the present invention, the excellent shape of the pattern means that the angle (cone angle) formed by the surface of the substrate on which the pattern is formed and the side surface of the pattern is close to the desired angle, and the cross-sectional shape of the pattern is not a constricted shape. As a result of in-depth research, the inventors learned that by using The film when it contains an organometallic complex and a hindered phenol compound and is heated at 100°C for 5 minutes to form a film made of the photosensitive resin composition (also referred to as a "specific film") with a film thickness of 15 μm A photosensitive resin composition having an absorbance of 0.2 to 0.6 at a wavelength of 405nm, or containing organometallic complexes and hindered phenol compounds, and for forming a film composed of the photosensitive resin composition, the film thickness of the film is 15μm As described above, the photosensitive resin composition having an absorbance at a wavelength of 405 nm of the film is 0.2 to 0.6, even when a thick film (for example, 15 μm or more) is formed, the pattern shape is excellent. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it can be presumed as follows. Since the absorbance at a wavelength of 405 nm of the specific film or the film composed of the photosensitive resin composition is 0.2 to 0.6, it is considered that the exposure light is easily transmitted to the deep part of the pattern and the pattern shape is excellent. In addition, since the hindered phenol compound has low volatility, it is considered that unnecessary polymerization reaction can be suppressed even in a position on the exposure light side of the pattern, and the pattern shape is excellent. In addition, for example, when the photosensitive film is formed in contact with the metal layer, and the photosensitive resin composition contains at least one resin selected from the group consisting of a polyimide precursor or a polybenzoxazole precursor, The hindered phenol compound is likely to be unevenly distributed on the surface of the metal layer, and the crosslinking density in the deep part of the film is likely to be in an appropriate range. Therefore, it is considered that the cyclization of the precursor is easy to proceed after pattern formation, and it is easy to obtain adhesion, mechanical properties, and chemical resistance. A cured film with excellent performance. Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

＜Absorbance＞ [First aspect] Regarding the photosensitive resin composition of the first aspect of the present invention, when a film composed of the photosensitive resin composition with a film thickness of 15 μm is formed by heating at 100°C for 5 minutes, the wavelength of the film is 405 nm The absorbance is 0.2～0.6. The above-mentioned heating is not particularly limited. For example, it can be performed by the method described in the below-mentioned Examples. The absorbance of the film having a film thickness of 15 μm at a wavelength of 405 nm is preferably 0.2 to 0.5, and more preferably 0.2 to 0.4. In addition, with regard to the photosensitive resin composition of the first aspect, the absorbance at a wavelength of 405 nm of a film with a film thickness of 20 μm formed in the same method is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and more preferably 0.2 to 0.4 To be further preferred. In addition, with regard to the photosensitive resin composition of the first aspect, the absorbance at a wavelength of 405 nm of a film with a thickness of 30 μm formed by the same method is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and more preferably 0.2 to 0.4 To be further preferred. The above-mentioned absorbance is not particularly limited. For example, it can be measured using an ultraviolet-visible spectrophotometer. The above-mentioned absorbance can be determined by, for example, the structure of the specific resin contained in the photosensitive resin composition (for example, the structure of the monomer used in the specific resin, the cyclic imine structure and the cyclic structure of the polyimide precursor). The total content of the isoimide structure contains the molar amount, the content of the benzoazole structure in the polybenzoxazole precursor, etc.), and the type and content of the compound that absorbs at a wavelength of 405nm.

[Second aspect] The photosensitive resin composition of the second aspect of the present invention is used for forming a film composed of the photosensitive resin composition, the film thickness of the film is 15 μm or more, and the absorbance at a wavelength of 405 nm of the film is 0.1 to 0.6. The method of forming the above-mentioned film is not particularly limited, and for example, the method of forming the film described in the film forming process described later can be mentioned. The film system composed of the photosensitive resin composition is preferably a dry film obtained by drying the photosensitive resin composition. The film thickness of the above-mentioned film can be 20 μm or more, and can also be 30 μm or more. The upper limit is not particularly limited, and for example, it can be 50 μm or less. The absorbance of the film at a wavelength of 405 nm is preferably 0.2 to 0.5, and more preferably 0.2 to 0.4. The above-mentioned absorbance is not particularly limited. For example, it can be measured using an ultraviolet-visible spectrophotometer. The above-mentioned absorbance can be determined by, for example, the structure of the specific resin contained in the photosensitive resin composition (for example, the structure of the monomer used in the specific resin, the cyclic imine structure and the cyclic structure of the polyimide precursor). The total content of the isoimide structure contains the molar amount, the content of the benzoazole structure in the polybenzoxazole precursor, etc.), and the type and content of the compound that absorbs at a wavelength of 405nm.

＜Specific resin＞ The photosensitive resin composition of the present invention includes at least one resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole . In the photosensitive resin composition of the present invention, as the specific resin, it is preferable to include a polyimide or a polyimine precursor, and it is more preferable to include a polyimine precursor. In addition, from the viewpoint of easily obtaining the above-mentioned cured film excellent in adhesion, mechanical properties, or chemical resistance, the photosensitive resin composition of the present invention contains a polyimide precursor or polybenzo-aperoxide as a specific resin. An azole precursor is preferred, and a polyimide precursor is more preferred. Moreover, it is preferable that the specific resin has a radically polymerizable group. When the specific resin has a radically polymerizable group, the photosensitive resin composition preferably contains a photo-radical polymerization initiator described later as the photosensitizer, and contains the photo-radical polymerization initiator described later as the photosensitizer and contains The radical crosslinking agent described later is more preferable, and it is more preferable to include the photoradical polymerization initiator described below as a photosensitizer, the radical crosslinking agent described below, and the sensitizer described below. From such a photosensitive resin composition, for example, a negative photosensitive film is formed.

〔Polyimide precursor〕 The polyimide precursor used in the present invention is a polyimide precursor containing at least one of a cyclic imine structure and a cyclic isoimide structure, and 1 g of the above polyimide precursor The total molar amount of the cyclic imine structure and the cyclic isoimine structure is 0.08 to 1.68 mmol/g, preferably 0.10 to 1.00 mmol/g, and more preferably 0.12 to 0.80 mmol/g Preferably, 0.15 to 0.60 mmol/g is particularly preferred. In addition, the polyimide precursor used in the present invention is preferably a polyimide precursor containing a cyclic imine structure. In addition, the polyimide precursor of the present invention is dissolved in a solvent, coated on a substrate, and the solvent is removed (dried) to obtain a film with a thickness of 0.2 to 0.6, preferably 0.2 to 0.6, Better. The polyimide precursor may have at least one of a cyclic imine structure and a cyclic isoimide structure in the side chain, but it is preferable to have it in the main chain. In this specification, the "main chain" refers to the relatively longest bonding chain in the molecules of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains.

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

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 monovalent organic group.

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

Preferably, R ^{111 is} derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, it includes a group consisting of a linear or branched aliphatic group having 2 to 20 carbons, a cyclic aliphatic group having 6 to 20 carbons, an aromatic group having 6 to 20 carbons, or a combination of these The diamine of the group is preferable, and the diamine containing the group which consists of a C6-C20 aromatic group is more preferable. As an example of an aromatic group, the following can be mentioned.

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

In the formula, A is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons which can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO- Or the group in a combination of these is preferred, a single bond or a C1-C3 alkylene group which may be substituted by a fluorine atom, -O-, -C(=O)-, -S- or The group in -SO ₂ -is more preferable, and -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -or -C(CH ₃ ) ₂ -are further good. In the formula, * indicates the bonding site with other structures.

As the diamine, specifically, at least one diamine selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1 ,4-Diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-di Aminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-amino) Cyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; meta- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenyl Phenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3, 3'-Diaminobenzophenone, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 2,2'-Dimethyl-4,4'-Diaminobiphenyl , 3,3'-Dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) Hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis( 3-amino-4-hydroxyphenyl) propane, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfide, double (4-Amino-3-hydroxyphenyl) sulfide, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4 -Aminophenoxy) phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, bis[4-(2-aminophenoxy)phenyl] ash, 1, 4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide , 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3, 3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diamino octa Fluorobiphenyl, 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'-diaminobiphenyl, 9,9'-bis(4-amine Phenyl) pyrene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonium, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 2,4- and 2,5 -Diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-tri Methyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4 -Aminophenyl) ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-amine) Phenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis( 4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4 -(4-Aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4 ,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4 ,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl Benzene, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4, 4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluoro Toluidine and 4,4'-diamino p-bitetraphenyl.

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

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

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

式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價的有機基團，R⁵⁰ ～R⁵⁷ 中的至少1個為氟原子、甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價的有機基團，可以舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式4]

式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子或三氟甲基。 作為提供式（51）或（61）的結構之二胺化合物，可以舉出2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用一種或者組合使用兩種以上。Moreover, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the divalent organic group represented by the formula (61) is more preferable. Formula (51) [Chemical Formula 3]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, ^{and at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group. ^Examples of the monovalent organic groups R ⁵⁰ to R 57 include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably carbons). Numbers 1 to 6) fluorinated alkyl groups, etc. [Chemical formula 4]

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

In addition, the following diamines can also be preferably used. [Chemical formula 5]

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

In formula (5), R ¹¹² is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ -and -NHCO- And the groups in these combinations are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons, -O-, -CO-, -S- and -SO ₂ -which may be substituted by fluorine atoms The group in is more preferred, and is selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO _2- The divalent group in the group of is further preferred.

式（O）中，R¹¹⁵ 表示4價的有機基團。R¹¹⁵ 的較佳範圍與式（2）中的R¹¹⁵ 同義，較佳範圍亦相同。Specifically, R ¹¹⁵ includes the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 7]

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

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic 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'-benzophenonetetracarboxylic 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-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10- Perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride Anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4- Phenyltetracarboxylic dianhydride and these C1-C6 alkyl groups and C1-C6 alkoxy derivatives.

In addition, as a preferred example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited.

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

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It ^{is preferred that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and it is more preferred that both of them contain a polymerizable group. As the polymerizable group, a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylenically unsaturated bonds, alkoxymethyl, hydroxymethyl, oxymethyl, epoxy, oxetanyl, and benzo Azole group, blocked isocyanate group, methylol group, amine group. As the radical polymerizable group possessed by the polyimide precursor, etc., a group having an ethylenically unsaturated bond is preferred. Examples of groups having ethylenically unsaturated bonds include vinyl groups, (methyl)allyl groups, groups represented by the following formula (III), etc. The groups represented by the following formula (III) are Better.

[Chemical formula 8]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. In formula (III), * represents the bonding site with other structures. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -or a polyalkyleneoxy group. Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy, ethylene, propylene, trimethylene, -CH ₂ CH( OH) CH ₂ -, polyalkyleneoxy is more preferred, and polyalkyleneoxy is even more preferred. In the present invention, polyalkoxyl group refers to a group to which two or more alkoxyl groups are directly bonded. The alkylene groups in the plurality of alkylene groups contained in the polyalkoxy group may be the same or different. When the polyalkylene group contains a plurality of different alkylene groups, the arrangement of the alkoxy group in the polyalkylene group can be a random arrangement or a block arrangement. , It can also be an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2-10, more preferably 2-6, more preferably 2-5 To be further preferred, 2 to 4 are further preferred, 2 or 3 is particularly preferred, and 2 is the most preferred. In addition, the above-mentioned alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. can be mentioned. In addition, the number of alkoxyl groups contained in the polyalkoxyl group (the number of repetitions of the polyalkoxyl group) is preferably 2-20, more preferably 2-10, and still more preferably 2-6. As polyoxyethylene group, from the viewpoint of solvent solubility and solvent resistance, polyoxyethylene group, polyoxypropylene group, polytrimethyleneoxy group, polytetramethyleneoxy group, or from a plurality of ethyleneoxy group A group formed by bonding an oxy group and a plurality of propyleneoxy groups is preferred, a polyethoxylate or a polypropyleneoxy group is more preferred, and a polyethoxylate group is even more preferred. In the group formed by bonding the above-mentioned plural ethoxy groups and plural propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, or they can be arranged in blocks, or they can be arranged into Alternate and other patterns. Preferred aspects of the number of repetitions of ethoxylates and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. As the monovalent organic group, one, two or three carbons constituting the aryl group can be exemplified, and an aromatic group and an aralkyl group having an acidic group bonded to one carbon are preferred. Specifically, an aromatic group having 6 to 20 carbons having an acidic group, and an aralkyl group having 7 to 25 carbons having an acidic group can be mentioned. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group. R ¹¹³ or R ¹¹⁴ is a hydrogen atom, and it is also more preferable that a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group are used.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1-30. The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. Base, octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethyl Oxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy, 2-(2-(2-(2-methoxyethoxy) Ethoxy)ethoxy)ethoxy and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl, and bicyclic Hexyl and pinenyl. Among them, the cyclohexyl group is the most preferable from the viewpoint of compatibility with high sensitivity. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with the aromatic group described later is preferred. As the aromatic group, specifically, substituted or unsubstituted benzene ring, naphthalene ring, pentacyclopentadiene ring, indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused five Benzene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, condensed benzene ring, benzene ring, terphenylene ring, pyrene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, Thiazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring , Nylidine ring, quinalidine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thien ring, chromene ring, Kou Yamaguchi star ring, brown ring, brown ring or brown ring. Benzene ring is the best.

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

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

In addition, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like is used can be mentioned.

式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示2價的有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基團，R¹¹³ 及R¹¹⁴ 中的至少一者為包含聚合性基之基團，兩者為聚合性基為較佳。The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors and the like used in the present invention is a precursor having a repeating unit represented by formula (2-A). With this structure, the width of the exposure latitude can be further expanded. 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 As a group, ^{at least one of R 113} and R ¹¹⁴ is a group containing a polymerizable group, and both of them are preferably a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ^{114 have the same meaning as A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ^{114 in} formula (2), respectively, and the preferred ranges are also the same. (5) In the formula ¹¹² R R ¹¹² is synonymous with, the preferred range is also the same.

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

式（2-1）～式（2-6）中，R¹¹¹ 、R¹¹³ 、R¹¹⁴ 、R¹¹⁵ 、A¹ 、及A² 分別與上述的式（2）中的R¹¹¹ 、R¹¹³ 、R¹¹⁴ 、R¹¹⁵ 、A¹ 、及A² 同義，較佳的態樣亦相同。The polyimide precursor, as a repeating unit having a cyclic imine structure or a cyclic isoimide structure, may also contain any one selected from the group consisting of the following formulas (2-1) to (2-6) At least one repeating unit in a group of indicated repeating units. [Chemical formula 10]

In formulas (2-1) to (2-6), R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , A ¹ , and A ^{2 are respectively the same as R 111} , R ¹¹³ , R in the above formula (2) ¹¹⁴ , R ¹¹⁵ , A ¹ , and A ^{2 have the} same meaning, and preferred aspects are also the same.

The total content of the repeating units represented by any one of the formula (2-1) to the formula (2-6) is 1 g of the cyclic imine structure and the cyclic isoimide structure in the polyimide precursor It is preferable that the total molar content of the content is within the above-mentioned range.

As an embodiment of the polyimide precursor in the present invention, there can be mentioned an aspect in which the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the 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 total content is not particularly limited, and all repeating units in the polyimide precursor at the end may be the repeating units represented by formula (2) and formulas (2-1) to (2-6) Any one of the repeating units represented by any one of ).

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

〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component. In this specification, the alkali-soluble polyimide means that 0.1 g or more of polyimide is dissolved at 23°C with respect to 100 g of 2.38% by mass tetramethylammonium aqueous solution. From the viewpoint of pattern formation, 0.5 Polyimine of g or more is preferable, and polyimide of 1.0 g or more is more preferable to dissolve. The upper limit of the above-mentioned dissolution amount is not particularly limited, but 100 g or less is preferable. In addition, from the viewpoint of the film strength and insulating properties of the obtained organic film, a polyimide-based polyimide having a plurality of imine structures in the main chain is preferable.

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

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

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

[Chemical formula 11]

In the formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferred.

In the formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH- , (Poly) alkoxylate having 2-30 carbon atoms (the carbon number of the alkylene group is preferably 2-12, more preferably 2-6, especially 2 or 3; repeating number is 1-12 Preferably, 1 to 6 are more preferable, and 1 to 3 are particularly preferable) or a group formed by combining two or more of them.

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

In the formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbons, a (poly)alkylene group having 2 to 30 carbons, or two or more of these are bonded. As a group, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with an oxygen atom bonded to ^{R 201 in formula (III).} In the formulas (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbons or the (poly)alkylene group having 2 to 30 carbons in L is the same as the number of carbons in the ^{above-mentioned R 21} The preferred aspects of the 2-12 alkylene group or the (poly)alkylene group having 2-30 carbon atoms are the same. In the formula (R1), the X-based oxygen atom is preferred. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same. The structure represented by the formula (R1) is formed, for example, by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate, etc.) Obtained by reaction. The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) get. As the polyoxyethylene group, from the viewpoint of solvent solubility and solvent resistance, polyoxyethylene group, polyoxypropylene group, polytrimethyleneoxy group, polytetramethyleneoxy group, or from a plurality of ethyleneoxy group A group formed by bonding an oxy group and a plurality of propyleneoxy groups is preferred, a polyethoxylate or a polypropyleneoxy group is more preferred, and a polyethoxylate group is even more preferred. In the group formed by bonding the above-mentioned plural ethoxy groups and plural propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, or they can be arranged in blocks, or they can be arranged into Alternate and other patterns. Preferred aspects of the number of repetitions of ethoxylates and the like in these groups are as described above.

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

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

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

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

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

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

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

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

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

In the formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meaning as in the formula (4). Formula (4-2) [Chemical Formula 15]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like. R ¹³¹ represents a divalent organic group. ^{As a divalent organic group, the same thing as R 111} in Formula (2) can be illustrated, and a preferable range is also the same. Moreover, as R ¹³¹ , the diamine residue remaining after removing the amine group of the diamine can be mentioned. Examples of diamines include aliphatic, cycloaliphatic, or aromatic diamines. As a specific example, an example ^{of R 111} in the formula (2) of the polyimide precursor can be given.

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

Examples of diamines containing two or more of ethylene glycol chains and propylene glycol chains or both in a molecule include JEFFAMINE (registered trademark) KH-511, ED-600, and ED-900 , ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2- Aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2- Amine etc. are not limited to these.

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

In addition, R ¹³² may include a tetracarboxylic acid residue remaining after removing an anhydride group from tetracarboxylic dianhydride. As a specific example, an example ^{of R 115} in the formula (2) of the polyimide precursor can be given. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

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

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

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

Furthermore, in order to improve the storage stability of the composition, it is preferable to seal the main chain end of the polyimide with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, and a monoactive ester compound. Among these, it is more preferable to use monoamines. As preferred compounds for monoamines, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8 can be mentioned. -Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7 -Aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 -Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-amino Benzenesulfonic 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, or multiple different end groups can be introduced by reacting a plurality of end-capping agents.

-Imidation rate (closed loop rate)-From the viewpoint of the film strength and insulation of the obtained organic film, the imidization rate of polyimide (also called "closed loop rate") is 70% The above is preferable, 80% or more is more preferable, and 90% or more is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, as long as it is 100% or less. The above-mentioned imidization rate is measured by the following method, for example. The infrared absorption spectrum of the polyimide was measured, and the peak intensity P1 in the vicinity ^{of 1377 cm-1} , which is an absorption peak derived from the imine structure, was determined. Next, after the polyimide was heat-treated at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 in the vicinity of ^{1377 cm-1 was determined.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be calculated according to the following formula. The imidization rate (%)=(peak intensity P1/peak intensity P2)×100

All of the polyimide may contain a ^{repeating structural unit of the above formula (4) including one kind of R 131} or R ¹³² , and may also include a repeat of the above formula (4) including two or more different types of R ¹³¹ or R ¹³² unit. In addition, the polyimide may include other types of repeating structural units in addition to the repeating unit of the above-mentioned formula (4).

Polyimide can be synthesized by, for example, the following method: a method of reacting tetracarboxylic dianhydride with a diamine compound (part of it is replaced by a monoamine capping agent) at a low temperature; Anhydride (replacement of a part with acid anhydride or monochloride compound or monoactive ester compound capping agent) is a method of reacting with diamine compound; the diester is obtained by tetracarboxylic dianhydride and alcohol, and then it is combined with diamine (Replace part of the monoamine capping agent) The method of reacting in the presence of a condensing agent; using tetracarboxylic dianhydride and alcohol to obtain a diester, and then chlorinating the remaining dicarboxylic acid and making The polyimide precursor is obtained by the method of reacting it with diamine (replacement of a part of monoamine capping agent) and other methods, and the known method of imidization is used to make it completely imidized; Alternatively, a method of stopping the imidization reaction in the middle and introducing a part of the imine structure; and a method of introducing a part of the imine structure by mixing a fully imidized polymer and the polyimide precursor. As commercially available products of polyimide, Durimide (registered trademark) 284 (manufactured by FUJIFILM Co., Ltd.) and Matrimide 5218 (manufactured by HUNTSMAN) can be exemplified.

The weight average molecular weight (Mw) of the polyimide can be 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when two or more types of polyimines are contained, the weight average molecular weight of at least one type of polyimines is preferably within the above-mentioned range.

〔Polybenzoxazole precursor〕 Regarding the polybenzoxazole precursor used in the present invention, the molar content of the benzoxazole structure in 1g of the above-mentioned polybenzoxazole precursor is 0.22～3.97mmol/g. Preferably, 0.25 to 3.00 mmol/g is more preferable, 0.28 to 2.50 mmol/g is still more preferable, and 0.30 to 2.00 mmol/g is particularly preferable.

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

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

In formula (3), R ¹²³ and R ^{124 have the same meaning as R 113} in formula (2), and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a straight-chain aliphatic group is preferred. 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 dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing linear or branched (preferably linear) aliphatic groups are preferred. A dicarboxylic acid composed of a family group and 2 -COOH is more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2-30, more preferably 2-25, more preferably 3-20, and still more preferably 4-15, 5～10 are particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid , Tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoro Glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methyl Glutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctane Diacid, azelaic acid, sebacic acid, hexadecanofluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, behenicanedioic acid, behenedioic acid, tricosanedioic acid , Tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triaconanedioic acid, three Undecanedioic acid, tridodecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

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

(In the formula, Z is a hydrocarbon group having 1 to 6 carbons, 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 preferable, and the following dicarboxylic acid consisting only of an aromatic group and two -COOH is more preferable.

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

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

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it has the ^{same meaning as 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 diaminophenol derivative. As a group derived from a diaminophenol derivative, for example, 3,3'-diamino-4,4'- Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfide, 4,4'-di Amino-3,3'-dihydroxydiphenyl benzene, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2 ,2-Bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino -3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino- 4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino -4,6-Dihydroxybenzene, etc. These diaminophenols can be used alone or in combination.

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

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

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

[Chemical formula 20]

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

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

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

In the above formula (As), it is believed that having a substituent at the ortho position of the phenolic hydroxyl group, that is, R ₃ will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, resulting in a high cyclization rate when cured at a low temperature. The point of view that the effect is further improved is particularly good.

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

Furthermore, 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 of R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms. Among them, it maintains high transparency to i-rays and It has the effect of high cyclization rate when hardened at low temperature, and it is possible to obtain polybenzoxazole precursors with sufficient solubility to solvents and excellent balance, -CH ₂ -, -CH(CH ₃ ) -, -C(CH ₃ ) ₂ -is better.

As a method for producing the diaminophenol derivative represented by the above formula (As), for example, paragraph numbers 0085 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP 2013-256506 A can be referred to. The content is compiled into this manual.

As a specific example of the structure of the bisaminophenol derivative represented by the above formula (As), there can be cited those described in paragraphs 0070 to 0080 of JP 2013-256506 A, and these contents are incorporated into this specification middle. Of course, it is not limited to this.

式（3-1）～式（3-3）中、R¹²¹ 、R¹²² 、R¹²³ 及R¹²⁴ 分別與式（3）中的R¹²¹ 、R¹²² 、R¹²³ 及R¹²⁴ 同義，較佳的態樣亦相同。In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also include other types of repeating structural units. As a repeating unit having a benzoxazole structure, the polybenzoxazole precursor may include a repeating unit represented by the following formula (3-1) and a repeating unit represented by the following formula (3-2) , And at least one repeating unit in the group of repeating units represented by the following formula (3-3). [Chemical formula 22]

Formula (3-1) to Formula ^{(3-3), R 121 (3} ) in R ^121, R ^122, R ¹²³ and R ^124, respectively of formula, R ^122, R ¹²³ and R ¹²⁴ is synonymous preferred The appearance is also the same.

The content of the repeating unit represented by the formula (3-1), the repeating unit represented by the formula (3-2), and the repeating unit represented by the formula (3-3) is in 1 g of the polybenzoxazole precursor The molar content of the benzoazole structure is preferably within the above-mentioned range.

In addition, from the viewpoint of suppressing the occurrence of warpage accompanying ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

式（SL）中，Z具有a結構和b結構，R^1s 為氫原子或碳數1～10的烴基，R^2s 為碳數1～10的烴基，R^3s 、R^4s 、R^5s 、R^6s 中的至少1個為芳香族基，其餘為氫原子或碳數1～30的有機基團，其分別可以相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合，亦可以為無規聚合。關於Z部分的莫耳%，a結構為5～95莫耳%、b結構為95～5莫耳%，a+b為100莫耳%。[Chemical formula 23]

In formula (SL), Z has a structure and a structure b, R ^1s is a hydrogen atom or a hydrocarbon group with ^{1 to 10 carbons, R 2s} is a hydrocarbon group with 1 to 10 carbons, R ^3s , R ^4s , R ^5s , R ^6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups 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 mole% of the Z part, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and a+b is 100 mole%.

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

When the diamine residue represented by the formula (SL) is included as another type of repeating structural unit, it may further include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating structural unit For better. As an example of such a tetracarboxylic acid residue, an example of R ¹¹⁵ in formula (2) can be given.

For example, when a polybenzoxazole precursor is used in the composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further Preferably it is 22,000-28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The molecular weight dispersion 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 dispersion 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 more preferred, 2.3 or less is more preferred, and 2.2 or less It is even better.

式（X）中，R¹³³ 表示2價的有機基團，R¹³⁴ 表示4價的有機基團。 當具有聚合性基的情況下，聚合性基可以位於R¹³³ 及R¹³⁴ 中的至少一者上，亦可以如下述式（X-1）或式（X-2）所示，位於聚苯并㗁唑的末端。 式（X-1） [化學式25]

式（X-1）中，R¹³⁵ 及R¹³⁶ 中的至少一者為聚合性基，當不是聚合性基的情況下為有機基團，其他基團與式（X）同義。 式（X-2） [化學式26]

式（X-2）中，R¹³⁷ 為聚合性基，其他為取代基，其他的基團與式（X）同義。[Polybenzoxazole] As polybenzoxazole, as long as it is a polymer compound having a benzoxazole ring, it is not particularly limited, but a compound represented by the following formula (X) is preferred, as A compound represented by formula (X) and having a polymerizable group is more preferable. As said polymerizable group, a radical polymerizable group is preferable. [Chemical formula 24]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When it has a polymerizable group, the polymerizable group may be located ^{on at least one of R 133} and R ¹³⁴ , or may be located on polybenzo The end of the azole. Formula (X-1) [Chemical Formula 25]

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as formula (X). Formula (X-2) [Chemical Formula 26]

In the formula (X-2), ^R137 is a polymerizable group, the others are substituents, and the other groups have the same meaning as in the formula (X).

The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic or aromatic group can be mentioned. As a specific example, an example ^{of R 121} in the formula (3) of the polybenzoxazole precursor can be given. In addition, the preferred example is the same as ^{R 121.}

R ¹³⁴ represents a tetravalent organic group. ^{Examples of the tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. In addition, its preferred example is the same as ^{R 122.} For example, ^{the four bonds of the tetravalent organic group exemplified as R 122} are bonded to the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical formula 27]

The azoleization rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. Since the azolization rate is over 85%, the shrinkage of the film caused by the closed loop generated during the azolization by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

All polybenzoxazoles may contain a ^{repeating structural unit of the above formula (X) containing one R 131} or R ¹³² , and may also contain the above formula (X) containing two or more different types of R ¹³¹ or R ¹³² Repeating unit. In addition, the polybenzoxazole may include other types of repeating structural units in addition to the repeating unit of the above formula (X).

Polybenzoxazole, for example, is obtained by combining a diaminophenol derivative with a ^{dicarboxylic acid containing R 133} or a dicarboxylic acid dichloride selected from the above-mentioned dicarboxylic acids and dicarboxylic acid derivatives. The compound is reacted to obtain a polybenzoxazole precursor, which is obtained by oxazole using a known oxazole reaction method. In addition, in the case of dicarboxylic acid, in order to increase the reaction yield, etc., an active ester-type dicarboxylic acid derivative obtained by preliminarily reacting 1-hydroxy-1,2,3-benzotriazole and the like can be used.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, and even more preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when two or more polybenzoxazoles are contained, the weight average molecular weight of at least one polybenzoxazole is preferably within the above-mentioned range.

[Manufacturing methods of polyimide precursors, etc.] The polyimide precursor and the like are obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting with a diamine. In the production method of polyimide precursors and 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 defined according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified. Polyimine can be cyclized by thermal imidization, chemical imidization (for example, by using a catalyst to promote the cyclization reaction) after synthesizing the polyimine precursor. For manufacturing, polyimide can also be synthesized directly.

In addition, it is also preferable to synthesize using a non-halogen-based catalyst without using the above-mentioned halogenating agent. As the above-mentioned non-halogen-based catalysts, well-known amination catalysts that do not contain halogen atoms can be used without particular limitation. Examples include boroxine compounds, N-hydroxy compounds, and tertiary amines. , Phosphate esters, amine salts, urea compounds, etc., carbodiimide compounds. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, and the like.

-Capping agent- When producing polyimide precursors, etc., in order to further improve the storage stability, it is better to seal the ends of the polyimide precursors with a blocking agent such as acid anhydrides, monocarboxylic acids, monochlorine compounds, and monoactive ester compounds. . As a blocking agent, it is more preferable to use a monoamine. As a preferable compound of a 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-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting a plurality of end-capping agents.

-Solid precipitation- When manufacturing polyimide precursors, etc., a process for precipitation of solids may be included. Specifically, by precipitating the polyimide precursor in the reaction liquid in water and dissolving it in a soluble solvent such as the polyimide precursor such as tetrahydrofuran, the solid can be precipitated. Then, by drying the polyimide precursor and the like, a powdery polyimide precursor and the like can be obtained.

〔content〕 The content of the specific resin in the composition of the present invention relative to the total solid content of the composition is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more To be further preferred. In addition, the content of the resin in the composition of the present invention relative to the total solid content of the composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass or less, 97% by mass The following is more preferable, and 95% by mass or less is even more preferable. The composition of the present invention may include only one type of specific resin, or may include two or more types. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range.

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

＜Organic metal complexes with photopolymerization initiation ability＞ The photosensitive resin composition of the present invention contains an organometallic complex having photopolymerization initiation ability (hereinafter, also referred to as "specific organometallic complex"). In the present invention, having photopolymerization initiation energy means that a polymerization initiation species capable of initiating polymerization can be generated by light irradiation. For example, when a composition containing a crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light and the crosslinking agent does not absorb light, it is possible to confirm the disappearance of the crosslinking agent. Check whether the photopolymerization can start. When confirming whether the disappearance or not, an appropriate method can be selected according to the type of crosslinking agent, for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography).

It is preferred that the specific organometallic complex has photo-radical polymerization initiation ability. In the present invention, having photo-radical polymerization initiation energy means that a free radical capable of initiating free-radical polymerization can be generated by light irradiation. For example, for a composition containing a free radical crosslinking agent and an organometallic complex, when irradiating light in a wavelength region where the organometallic complex absorbs light and the free radical crosslinking agent does not absorb light, by confirming the presence or absence of free radical crosslinking The disappearance of the linking agent can confirm the initiation of photo-radical polymerization. When confirming the disappearance, an appropriate method can be selected according to the type of the radical crosslinking agent, for example, IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography) can be used to confirm.

The metal contained in the specific organometallic complex is not particularly limited. Transition metals are preferred, metals corresponding to Group 4 elements are preferred, and at least one selected from the group consisting of titanium, zirconium and hafnium One kind of metal is more preferred, at least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

Regarding the specific organometallic complex, a compound in which an organic group is coordinated with a metal atom is preferred, and a metallocene compound is more preferred. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl derivatives that may have substituents as η5-coordinators. The organic group is not particularly limited, but a group composed of a hydrocarbon group or a combination of a hydrocarbon group and a heteroatom is preferred. As the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one cyclic group in the organic group is preferable, and at least two cyclic groups are more preferable. The above-mentioned cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and a 5-membered cyclic group is more preferable. 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 preferred. In addition, the specific organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

Among them, as specific organometallic complexes, titanocene compounds are preferred, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3- (1H-pyrrol-1-yl)phenyl)titanium or bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium is more preferred.

The content of the specific organometallic complex is preferably 0.1 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The upper limit is more preferably 10% by mass or less, and more preferably 5.0% by mass or less. One type or two or more types of specific organometallic complexes can be used. When two or more are used, the total amount is preferably within the above range.

<Hindered phenol compound> The photosensitive resin composition of the present invention contains a hindered phenol compound. The hindered phenol compound is not particularly limited, but a compound represented by the following formula (1-1) or a compound represented by the formula (1-1) as a partial structure is preferably included. It is more preferable that the structure represented by) is included as a partial structure. [Chemical formula 28]

In formula (1-1), Ar represents an aromatic ring structure, a represents an integer of 1 or more, R ¹ represents an integer of 1 or more, b represents an integer of 1 or more, R ² represents a substituent, and c represents an integer of 1 or more.

In formula (1-1), Ar represents an aromatic ring structure, an aromatic hydrocarbon ring structure is preferred, and a benzene ring structure is more preferred. a represents an integer of 1 or more, an integer of 1 to 3 is preferred, 1 or 2 is more preferred, and 1 is even more preferred. R ¹ represents a branched alkyl group, and a branched alkyl group containing at least one quaternary carbon atom is preferable, a branched alkyl group containing one quaternary carbon atom is more preferable, and a tertiary butyl group is even more preferable. b represents an integer of 1 or more, and an integer of 1 to 3 is preferred, 1 or 2 is more preferred, and 1 is even more preferred. R ² represents a substituent, and an alkyl group having 1 to 4 carbons or an aryl group having 6 to 20 carbons is preferred, and an alkyl group having 1 to 4 carbons is more preferred. When the hindered phenol compound is a compound contained in the structure represented by formula (1-1) as a partial structure, it has an aromatic ring structure represented by Ar directly bonded to formula (1-1) removed Compounds with hydrogen atoms of the ring members are preferred.

It is preferable that at least one of the hydroxyl groups described in the formula (1-1) and at least one of R ¹ are present at adjacent positions in the aromatic ring structure represented by Ar. In this specification, the presence of two groups in adjacent positions in the ring structure means that the ring members in the above-mentioned ring structure where a certain group exists and the ring members in the above-mentioned ring structure where other groups exist are in the ring The adjacent ring members in the structure. For example, when the ring structure is a benzene ring structure, the adjacent positions are ortho positions.

Furthermore, the hindered phenol compound is preferably a compound containing a nitrogen atom. Since the hindered phenol compound contains nitrogen atoms, it is considered that the hindered phenol compound is likely to be unevenly distributed on the surface of the metal layer, and the crosslinking density under the deep part of the film is likely to be in an appropriate range. In particular, the hindered phenol compound contains a nitrogen atom and contains a polyimide precursor and a polybenzoxazole precursor as a specific resin, which is one of the preferred aspects of the present invention. When the hindered phenol compound is a compound containing a nitrogen atom, for example, the hindered phenol compound contains an aromatic ring structure such as a tricyclic ring structure and a toluidine ring structure, or an aliphatic ring structure such as an isocyanuric acid ring structure. Nitrogen-containing ring structure compounds are preferred, and compounds containing nitrogen-containing aliphatic ring structures such as isocyanuric acid ring structures are more preferred. When the hindered phenol compound contains a nitrogen-containing ring structure, the hindered phenol compound has a ring member that is directly bonded to the nitrogen-containing ring structure and the aromatic ring structure represented by Ar in the above formula (1-1) The hydrogen atom compound is preferred.

Examples of hindered phenol compounds include compounds represented by the following formula (1-1-1) to (1-1-7), but are not limited to these. Among them, the compound represented by formula (1-1-1) is preferred. [Chemical formula 29]

The content of the hindered phenol compound is preferably 0.05 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. The upper limit is more preferably 5% by mass or less, and more preferably 3% by mass or less. One kind or two or more kinds of hindered phenol compounds can be used. When two or more are used, the total amount is preferably within the above range.

＜Other organometallic compounds＞ The photosensitive resin composition of the present invention may contain another organometallic compound different from the above-mentioned specific organometallic complex (hereinafter, also simply referred to as “organometallic compound”). It is preferable that other organometallic compounds do not have radical polymerization initiation ability. The organometallic compound is only required to be an organic compound containing a metal atom, but a compound containing a metal atom and an organic base diagram is preferable. A compound in which the organic base diagram is coordinated with respect to the metal atom is more preferable, and a metallocene compound is even more preferable. . In the present invention, the metallocene compound refers to an organometallic compound having two cyclopentadienyl derivatives which may have substituents as η5-coordinators. The organic group is not particularly limited, but a group composed of a hydrocarbon group or a combination of a hydrocarbon group and a heteroatom is preferred. As the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one cyclic group in the organic group is preferable, and at least two cyclic groups are more preferable. The above-mentioned cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and a 5-membered cyclic group is more preferable. 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 preferred. In addition, the organometallic compound used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic compound is not particularly limited. It is preferably a metal corresponding to a group 4 element, and more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium. At least one metal in the group of titanium and zirconium is further preferred, and titanium is particularly preferred.

The organometallic compound 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 compound contains two or more metal atoms, it may contain only one kind of metal atom, or may contain two or more kinds of metal atoms.

The organometallic compound is preferably a titanocene compound, a zirconocene compound or a hafnium compound, a titanocene compound or a zirconocene compound is more preferable, and a titanocene compound is even more preferable. The organometallic compound is preferably at least one compound selected from the group consisting of a titanocene compound, a tetraalkoxy titanium compound, a titanium acylate compound, a chelated titanium compound, a zirconocene compound, and a hafnium compound. At least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and hafnium compounds is more preferred, and at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds is further Preferably, the titanocene compound is particularly preferred.

The molecular weight of the organometallic compound is preferably 50 to 2,000, and 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 the organometallic compound, a compound represented by the following formula (P) can be preferably used. [Chemical formula 30]

In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the above-mentioned R is 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, a titanium atom, a zirconium atom, or a hafnium atom is preferred, a titanium atom or a zirconium atom is more preferred, and a titanium atom is even more preferred. As the aromatic group in R in the formula (P), an aromatic group having 6 to 20 carbon atoms is mentioned, and an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, and phenyl group and 1-naphthyl group are mentioned. , Or 2-naphthyl and so on. As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Examples include methyl, ethyl, propyl, and octyl. Base, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. Examples of the halogen atom in the above R include F, Cl, Br, and I. As the alkyl group constituting the alkylsulfonyloxy group in R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Examples include methyl, ethyl, and propylene. Base, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. The above-mentioned R may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, Aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, monoarylamino and diarylamino groups, etc.

Specific examples of the organometallic compound are not particularly limited, and examples include tetraisopropoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxy bis(ethyl acetylacetate) titanium, and Propoxy bis(acetone) titanium, pentamethylcyclopentadienyl titanium trimethoxide, and the following compounds. [Chemical formula 31]

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 to these.

The content of the organometallic compound is preferably 0.1 to 30% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic compounds can be used. When two or more are used, the total amount is preferably within the above range.

＜Other resins＞ The composition of the present invention may include the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also referred to simply as "other resin"). Examples of other resins include polyamide imides, polyamide imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing silicone structures, acrylic resins, etc. . For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained. For example, by replacing the crosslinking agent described later or in addition to the crosslinking agent described later, adding a polymerizable acrylic resin with a weight average molecular weight of 20,000 or less to the composition with a high base value can improve the coating of the composition. Performance, solvent resistance of organic film, etc.

When the composition of the present invention contains other resins, the content of the other resin relative to the total solid content of the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more. Preferably, 2% by mass or more is more preferable, 5% by mass or more is still more preferable, and 10% by mass or more is still more preferable. In addition, the content of other resins in the composition of the present invention relative to the total solid content of the composition is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, and 60% by mass % Or less is more preferable, and 50 mass% or less is still more preferable. In addition, as a preferable aspect of the composition of the present invention, the content of other resins can also be a low content aspect. In the above aspect, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and 5% by mass or less More preferably, 1% by mass or less is still more preferable. The lower limit of the above content is not particularly limited as long as it is 0% by mass or more. The composition of the present invention may include only one kind of other resin, or may include two or more kinds. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range.

＜Solvent＞ The photosensitive resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. Solvent-based organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfenes, amines, ureas, and alcohols.

As esters, preferred ones include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. , Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (for example, alkoxy Methyl acetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, etc.)), 3-alkoxy propionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionate Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate ( For example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate Ester and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) , Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Methyl 2-oxobutyrate, Ethyl 2-oxobutyrate, Ethyl Caproate , Ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

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

As the ketones, preferred ones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucan, Dihydrolevoglucan and so on.

Preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As a sulfenite, as a preferable one, for example, dimethyl sulfenite can be mentioned.

As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropane Amide, N-formylmorpholine, N-acetylmorpholine, etc.

As the ureas, preferable ones 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-methoxy 2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol Monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-pentanol, methyl pentanol and Diacetone alcohol and so on.

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

In the present invention, it is selected from the group consisting of 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cyrus acetoacetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more types is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. In addition, combinations of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone are also preferred.

From the viewpoint of coatability, the content of the solvent is preferably 5 to 80% by mass of the total solid content of the photosensitive resin composition of the present invention, and more preferably 5 to 75% by mass. Preferably, it is more preferable to set it as 10-70 mass %, and it is more preferable to set it as 40-70 mass %. The solvent content can be adjusted according to the required thickness of the coating film and the coating method.

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

＜Sensitizer＞ The composition of the present invention preferably contains a photosensitizer. It is assumed that the compound corresponding to the above-mentioned specific organometallic complex is not contained in the photosensitizer. The composition of the present invention may contain a photopolymerization initiator different from the above-mentioned specific organometallic complex.

〔Photopolymerization initiator〕 In the composition of the present invention, a photopolymerization initiator may be contained as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can also be an active agent that generates active free radicals by having a certain effect with a sensitizer excited by light.

It is also preferable that the composition of the present invention does not substantially contain a photopolymerization initiator other than the specific organometallic complex. The fact that the photopolymerization initiator other than the specific organometallic complex is not substantially contained means that the content of the photopolymerization initiator other than the specific organometallic complex in the composition of the present invention is relative to the content of the photopolymerization initiator other than the specific organic metal complex. The total mass of the metal complex is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass. In addition, it is also preferable that the composition of the present invention contains the above-mentioned specific organometallic complex and a photo-radical polymerization initiator. According to this aspect, the exposure sensitivity can be improved. When the composition of the present invention contains the specific organometallic complex and the photo-radical polymerization initiator, the content of the specific organometallic complex is relative to the total of the specific organometallic complex and the photo-radical polymerization initiator The content is preferably 20 to 80% by mass, more preferably 30 to 70% by mass. In addition, as the above-mentioned radical photopolymerization initiator, an oxime compound described later is preferred.

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

As the photoradical polymerization initiator, a known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as phosphonium oxide, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Organoboron compounds, iron arene complexes, etc. For the details, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and this content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one aspect of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the phosphonium oxide-based initiator described in Japanese Patent No. 4225898 can be used.

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

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

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 that has an absorption maximum wavelength matched with a wavelength light source such as 365 nm or 405 nm can also be used.

Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (brand name: both manufactured by BASF Corporation), which are commercially available products, can be used.

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

As specific examples of the oxime compound, the compounds described in Japanese Patent Application Publication No. 2001-233842, the compounds described in Japanese Patent Application Publication No. 2000-080068, and the compounds described in Japanese Patent Application Publication No. 2006-342166 can be used. .

As a preferable oxime compound, for example, a compound having the following structure or 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one and the like. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 32]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF Corporation), Adeka Optomer N-1919 (made by ADEKA CORPORATION, Japan Special Publication 2012- The photo-radical polymerization initiator described in 014052 No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 33]

As the photopolymerization initiator, an oxime compound having a sulphur ring can also be used. As a specific example of the oxime compound which has a sulphur ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466, and the compound described in Japanese Patent No. 06636081 can be mentioned.

As the photopolymerization initiator, an oxime compound in which at least one benzene ring having a carbazole ring becomes the skeleton of the naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 can be cited.

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

As the optimal oxime compound, the oxime compound having a specific substituent shown in JP 2007-269779 A, or the oxime compound having a thioaryl group shown in JP 2009-191061, etc. can be mentioned.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl trimethyl ketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene -The present-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.

Further preferred photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium Salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one of the compounds is further preferred, the use of a metallocene compound or an oxime compound is even more preferred, and an oxime compound is even more preferred.

In addition, the photoradical polymerization initiator can also use N,N'- such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michele ketone), etc. Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methanone 1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkylanthraquinones and other quinones condensed with aromatic rings, benzoin alkyl ethers Benzoin ether compounds, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 34]

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

[Chemical formula 35]

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

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

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

〔Photoacid generator〕 Furthermore, in the composition of the present invention, it is also preferable to include a photoacid generator as a photosensitizer. In addition, it can also be set as a form in which the composition contains a photoacid generator and a crosslinking agent other than the free radical crosslinking agent described later, for example, the crosslinking of the crosslinking agent is promoted by the acid generated in the exposed portion In response, the exposed part is less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative pattern can be obtained.

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

As the quinonediazide compound, a sulfonic acid in which quinonediazide is bonded to a polyhydroxy compound through an ester, and a sulfonic acid in which a quinonediazide is bonded to a polyamine compound through a sulfonamide can be mentioned. Acids, sulfonic acids in which quinonediazide is bonded to a polyhydroxypolyamine compound through at least one of an ester bond and a sulfonamide bond, and the like. In the present invention, for example, it is preferable that 50 mol% or more of the entire functional group of the polyhydroxy compound or polyamine compound is substituted with a quinonediazide group.

In the present invention, the quinone diazide can preferably use any of 5-naphthoquinone diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-ray region of the mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonate compound extends to the g-ray region of the mercury lamp, which is suitable for g-ray exposure. In the present invention, it is preferable to select the 4-naphthoquinone diazide sulfonate compound and the 5-naphthoquinone diazide sulfonate compound according to the exposure wavelength. In addition, it may contain a naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule, or 4-naphthoquinone diazide sulfonyl ester compound Azosulfonate compound and 5-naphthoquinone diazide sulfonate compound.

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

Examples of the onium salt compound or sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP 2008-013646 A, and the like.

The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also referred to simply 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), formula (OS-104) or formula (OS-105) The oxime sulfonate compound represented is preferred.

[Chemical formula 36]

In the formula (OS-1), X ³ represents an alkyl group, an alkoxy group, or a halogen atom. When there are a plurality of X ³ , they may be the same or different. The alkyl group and alkoxy group in the above X ^{3 may have a substituent.} As the ^{alkyl group in X 3} , a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As ^{the alkoxy group in X 3} , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in the above 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 preferred. When m3 is 2 or 3, a plurality of X ³ may be the same or different. In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, a halogenated alkyl group having 1 to 5 carbons, and a carbon number of 1 to The halogenated alkoxy group of 5, the phenyl group which may be substituted by W, the naphthyl group which may be substituted by W, or the anthryl group which may be substituted by W is preferable. W represents halogen atom, cyano group, nitro group, C1-C10 alkyl group, C1-C10 alkoxy group, C1-C5 halogenated alkyl group or C1-C5 halogenated alkoxy group , C6-C20 aryl group, C6-C20 halogenated aryl group.

In the formula (OS-1), m3 is 3, X ³ is a methyl group, ^{the substitution position of X 3} is an ortho position, R ³⁴ is a linear alkyl group having 1 to 10 carbons, and 7,7-dimethyl- Compounds of 2-oxonorkanylmethyl or p-tolyl are particularly preferred.

As specific examples of the oxime sulfonate compound represented by the formula (OS-1), paragraph numbers 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraph numbers 0158 to paragraph numbers of Japanese Patent Application Publication No. 2015-194674 can be exemplified. The following compounds described in 0167 are incorporated in this specification.

[Chemical formula 37]

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are plural R ^s2 each independently represents 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, alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group, Xs represents O or S, ns represents 1 Or 2, ms represents an integer of 0-6. In formulas (OS-103) to (OS-105), ^{the alkyl group represented by R s1} (the carbon number is preferably 1 to 30), the aryl group (the carbon number is preferably 6 to 30), or the heteroaryl group ( (4 to 30 carbon atoms are preferred) may have a substituent T.

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

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

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) The compound represented by) is particularly preferably represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compound shown is particularly good. [Chemical formula 38]

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 and an alkane with 1 to 8 carbon atoms. Group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents a hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen Atom or methyl. In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and a hydrogen atom is preferred.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, a C 1-8 alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group , Phenyl or chlorophenyl, preferably C1-C8 alkyl group, halogen atom or phenyl group, C1-C8 alkyl group is more preferable, C1-C6 alkyl group is more preferable , Methyl is particularly preferred.

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 preferred. R ^t2 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. In addition, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be any one of them, or a mixture. As specific examples of the oxime sulfonate compound represented by the above formula (OS-103) to formula (OS-105), paragraph numbers 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and Japanese Patent Application Publication No. 2015- The compounds described in paragraph numbers 0168 to 0194 of 194674 Bulletin are incorporated in this specification.

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

[Chemical formula 39]

In the 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 carbamethan group, a sulfamoyl group, a sulfonyl group 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 even more preferable. In formula (OS-101) or formula (OS-102), ^Ru2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu means -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7- , ^Ru5 to ^Ru7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkyl group Carbonyl, arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may 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 preferred, and it is also preferred that ^{at least two of R u1} to R ^u4 are bonded to each other to form an aryl group. Wherein, R ^u1 ~ R ^u4 are hydrogen atoms are preferred aspect. Each of the above-mentioned substituents may further have a substituent.

It is more preferable that the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). In addition, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them, or may be a mixture. As specific examples of the compound represented by the formula (OS-101), there can be exemplified those described in paragraphs 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. The contents of these compounds are included in this specification. Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferred.

In addition, as a photoacid generator, a commercially available product can also be used. As commercially available products, WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG- 699 (all made by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (all made by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all made by BASF), MBZ-101 (Midori Kagaku Co .,Ltd.) etc.

Moreover, as a preferable example, the compound represented by the following structural formula can also be mentioned. [Chemical formula 40]

As a photoacid generator, organic halogenated compounds can also be applied. Specific examples of the organic halogenated compound include "Bull Chem. Soc Japan" 42 and 2924 (1969) such as Wakabayashi, US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, and Japanese Patent Application Publication No. 48-036281 No. 55-032070, Japanese Special Publication No. 55-032070, Japanese Special Publication No. 60-239736, Japanese Special Publication No. 61-169835, Japanese Special Publication No. 61-169837, Japanese Special Publication No. 62-058241, Japanese Special Publication The compounds described in Sho 62-212401, JP Sho 63-070243, JP Sho 63-298339, MP Hutt "Jurnal of Heterocyclic Chemistry" 1 (No 3), (1970), etc., in particular, include A azole compound substituted by a trihalomethyl group: S-tri 𠯤 compound. More preferably, at least one mono-, di-, or tri-halogen substituted s-tris derivative bonded to the s-tris ring can be cited. Specifically, for example, 2,4,6-tris (Monochloromethyl)-s-tris, 2,4,6-tris(dichloromethyl)-s-tris, 2,4,6-tris(trichloromethyl)-s-tris, 2-Methyl-4,6-bis(trichloromethyl)-s-tris, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris, 2-(α, α,β-Trichloroethyl)-4,6-bis(trichloromethyl)-s-tris, 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) )-S-tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris, 2-[1-(p-methoxyphenyl)-2,4 -Butadienyl]-4,6-bis(trichloromethyl)-s-tris, 2-styryl-4,6-bis(trichloromethyl)-s-tris, 2-( P-Methoxystyryl)-4,6-bis(trichloromethyl)-s-tris, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) -s-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris, 2-(4-naphthyloxynaphthyl)-4,6-bis(tris Chloromethyl)-s-tris, 2-phenylthio-4,6-bis(trichloromethyl)-s-tris, 2-benzylthio-4,6-bis(trichloromethyl) -s-tris, 2,4,6-tris(dibromomethyl)-s-tris, 2,4,6-tris(tribromomethyl)-s-tris, 2-methyl-4 ,6-bis(tribromomethyl)-s-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-tris, etc.

As a photoacid generator, an organic borate compound can also be applied. As the organoborate compound, specific examples include, for example, JP-A 62-143044, JP-A 62-150242, JP-A 9-188685, JP-A 9-188686, and JP-A. 9-188710, Japanese Patent Publication 2000-131837, Japanese Patent Publication 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc. and Kunz, Martin "Rad Tech'98. Proceeding April 19-22 , 1998, "Chicago" and other organoborates, Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, and Japanese Patent Laid-Open No. 6-175561 Or organoboron oxoaluminium complexes, the organoboron complexes described in Japanese Patent Application Laid-Open No. 6-175554, Japanese Patent Application Laid-Open No. 6-175553, and those described in Japanese Patent Application Laid-Open No. 9-188710 Organoboron phosphonium complexes, Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, Japanese Patent Application Publication No. 7-292014 Bulletin and other organoboron transition metal coordination complexes, etc.

As a photoacid generator, disulfite compounds can also be applied. Examples of the diazonium compound include compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318, etc. and diazonium compounds.

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

式（RI-I）中，Ar11表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z11^- 表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式（RI-II）中，Ar21、Ar22各自獨立地表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z21^- 表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式（RI-III）中，R31、R32、R33各自獨立地表示可以具有1～6個取代基之碳數20以下的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面而言，芳基為較佳。作為較佳的取代基，可以舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z31^- 表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。Examples of onium salts include onium salts represented by the following general formulas (RI-I) to (RI-III). [Chemical formula 41]

In the formula (RI-I), Ar11 represents an aryl group with a carbon number of 20 or less that may have 1 to 6 substituents. Preferred substituents include an alkyl group with 1 to 12 carbons, and an alkyl group with 1 to 12 carbon atoms. 12 alkenyl, carbon 1-12 alkynyl, carbon 1-12 aryl, carbon 1-12 alkoxy, carbon 1-12 aryloxy, halogen atom, carbon 1 to 12 alkylamino group, dialkylamino group with 1 to 12 carbons, alkylamino group or arylamino group with 1 to 12 carbons, carbonyl group, carboxyl group, cyano group, sulfonyl group, carbon number A thioalkyl group having 1 to 12, and a thioaryl group having 1 to 12 carbons. Z11 ^- represents a monovalent anion, which is halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfuric acid ion, from stability In terms of ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In the formula (RI-II), Ar21 and Ar22 each independently represent an aryl group with a carbon number of 20 or less that may have 1 to 6 substituents. As a preferred substituent, an alkyl group with 1 to 12 carbons can be mentioned. , Alkenyl groups with 1 to 12 carbons, alkynyl groups with 1 to 12 carbons, aryl groups with 1 to 12 carbons, alkoxy groups with 1 to 12 carbons, aryloxy groups with 1 to 12 carbons, halogen atoms , Alkylamino groups with 1-12 carbons, dialkylamino groups with 1-12 carbons, alkylamino or arylamino groups with 1-12 carbons, carbonyl, carboxyl, cyano, sulfonic acid An acyl group, a thioalkyl group having 1 to 12 carbons, and a thioaryl group having 1 to 12 carbons. Z21 ^- represents a monovalent anion, which is halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfuric acid ion, from stability In terms of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylic acid ion are preferred. In formula (RI-III), R31, R32, and R33 each independently represent an aryl or alkyl, alkenyl, or alkynyl group with a carbon number of 20 or less that may have 1 to 6 substituents. Preferably, from the reactivity In terms of stability, aryl groups are preferred. Preferred substituents include alkyl groups having 1 to 12 carbons, alkenyl groups having 1 to 12 carbons, alkynyl groups having 1 to 12 carbons, aryl groups having 1 to 12 carbons, and aryl groups having 1 to 12 carbons. 12 alkoxy, C 1-12 aryloxy, halogen atom, C 1-12 alkylamino group, C 1-12 dialkylamino group, C 1-12 alkyl group Amido or arylamido, carbonyl, carboxy, cyano, sulfonyl, thioalkyl having 1 to 12 carbons, and thioaryl having 1 to 12 carbons. Z31 ^- represents a monovalent anion, which is halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfuric acid ion, from stability In terms of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylic acid ion are preferred.

[化學式43]

[化學式44]

[化學式45]

As a specific example, the following can be mentioned. [Chemical formula 42]

[Chemical formula 43]

[Chemical formula 44]

[Chemical formula 45]

When a photoacid generator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, and more preferably 2-15% by mass. Better. The photoacid generator may contain only one type or two or more types. When two or more kinds of photoacid generators are contained, the total of them is preferably within the above-mentioned range.

〔Photobase generator〕 The photosensitive resin composition of the present invention may contain a photobase generator as a photosensitizer. When the photosensitive resin composition contains a photobase generator and a crosslinking agent described later, it can be configured as follows. For example, the alkali generated in the exposed portion promotes the cyclization of the specific resin and promotes the crosslinking of the crosslinking agent. Due to the effect of reaction, the exposed part is less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative pattern can be obtained.

The photobase generator is not particularly limited as long as it generates an alkali by exposure, and known ones can be used. For example, such as M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Kadooka Masahiro, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev. , 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol. , 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol. , 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006). It is described in the transition metal compound complex, having ammonium Salts and other structural substances, amidine moieties that are latentized by forming salts with carboxylic acids, alkali components such as ionic compounds that are neutralized by the formation of salts, urethane derivatives, oxime ester derivatives , Nonionic compounds in which alkali components such as acyl compounds are latentized by urethane bonds or oxime bonds. In the present invention, examples of photobase generators include carbamate derivatives, amide derivatives, imine derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, and oxime derivatives. Things, etc. as a better example.

The basic substance generated from the photobase generator is not particularly limited, and examples include compounds having an amine group, especially polyamines such as monoamines and diamines, and amidines. From the viewpoint of the imidization rate, it is preferable that the above-mentioned basic substance has a larger pKa in the DMSO (dimethyl sulfide) of the conjugate acid. The above-mentioned pKa is preferably 1 or more, and more preferably 3 or more. The upper limit of the above pKa is not particularly limited, but 20 or less is preferable. Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, which can be found in Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compiled: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software ACD/pKa (manufactured by ACD/Labs) is used as the pKa.

From the viewpoint of the storage stability of the photosensitive resin composition, as the photobase generator, a photobase generator that does not contain salt in the structure is preferable. No charge is better. As a photobase generator, the base produced is potentially made better by covalent bonds. The production mechanism of the base is that the covalent bond between the nitrogen atom of the produced base part and the adjacent atom is cut to produce the base. The mechanism is better. If it is a photobase generator that does not contain salt in the structure, the photobase generator can be made neutral, so the solvent solubility is better and the service life is extended. For these reasons, the amine-based primary amine or secondary amine produced from the photobase generator used in the present invention is preferable. In addition, from the viewpoint of the chemical resistance of the pattern, as the photobase generator, a photobase generator including a salt in the structure is preferable.

In addition, considering the above reasons, as a photobase generator, as described above, the generated base is latently converted by covalent bonds, and the generated base is protected by amide bonds, urethane bonds, and oxime bonds. Potentially better. As the photobase generator of the present invention, for example, the photobase generator having a cinnamamide structure disclosed in Japanese Patent Application Publication No. 2009-080452 and International Publication No. 2009/123122, such as Japanese Patent Application Publication No. 2006- Photobase generators having a urethane structure disclosed in 189591 and JP 2008-247747, such as oximes disclosed in JP 2007-249013 and 2008-003581 The structure, the photobase generator of the urethane oxime structure, etc., but it is not limited to these, In addition, the structure of a well-known photobase generator can be used.

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

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

When the photobase generator is contained, its content is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, and more preferably 2-15% by mass relative to the total solid content of the photosensitive resin composition of the present invention Better. The photobase generator may contain only one type, or may contain two or more types. When two or more photobase generators are contained, the total amount is preferably within the above-mentioned range.

＜Thermal polymerization initiator＞ The composition of the present invention may include a thermal polymerization initiator, and in particular, may include a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that initiates or promotes the polymerization reaction of a polymerizable compound by generating free radicals by thermal energy. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the crosslinking agent also proceeds in the heating process described later, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

When the thermal polymerization initiator is included, its content is preferably 0.1-30% by mass relative to the total solid content of the composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5-15% by mass %. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are contained, the total amount thereof is preferably within the above-mentioned range.

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

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, if the composition is applied to the substrate after drying (pre-baking: about 70-140°C), acid is not generated, and the final heating after patterning in subsequent exposure and development (curing: about 100 to 400°C), which generates acid at 100 to 400°C), is preferably used as a thermal acid generator to suppress the decrease in sensitivity during development. The thermal decomposition start temperature is determined as the peak temperature of the heat generation peak with the lowest temperature when the thermal acid generator is heated to 500°C at 5°C/min in the pressure-resistant capsule. As a device used when measuring the start temperature of thermal decomposition, Q2000 (manufactured by TA Instruments) and the like can be cited.

Strong acids generated from thermal acid generators are preferred, such as aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or trifluorosulfonic acid Halogenated alkyl sulfonic acids such as methanesulfonic acid and the like are preferred. As an example of such a thermal acid generator, the one described in paragraph 0055 of JP 2013-072935 A can be cited.

Among them, from the point of view that the organic film has little residue and is difficult to reduce the physical properties of the organic film, it is more preferable to produce alkyl sulfonic acid with 1 to 4 carbons or halogenated alkyl sulfonic acid with 1 to 4 carbons, and methanesulfonate Acid (4-hydroxyphenyl) dimethyl sulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl sulfonate, methanesulfonate benzyl (4-hydroxyphenyl) methane Methanesulfonate, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methylsulfonate, methanesulfonate (4-hydroxyphenyl)methyl((2-methylphenyl)methane Group) alumite, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethyl alumite, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl alumite, trifluoromethane Sulfonic acid benzyl (4-hydroxyphenyl) methyl alumite, trifluoromethanesulfonate benzyl (4-((methoxycarbonyl)oxy) phenyl) methyl alumite, trifluoromethanesulfonic acid (4- Hydroxyphenyl)methyl((2-methylphenyl)methyl)aluminium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-subunit )-2-(o-tolyl)propionitrile and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as the thermal acid generator.

In addition, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable as a thermal acid generator.

The content of the thermal acid generator relative to 100 parts by mass of the specific resin is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more to promote the crosslinking reaction, the mechanical properties and solvent resistance of the organic film can be further improved. Moreover, from the viewpoint of the electrical insulation of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is more preferable.

＜Onium salt＞ The photosensitive resin composition of the present invention may further contain an onium salt. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain an onium salt. The type of onium salt and the like are not particularly specified, and preferably ammonium salt, imino (Iminium) salt, sulfonium salt, phosphonium salt, or phosphonium salt can be mentioned. Among them, from the viewpoint of high thermal stability, ammonium salt or iminium salt is preferable, and from the viewpoint of compatibility with the polymer, sulfonium salt, phosphonium salt or phosphonium salt is preferable .

In addition, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded via a covalent bond, or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or an intermolecular salt formed by ionic bonding of cation molecules and anion molecules of different molecules, but intermolecular salts For better. In addition, in the photosensitive resin composition of the present invention, the cation portion or cation molecule and the anion portion or anion molecule may be bonded by an ionic bond or may be dissociated. As the cation in the onium salt, ammonium cation, pyridinium cation, sulfonium cation, iodonium cation or phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cation, sulfonium cation and iodonium cation is more preferred. good.

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

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

<Thermal base generator> The photosensitive resin composition of the present invention may further contain a thermal base generator. In particular, when the photosensitive resin composition of the present invention includes a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to include a thermal base generator. The other thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt. Examples of thermal base generators other than the above-mentioned onium salts include nonionic thermal base generators. Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2). [Chemical formula 46]

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

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

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), alkenyl group (the carbon number is 2-24 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 aryl group Alkyl groups (7 to 25 carbon atoms are preferred, 7 to 19 are more preferred, and 7 to 12 are more preferred) are preferred. These groups may have a substituent in the range which exhibits the effect of this invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. Rb ¹ and Rb ^{2 are} especially linear, branched or cyclic alkyl groups which may have substituents (the carbon number is preferably 1-24, 2-18 is more preferably, and 3-12 is more preferably). , A cycloalkyl group that may have a substituent (the carbon number is preferably 3-24, more preferably 3-18, and even more preferably 3-12) is more preferable, and a cyclohexyl group that may have a substituent is even more preferable.

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

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 47]

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

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

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

It is also preferable that the compound represented by formula (B1-1) is the compound represented by formula (B1-1a). [Chemical formula 48]

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

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

As specific examples of compounds that are thermal base generators among the above-mentioned onium salts or specific examples of thermal base generators other than the above-mentioned onium salts, the following compounds can be given.

[Chemical formula 49]

[Chemical formula 50]

[Chemical formula 51]

The content of the other thermal alkali generator is preferably 0.1 to 50% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably within the above range.

＜Crosslinking agent＞ The photosensitive resin composition of the present invention preferably contains a crosslinking agent. As a crosslinking agent, a radical crosslinking agent or other crosslinking agents can be mentioned.

＜Free radical crosslinking agent＞ The photosensitive resin composition of the present invention preferably further contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. Among them, as the above-mentioned ethylenically unsaturated bond-containing group, a (meth)acryloyl group is preferable, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable.

The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, and a compound having two or more is more preferable. The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above-mentioned ethylenically unsaturated bond. Moreover, from the viewpoint of the film strength of the obtained pattern, the photosensitive resin composition of the present invention preferably contains three or more compounds having ethylenically unsaturated bonds as a radical crosslinking agent. As the above-mentioned compound having 3 or more ethylenic unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is preferred, and a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, with 3 to 15 ethylenic unsaturated bonds being more preferred. Six compounds are further preferred. In addition, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more of the above-mentioned ethylenically unsaturated bond-containing groups, and a compound having 3 to 15 is more preferred, having 3 Compounds with -10 are more preferred, and compounds with 3-6 are particularly preferred. In addition, from the viewpoint of the film strength of the obtained pattern, the photosensitive resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds. .

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and 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 free radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, The amines are preferably esters of unsaturated carboxylic acids and polyol compounds and amines of unsaturated carboxylic acids and polyamine compounds. In addition, unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amine, and sulfanyl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. The addition reactant of, or the dehydration condensation reactant with monofunctional or polyfunctional carboxylic acid, etc. In addition, the addition of unsaturated carboxylic acid esters or amides having electron withdrawing substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols can also be preferably used. Reactants, as well as unsaturated carboxylic acid esters or amides with detachable substituents such as halogeno group or tosyloxy group, and monofunctional or polyfunctional alcohols, amines, Substitution reactant of mercaptans. Furthermore, as another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, and allyl ether in place of the above-mentioned unsaturated carboxylic acid. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of JP 2016-027357 A, and these contents are incorporated in this specification.

Furthermore, it is also preferable that the radical crosslinking agent is a compound having a boiling point of 100°C or higher under normal pressure. As an example, the addition of ethylene oxide or propylene oxide to polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate (Meth) acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dineopentaerythritol penta(meth)acrylate, dineopentaerythritol hexa (Meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trihydroxymethyl Compounds that have been (meth)acrylated with polyfunctional alcohols such as methyl ethane, such as Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193. Urethane (meth)acrylates described in the gazette, and polyesters described in each gazette of JP Sho 48-064183, JP Sho 49-043191, and JP Sho 52-030490 Polyfunctional acrylates or methacrylates such as acrylates, epoxy acrylates, which are the reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. In addition, a polyfunctional (meth)acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid and the like can also be mentioned.

In addition, as a preferable free radical crosslinking agent other than the above, it is also possible to use those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. A compound or cardo resin with two or more groups containing ethylenically unsaturated bonds.

In addition, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or Japanese Patent Application Publication No. 02 Vinylphosphonic acid-based compounds and the like described in Bulletin -025493. In addition, the perfluoroalkyl group-containing compound described in JP 61-022048 A can also be used. In addition, it is also possible to use those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesive Association of Japan vol.20, No.7, pages 300 to 308 (1984).

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. It is included in this manual.

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

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

As a free radical crosslinking agent, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dineopentylene pentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentyl erythritol hexa(meth)acrylate (as a commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

As a commercial product of a radical crosslinking agent, for example, SR-494 manufactured by Sartomer Company, Inc. as a 4-functional acrylate having 4 ethoxy chains, and SR-494 as having 4 ethoxy chains are mentioned. SR-209, 231, 239 manufactured by Sartomer Company, Inc., and DPCA-60 as a 6-functional acrylate with 6 pentenoxy chains manufactured by Nippon Kayaku Co., Ltd. , TPA-330 as a trifunctional acrylate with 3 methacryloxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M- 40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As a free radical crosslinking agent, for example, Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Application Publication No. 02-016765, urethane Acrylic acid esters, 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 have ethylene oxide based Carbamate compounds of the backbone are also preferred. In addition, as the free radical crosslinking agent, those described in JP-A 63-277653, JP-A 63-260909, and JP-A 01-105238 that have an amino group in the molecule can also be used. Structure or sulfide structure compound.

The free radical crosslinking agent may also be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphoric acid groups. The free radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. The non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The free radical crosslinking agent is more preferable. Particularly preferably, in the free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is neopentyl erythritol or di-neopentyl Tetraol compound. As a commercially available product, for example, as a polyacid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD., M-510, M-520, etc. can be mentioned.

The preferred acid value of the free radical crosslinking agent with an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. If the acid value of the radical crosslinking agent is in the above range, the workability in production is excellent, and furthermore, the developability is excellent. In addition, the polymerizability is good. On the other hand, from the viewpoint of the development speed during alkali development, the radical crosslinking agent having an acid group preferably has an acid value of 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. The above-mentioned acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of the resolution of the pattern and the stretchability of the film, the photosensitive resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, and PEG200 diacrylate can be used. Methacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Diacrylate Methacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tri Cyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct of bisphenol A diacrylate, EO adduct of bisphenol A dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylic acid Ester, isocyanuric acid modified dimethacrylate, and bifunctional acrylate with urethane bond, and bifunctional methacrylate with urethane bond. These can mix and use two or more types as needed. In addition, from the viewpoint of suppressing the warpage accompanying the control of the elastic modulus of the pattern, as the radical crosslinking agent, a monofunctional radical crosslinking agent can be preferably used. As a monofunctional free radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) Butoxyethyl 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 and other (meth)acrylic acid derivatives, N-ethylene N-vinyl compounds such as pyrrolidone and N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Class etc. As a 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 preferred.

When a radical crosslinking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the photosensitive resin composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less.

One kind of radical crosslinking agent may be used alone, but two or more kinds may be used in combination. When two or more are used in combination, it is preferable that the total amount thereof falls within the above-mentioned range.

＜Other crosslinking agents＞ The photosensitive resin composition of the present invention preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent. In the present invention, other cross-linking agents refer to cross-linking agents other than the above-mentioned free radical cross-linking agents, and there are multiple other compounds in the molecule or their reaction products that are accelerated by the photosensitivity of the above-mentioned photosensitizer in the composition. Compounds with groups that form a covalent bond reaction are preferred, and have multiple in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of acids or bases The compound of the reactive group is preferred. The above-mentioned acid or base is preferably an acid or base produced from a photoacid generator or a photobase generator as a photosensitizer in the exposure process. As other crosslinking agents, compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl are preferred, with compounds selected from the group consisting of hydroxymethyl and alkoxymethyl Compounds in which at least one group is directly bonded to the nitrogen atom are more preferred. As other crosslinking agents, for example, there can be mentioned a compound containing amine groups such as formaldehyde or formaldehyde and alcohol and melamine, acetylene urea, urea, alkylene urea, benzoguanamine, etc. to react with methylol or alkoxy. A compound in which the hydrogen atom of the above-mentioned amino group is replaced by a methyl group. The method for producing 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. Furthermore, it may be an oligomer formed by self-condensation of the methylol groups of these compounds. The crosslinking agent using melamine as the above-mentioned amine group-containing compound is called melamine-based crosslinking agent, and the crosslinking agent using acetylene urea, urea or alkylene urea is called urea-based crosslinking agent. The crosslinking agent of alkylene urea is called alkylene urea-based crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine-based crosslinking agent. Among them, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent. At least one compound from the group of the crosslinking agent and the melamine-based crosslinking agent is more preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

Specific examples of urea-based crosslinking agents include, for example, monohydroxymethylated acetylene carbamide, dihydroxymethylated acetylene carbamide, trihydroxymethylated acetylene carbamide, tetrahydroxymethylated acetylene carbamide, and monomethoxymethylated acetylene carbamide. Methylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxy Methylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxy Methylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide Acetylene carbamide crosslinking agents such as methylated acetylene carbamide; Urea crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; Monohydroxymethylated ethylene urea or dihydroxy methylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxy methylated ethylene urea, monoethoxy methylated ethylene urea , Diethoxy methylated ethylene urea, monopropoxy methylated ethylene urea, dipropoxy methylated ethylene urea, monobutoxy methylated ethylene urea or dibutoxy methyl Ethidium urea cross-linking agent such as oxyethylene urea; Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxy methylated propylene urea, monoethoxy methylated propylene urea , Diethoxy methylated propylene urea, monopropoxy methylated propylene urea, dipropoxy methylated propylene urea, monobutoxy methylated propylene urea or dibutoxy methyl Propionyl urea crosslinking agents such as oxypropionyl urea; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole Pyridone and so on.

As specific examples of the benzoguanamine-based crosslinking agent, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethyl Alkylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene Guanidine, 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 hydroxymethyl and alkoxymethyl, a group selected from the group consisting of hydroxymethyl and alkoxymethyl can also be preferably used. A compound in which at least one group in the group is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) Base) benzophenone, hydroxymethyl phenyl hydroxymethyl benzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, double (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 Tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy -1,3-Benzyldimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products can also be used. Preferred commercially available 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.), etc.

In addition, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzophenone compounds as the other crosslinking agent.

[Epoxy compound (compound with epoxy group)] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction at 200°C or less, and does not generate a dehydration reaction derived from the crosslinking, so film shrinkage is unlikely to occur. Therefore, containing an epoxy compound is effective for the low-temperature curing of the photosensitive resin composition and suppression of warpage.

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

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

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

〔Benzo 㗁 𠯤 compounds (compounds with benzo azole group)〕 Since the benzoxa compound is derived from the cross-linking reaction of the ring-opening addition reaction, outgassing is not generated during hardening, and the heat shrinkage is further reduced and the generation of warping is suppressed, so it is preferable.

As preferred examples of the benzoglyph compound, Ba-type benzoglyph, Bm-type benzoglyph, Pd-type benzoglyph, Fa-type benzoglyph (the above are the trade names, SHIKOKU CHEMICALS CORPORATION Manufacturing), polyhydroxy styrene resin benzo 㗁 adduct, phenol novolak type dihydrobenzo 㗁 𠯤 compound. These can be used alone or in a mixture of two or more.

The content of the other crosslinking agent relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, and still more preferably 0.5-15% by mass. 1.0-10% by mass is particularly preferred. The other crosslinking agent may contain only one kind, or may contain two or more kinds. When two or more other crosslinking agents are contained, it is preferable that the total thereof is within the above-mentioned range.

＜Compounds with sulfonamide structure, compounds with thiourea structure＞ From the viewpoint of improving the adhesion to the base material of the obtained pattern, the photosensitive resin composition of the present invention further includes a compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure At least one compound is preferred.

在式（S-1）中，R表示氫原子或有機基團，R可以與其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。 上述R係與下述式（S-2）中的R² 相同的基團為較佳。 具有磺醯胺結構之化合物可以為具有2個以上磺醯胺結構之化合物，具有1個以上磺醯胺結構之化合物為較佳。[The compound having a sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical formula 52]

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

在式（S-2）中，R¹ 、R² 及R³ 分別獨立地表示氫原子或1價有機基團，R¹ 、R² 及R³ 中的2個以上可以相互鍵結而形成環結構。 R¹ 、R² 及R³ 分別獨立地表示1價有機基團為較佳。 作為R¹ 、R² 及R³ 的例子，可以舉出氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、或者將該等組合2個以上之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如，可以舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為上述環烷基，例如，可以舉出環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可以舉出甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基甲矽烷基，碳數1～10的烷氧基甲矽烷基為較佳，碳數1～4的烷氧基甲矽烷基為更佳。作為上述烷氧基甲矽烷基，可以舉出甲氧基甲矽烷基、乙氧基甲矽烷基、丙氧基甲矽烷基及丁氧基甲矽烷基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。上述芳基可具有烷基等取代基。作為上述芳基，可以舉出苯基、甲苯基、二甲苯基及萘基等。 作為上述雜環基，可以舉出從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、嗎啉環、二氫哌喃環、四氫哌喃環、三𠯤環等雜環結構去除1個氫原子之基團等。The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical formula 53]

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, ^{and two or more of R 1} , R ² and R ³ may be bonded to each other to form a ring structure. Preferably, R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, Aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, or a combination of two or more of these groups, etc. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the aforementioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. As said cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. are mentioned, for example. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The aforementioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, Heterocyclic structures such as pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, dihydropiperan ring, tetrahydropiperan ring, trihydropyran ring, etc. remove 1 hydrogen atom The group and so on.

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

Examples of compounds having a sulfonamide structure include toluenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, Hydroxynaphthyl sulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzene sulfonamide, p-chlorobenzene sulfonamide, toluene sulfonamide, N,N-di Methanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide Amine, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.

在式（T-1）中，R⁴ 及R⁵ 分別獨立地表示氫原子或1價有機基團，R⁴ 及R⁵ 可以鍵結而形成環，R⁴ 可以與*所鍵結之其他結構鍵結而形成環結構，R⁵ 可以與*所鍵結之其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。[Compound with thiourea structure] The thiourea structure is a structure represented by the following formula (T-1). [Chemical formula 54]

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

It ^{is preferable that R 4} and R ⁵ are each independently a hydrogen atom. Examples of R ⁴ and R ⁵ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, and an aryl ether group. Group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group or a combination of two or more of these groups, etc. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the aforementioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. As said cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. are mentioned, for example. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The aforementioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, Heterocyclic structures such as pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, dihydropiperan ring, tetrahydropiperan ring, trihydropyran ring, etc. remove 1 hydrogen atom The group and so on. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

在式（T-2）中，R⁴ ～R⁷ 分別獨立地表示氫原子或1價有機基團，R⁴ ～R⁷ 中的至少2個可以相互鍵結而形成環結構。The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical formula 55]

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

In formula (T-2) in, R (T-1) and R ⁴ in Formula ⁴ and R ⁵ have meaning as R ^5, preferred aspects are also the same. In formula (T-2), it ^{is preferable that R 6} and R ⁷ are independently a monovalent organic group. In the formula (T-2), the preferred aspect of the monovalent organic group in ^{R 6} and R ^{7 is the same as that of the monovalent organic group in R 4} and R ⁵ in the formula (T-1) The appearance is the same.

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

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

＜Migration inhibitor＞ The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions originating from the metal layer (metal wiring) into the photosensitive film.

The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring). Ring, tetrazole ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tricyclic ring) , Thioureas and compounds with hydrogen sulfide groups, salicylic acid derivative compounds, hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion scavenger that traps 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, and JP 2011 can be used. The compound described in paragraph 0052 of JP-059656, the compound described in paragraphs 0114, 0116, and 0118 of JP 2012-194520, and the compound described in paragraph 0166 of International Publication No. 2015/199219 Compound etc.

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

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

＜Polymerization inhibitor＞ The photosensitive resin composition of the present invention may also contain a polymerization inhibitor other than the hindered phenol-based compound.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, pyrogallol, 1,4-benzoquinone, and diphenyl-p-benzene can be preferably used. Quinone, N-nitroso-N-phenylhydroxylamine aluminum salt, phenanthrene, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanedi Aminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2- Naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxyamine first Cerium salt, N-nitroso-N-(1-naphthyl) hydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, di-tertiary butylhydroxytoluene, 1,4 -Naphthoquinone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-( 1H,3H,5H)-Triketone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, phenothionine, 1,1-diphenyl-2-picryl Hydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds can be used.

[Chemical formula 56]

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

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

＜Metal adhesion improver＞ The photosensitive resin composition of the present invention preferably contains a metal adhesive modifier for improving the adhesiveness with metal materials used in electrodes, wiring, and the like. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and β-keto acids Esters (β keto ester) compounds, amine-based compounds, etc.

Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and International Publication No. 2011/ The compound described in paragraphs 0063 to 0071 of 080992, the compound described in paragraphs 0060 to 0061 of JP 2014-191252, and the compound described in paragraphs 0045 to 0052 of JP 2014-041264 , The compound described in paragraph 0055 of International Publication No. 2014/097594. In addition, 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 compound as a silane coupling agent. In the following formulae, Et represents an ethyl group.

作為其他矽烷偶合劑，例如可以舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-（三甲氧基甲矽烷基丙基）異氰脲酸酯、3-脲基丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基甲矽烷基丙基丁二酸酐。該等能夠單獨使用一種或者組合使用兩種以上。[Chemical formula 57]

Examples of other silane coupling agents include vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, and 3-glycidoxy silane. Propylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxy Silane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methylpropene Acrylic oxypropyl methyl diethoxy silane, 3-methacrylic oxy propyl triethoxy silane, 3- propylene oxy propyl trimethoxy silane, N-2-(amino ethyl Group)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethyl Oxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-trimethoxy silyl propyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔Aluminum series adhesive additives〕 As an aluminum-based adhesive agent, for example, tris(ethylacetate) aluminum, tris(acetoneacetone)aluminum, ethylacetate ethylacetate aluminum diisopropoxide, and the like can be mentioned.

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

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. By setting it as the above-mentioned lower limit value or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as below the said upper limit value, the heat resistance and mechanical characteristics of a pattern become favorable. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, the total of them is preferably within the above-mentioned range.

＜Metal adhesion improver＞ The photosensitive resin composition of the present invention preferably contains a metal adhesive modifier for improving the adhesiveness with metal materials used in electrodes, wiring, and the like. As the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide compounds described in paragraphs 0032 to 0043 of JP 2013-072935 can also be used. .

The content of the metal adhesion modifier is preferably 0.1-30 parts by mass relative to 100 parts by mass of the heterocyclic ring-containing polymer precursor, more preferably in the range of 0.5-15 parts by mass, and still more preferably 0.5- Within the range of 5 parts by mass. By setting it to more than the above lower limit, the adhesion between the pattern and the metal layer after the heating process becomes better, and by setting it below the above upper limit, the heat resistance and mechanical properties of the cured product after the heating process become better. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, the total of them is preferably within the above-mentioned range.

＜Other additives＞ The photosensitive resin composition of the present invention can be blended with various additives, such as sensitizers, basic compounds, chain transfer agents, surfactants, higher fatty acid derivatives, and inorganic particles as needed, within the range where the effects of the present invention can be obtained. , Hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, anti-cohesion agents, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

〔Sensitizer〕 The photosensitive resin composition of this invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with specific organometallic complexes, thermal radical polymerization initiators, photo-radical polymerization initiators, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the specific organometallic complex, the thermal radical polymerization initiator, and the photo radical polymerization initiator undergo chemical changes to decompose and generate free radicals, acids, or bases. As the sensitizer, for example, Michelone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylamino)benzylidene) cyclopentan 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-dimethylaminobenzene allylindanone, p-di Methylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene) benzothiazole , 2-(p-dimethylaminophenyl vinylene) isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-di Ethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Benzylcarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3 -Ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4 -Morpholinyl benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2- Mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene) ) Naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzaniline, N-methylacetaniline, 3 ',4'-Dimethylacetaniline, etc. As a sensitizer, a sensitizing dye can also be used. For the details of the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, which is incorporated into this specification.

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

〔Basic Compound〕 The photosensitive resin composition of this invention may contain a basic compound. The basic compound may also be a compound corresponding to the above-mentioned sensitizer, thermal acid generator, photoacid generator, or migration inhibitor. In the present invention, the basic compound is not particularly limited as long as it is a compound that is basic in the curable resin composition. The pKa in the conjugate acid DMSO is preferably 1.0 to 7.0, and more preferably 1.5 to 7.0. , 2.0-7.0 is further preferred. The basic compound is not particularly limited, but an amine compound is preferred, and a secondary amine compound or a tertiary amine compound is more preferred. In addition, the basic compound preferably includes a compound having at least one structure selected from the group consisting of an aromatic amine structure and an alcoholic hydroxyl group, and a compound including an aromatic amine structure and an alcoholic hydroxyl group is more preferred. In this specification, the aromatic amine structure refers to a structure with an amine group or a substituted amine group directly bonded to the aromatic ring. A structure with a substituted amine group bonded to the aromatic ring is preferred, and the aromatic ring is bonded A structure with a disubstituted amino group is more preferable. The substituent in the above-mentioned substituted amino group or disubstituted amino group is not particularly limited, but a hydrocarbon group that may have a substituent is preferable, and a hydrocarbon group having at least an alcoholic hydroxyl group as a substituent is preferable. As the above-mentioned hydrocarbon group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group of 1 to 8 is more preferable, and an alkyl group of 1 to 4 is more preferable. The substituents in the disubstituted amino group may be the same or different. Specific examples of basic compounds include diethanolamine, N-phenyl-N'-ethylethanolamine, N-p-tolyldiethanolamine, or N-phenylethanolamine, but are not limited to these.

When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.01-10% by mass, 0.05-5 The mass% is more preferable, and 0.1 to 3 mass% is still more preferable. One type of basic compound may be used alone, or two or more types may be used in combination.

〔Chain transfer agent〕 The photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in pages 683-684 of the third edition of the Polymer Dictionary (Edited by the Society of Polymer Science, 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These can supply hydrogen to low-activity free radicals to generate free radicals, or generate free radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

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

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

又，界面活性劑亦能夠使用國際公開第2015/199219號的0159～0165段中所記載之化合物。 關於氟系界面活性劑，亦能夠將在側鏈中具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可以舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中所記載之化合物，例如DIC Corporation製造之MEGAFACE RS-101、RS-102、RS-718K等。[Surfactant] From the viewpoint of further improving coating properties, a surfactant can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. In the following formula, the parentheses representing the repeating unit of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating unit of the side chain represent the repeating number of each repeating unit. [Chemical formula 58]

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

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. From the viewpoint of uniformity of the thickness of the coating film and liquid-saving properties, a fluorine-based surfactant having a fluorine content within this range is effective, and its solubility in the composition is also good.

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

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

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

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

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.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one type or two or more types. When there are two or more surfactants, the total amount is preferably within the above-mentioned range.

〔Higher fatty acid derivatives〕 In order to prevent polymerization inhibition caused by oxygen, the photosensitive resin composition of the present invention may be added with higher fatty acid derivatives such as behenic acid or behenic acid amide to make it uneven during the drying process after coating. It is distributed on the surface of the photosensitive resin composition.

In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the photosensitive 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 photosensitive resin composition of the present invention. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total amount is preferably within the above-mentioned range.

〔Thermal polymerization initiator〕 The resin composition of the present invention may also include a thermal polymerization initiator, and in particular, may include a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that initiates or promotes the polymerization reaction of a polymerizable compound by generating free radicals by thermal energy. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, and therefore the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

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

〔Inorganic particles〕 The resin composition of the present invention may contain inorganic particles. As the inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be contained.

The average particle diameter of the aforementioned inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. If the average particle diameter of the inorganic particles is less than 0.01 μm, the mechanical properties of the cured film may be deteriorated. In addition, if the average particle diameter of the aforementioned inorganic particles exceeds 2.0 μm, the resolution may decrease due to the scattering of exposure light.

〔Ultraviolet absorber〕 The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, it is possible to use ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tris-based ultraviolet absorbers. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc., as benzophenone-based ultraviolet absorbers Examples of agents 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-octoxybenzophenone Methyl ketone and so on. Also, as an example of the benzotriazole-based ultraviolet absorber, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tertiary 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-tetra Methyl)phenyl]benzotriazole and the like.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenyl acrylate and 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate. Ester etc. In addition, as an example of the tris-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -Bis(2,4-dimethylphenyl)-1,3,5-tris, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl) tris(hydroxyphenyl) compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl) -1,3,5-tris, and other bis(hydroxyphenyl) tris compounds; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis Butoxyphenyl)-1,3,5-tris, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris, 2,4, 6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris (hydroxyphenyl) tris (hydroxyphenyl) tris compound, etc.

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

〔Organic Titanium Compounds〕 The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, even when it is cured at a low temperature, a resin layer with excellent chemical resistance can be formed.

Examples of the organotitanium compound that can be used include those having an organic group bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable from the viewpoint of the good storage stability of the negative photosensitive resin composition and the ability to obtain a good hardened pattern . Specific examples are bis(triethanolamine)titanium diisopropoxide, bis(2,4-glutarate)bis(n-butoxy)titanium, and diisopropoxytitanium bis(2,4-glutarate) ), titanium diisopropoxide bis(tetramethylpimelate), titanium diisopropoxide bis(ethyl acetate), etc. II) Tetraalkoxide titanium compound: for example, tetra(n-butoxy) titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxy Titanium, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, tetra(n-nonyloxy) titanium, tetra(n-propoxy)titanium, tetrastearyl titanium, tetra[double {2,2-(allyloxymethyl)butoxy}] titanium etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, 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) Monoalkoxide titanium compound: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylbenzene sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, bis(glutarate) titanium oxide, bis(tetramethylpimelate) titanium oxide, phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

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

When the organotitanium compound is blended, the blending amount is preferably 0.05-10 parts by mass relative to 100 parts by mass of the precursor of the cyclized resin, and more preferably 0.1-2 parts by mass. When the compounding amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are shown in the obtained hardened pattern. On the other hand, when the amount is less than 10 parts by mass, the storage stability of the composition is excellent. .

〔Antioxidants〕 The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the ductility of the cured film and the adhesion to the metal material can be improved. Examples of antioxidants include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferable phenol compound, hindered phenol compound can be mentioned. A compound having a substituent at the position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Furthermore, 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 antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]Diphosphoheptin-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenol) ethyl phosphite, etc. . Commercial products of antioxidants include, for example, ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO- 80. ADKSTAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant as necessary. As a potential antioxidant, it can be mentioned that the part that functions as an antioxidant is protected by a protective group, and the protective group is detached by heating at 100-250°C or at 80-200°C in the presence of an acid/base catalyst So as to act as an antioxidant compound. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Publication No. 2017-008219. As a commercially available product of a potential antioxidant, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like can be cited. As examples of preferable antioxidants, 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiary butylphenol, and general formula (3 ) Represented by the compound.

[Chemical formula 59]

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

The compound represented by the general formula (3) suppresses the oxidative degradation of the aliphatic group or phenolic hydroxyl group of the resin. In addition, due to the anti-rust effect on metal materials, metal oxidation can be suppressed.

Since it can act on the resin and the metal material at the same time, it is more preferable that k is an integer of 2 to 4. Examples of R ⁷ include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, and allyl groups. A group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may further have a substituent. Among them, from the viewpoint of solubility in the developer or metal adhesion, it is preferable to have an alkyl ether and -NH-, and from the viewpoint of the interaction with the resin and the metal adhesion based on the formation of metal complexes In general, -NH- is better.

As an example of the compound represented by the following general formula (3), the following can be mentioned, but it is not limited to the following structure.

[Chemical formula 60]

[Chemical formula 61]

[Chemical formula 62]

[Chemical formula 63]

The amount of the antioxidant added is preferably 0.1-10 parts by mass relative to the resin, and more preferably 0.5-5 parts by mass. When the addition amount is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the ductility after the reliability test or the adhesion to metal materials, and when it is more than 10 parts by mass, it may be The interaction of the agent causes the sensitivity of the resin composition to decrease. Only one type of antioxidant may be used, or two or more types may be used. When two or more are used, the total amount of these is preferably within the above-mentioned range.

＜Regarding restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass. As a method of maintaining the moisture content, there can be mentioned adjusting the humidity under storage conditions and reducing the porosity of the container.

From the viewpoint of insulation, the photosensitive resin composition of the present invention preferably has a metal content of less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Further better. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably within the above-mentioned range.

In addition, as a method of reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, there can be mentioned the following methods: selecting a raw material with a low metal content as a raw material constituting the photosensitive resin composition of the present invention; The raw material of the photosensitive resin composition of the present invention is filtered by a filter; the inside of the device is lined with polytetrafluoroethylene, etc., and the distillation is performed under the condition of suppressing pollution as much as possible.

In the photosensitive resin composition of the present invention, considering the use as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass is more preferable. Among them, less than 5 mass ppm is preferred in the state of halogen ions, less than 1 mass ppm is more preferred, and less than 0.5 mass ppm is more preferred. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom, or the chlorine ion and the bromine ion each fall within the above-mentioned range. As a method of adjusting the content of halogen atoms, ion exchange treatment or the like can be preferably cited.

As the storage container of the photosensitive resin composition of the present invention, a conventionally known storage container can be used. In addition, as a container, it is also possible 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 with 6 kinds of resins in a 7-layer structure for the purpose of suppressing the mixing of impurities into the raw materials or photosensitive composition. Better. As such a container, for example, the container described in JP 2015-123351 A can be cited.

＜Use of photosensitive resin composition＞ The photosensitive resin composition of the present invention is preferably used for the formation of an interlayer insulating film for a rewiring layer. Furthermore, in addition to this, it can also be used for the formation of an insulating film of a semiconductor device, the formation of a stress buffer film, and the like.

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

Furthermore, for the purpose of removing foreign matter such as dust or particles in the photosensitive resin composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filter filtration process, multiple filters can be connected in series or in parallel. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. In the case of filtering multiple times, it can be cyclic filtering. In addition, filtration can be performed by applying pressure. When filtering by pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less are preferable, 0.03 MPa or more and 0.9 MPa or less are more preferable, and 0.05 MPa or more and 0.7 MPa or less are more preferable. In addition to filtration using filters, it can also be used to remove impurities using adsorbent materials. 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 cited.

(Cured film, laminated body, semiconductor device and manufacturing method of these) Next, the cured film, the laminate, the semiconductor device, and the manufacturing method thereof will be described.

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

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated to form a laminated body. The laminated system of the present invention preferably includes two or more cured films, and preferably includes a metal layer between any of the cured films. For example, a preferable one may include a laminate having at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are sequentially laminated. The first cured film and the second cured film are both the cured film of the present invention. Preferably, for example, the first cured film and the second cured film are both the photosensitive resin composition of the present invention. The state of the hardened film. The photosensitive resin composition of the present invention used for the formation of the above-mentioned first cured film and the photosensitive resin composition of the present invention used for the formation of the above-mentioned second cured film may have the same composition or different compositions The composition. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.

Examples of the field to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition to this, patterning of a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), or an insulating film for packaging purposes as described above by etching, and the like can be mentioned. Regarding these uses, for example, you can refer to SCIENCE AND TECHNOLOGY CO., LTD. "High-functionalization and application technology of polyimide" April 2008, Kakimoto Yamin/Supervisor, CMC Technical library "Polyimide material Fundamentals and Development" issued in November 2011, Japan Polyimide and Aromatic Polymer Research Association/Edition "Latest Polyimide Fundamentals and Applications" NTS Inc., August 2010, etc.

In addition, the cured film of the present invention can also be used in the manufacture of printing plates such as offset printing plates or screen printing plates, use in the etching of molded components, and protective paints and media in electronics, especially microelectronics. Manufacturing of electrical layers, etc.

The production method of the cured film of the present invention (hereinafter, also simply referred to as "the production method of the present invention".) includes a film formation process of applying the photosensitive resin composition of the present invention to a substrate to form a film (resin film) For better. The method for producing a cured film of the present invention preferably includes the above-mentioned film formation process, an exposure process for exposing the film, and a development process for developing the film. Through the above-mentioned exposure process and development process, the pattern of the cured film can be obtained. In addition, the method for producing a cured film of the present invention includes the above-mentioned film forming process and the above-mentioned development process if necessary, and preferably includes a heating process of heating the above-mentioned film at 50 to 450°C. Specifically, the following processes (a) to (d) are also preferable. (A) Film formation process of applying photosensitive resin composition to a substrate to form a film (resin composition layer) (B) Exposure process for exposing the film after the film formation process (C) Development process for developing the exposed film (D) A heating process in which the developed film is heated at 50～450℃ By heating in the above heating process, the resin layer hardened by exposure can be further hardened. In this heating process, for example, the above-mentioned hot alkali generator is decomposed to obtain sufficient curability.

The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment forms a cured film according to the manufacturing method of the said cured film, and further performs the process of (a), the process of (a)-(c), or the process of (a)-(d) again. In particular, it is preferable to perform the above-mentioned processes multiple times in sequence, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the part provided with the cured film or between the cured films, or between the part provided with the cured film and between the cured films. In addition, when manufacturing a laminate, it is not necessary to repeatedly perform all the processes of (a) to (d). As described above, by performing (a) at least a plurality of times, preferably (a) to (c) or (a) The process of ~(d) can obtain a laminate of a cured film.

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

The type of substrate can be appropriately specified according to the application. It can be used for semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, and reflective materials. Film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of plasma display panels (PDP), etc., There are no special restrictions. In addition, these substrates may be provided with layers such as an adhesive layer or an oxide layer on the surface. In the present invention, semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred. In addition, the substrates may be provided with layers such as an adhesion layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like on the surface. In addition, as the base material, for example, a plate-shaped base material (substrate) can be used. The shape of the substrate is not particularly limited, and may be circular or rectangular, but rectangular is preferable. As the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

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

As a method of applying the photosensitive resin composition to a substrate, coating is preferred.

Specifically, as the applicable method, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, and the spin coating method can be exemplified. Coating method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. By appropriately adjusting the solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. For round substrates such as wafers, spin coating, spray coating, inkjet, etc. are preferred, and for rectangular substrates, narrow A slit coating method, a spray coating method, an inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Furthermore, depending on the viscosity of the photosensitive resin composition or the film thickness to be set, it is also preferable to apply it at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. In addition, in order to obtain uniformity of the film thickness, it is also possible to combine a plurality of rotation speeds for coating. In addition, it is also possible to apply a method of transferring a coating film previously applied by the above-mentioned applying method and formed on a temporary support onto a substrate. Regarding the transfer method, the production described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used in the present invention. method. In addition, a process of removing excess film can be performed at the end of the substrate. Examples of this process include edge bead-like residue rinse (EBR), air knife, back rinse, and so on. In addition, the following pre-wetting process may also be used: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

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

<Exposure Process> The manufacturing method of the present invention may include an exposure process of exposing the above-mentioned film (resin composition layer). The exposure amount is not particularly specified as long as it can harden the photosensitive resin composition. For example, it ^{is better to irradiate 100 to 10,000 mJ/cm 2 in terms} of exposure energy at a wavelength of 365 nm, and more preferably to irradiate 200 to 8,000 mJ/cm ² .

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

Regarding the exposure wavelength, the wavelength is described in terms of the relationship with the light source, such as: (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp , G-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broadband (g, h, i-ray three wavelengths), (4) excimer laser, KrF excimer laser (Wavelength 248nm), ArF excimer laser (wavelength 193nm), F ₂ excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of radiation is 532nm and the third harmonic is 355nm. For the photosensitive resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained. In addition, from the viewpoint of operation and productivity, a wide (3 wavelengths of g, h, and i rays) light source for a high-pressure mercury lamp or a semiconductor laser of 405 nm is also preferable.

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

＜Development process＞ The manufacturing method of the present invention may include a development process of developing the exposed film (resin composition layer) (developing the above-mentioned film). The unexposed part (non-exposed part) is removed by developing. The development method is not particularly limited as long as it can form a desired pattern. For example, spraying of the developer from a nozzle, spray spray, and immersion of the substrate in the developer, etc., can be preferably used. In the development process, the process of continuously supplying the developer to the substrate, the process of holding the developer on the substrate in a substantially stationary state, the process of vibrating the developer with ultrasonic waves, etc., and combinations thereof The manufacturing process and so on.

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

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

When the developer is a developer containing an organic solvent, as for the organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, and isobutyl acetate can be preferably cited. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkane Alkyl oxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, ethyl methoxyacetate) Butyl ester, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), 3-alkoxy propionic acid alkyl esters (for example: 3-alkoxy propionic acid methyl ester, 3-alkoxy propane Ethyl ester, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), Alkyl 2-alkoxypropionate (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, 2-methyl propionate) Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2 -Methyl alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, 2 -Ethyl oxobutyrate, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrus Acetate, ethyl siloxol acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. Ketones, N-methyl-2-pyrrolidone, etc., and, as the cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably mentioned, and as the sulfenes, for example, Specifically, dimethyl sulfoxide can be cited, and a mixture of these organic solvents can also be preferably cited.

When the developer is a developer containing an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. In addition, when the developer contains an organic solvent, one type of organic solvent can be used, or two or more types can be used in combination.

When the developer is a developer containing an organic solvent, it is better that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more than 90% by mass is an organic solvent. good. In addition, in the developer, 100% by mass may be an organic solvent.

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

When the developer is an alkaline aqueous solution, examples of the alkaline compound that can be contained in the alkaline aqueous solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc., and TMAH is preferred. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01-10% by mass in the total mass of the developer, more preferably 0.1-5% by mass, and more preferably 0.3-3% by mass. Better.

〔Method of supplying developer〕 The supply method of the developer solution is not particularly limited as long as it can form the desired pattern. There are methods of immersing the substrate in the developer solution, spin immersion development in which the developer is supplied onto the substrate using a nozzle, or continuous supply of the developer solution. method. The type of nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, spray nozzles, and the like. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the efficiency of manufacturing, the method of supplying the developer with a straight nozzle or the method of continuous supply with a spray nozzle is preferable. From the viewpoint of the permeability of the image area, the method of supplying with a spray nozzle is more preferable. In addition, it is possible to use a straight nozzle to continuously supply the developer solution, rotate the substrate to remove the developer solution from the substrate, spin-dry it, and then continuously supply it again with a straight nozzle, and then rotate the substrate to remove it from the substrate. The manufacturing process of the developer solution, and the process can be repeated several times. In addition, as a method of supplying the developer in the development process, a process of continuously supplying the developer to the substrate, a process of holding the developer on the substrate in a substantially stationary state, and the use of ultrasonic waves to make the developer The process of vibrating on the substrate and the process of combining these.

As the development time, 5 seconds to 10 minutes are preferable, and 10 seconds to 5 minutes are more preferable. The temperature of the developer during development is not particularly defined, and it can usually be performed at 10 to 45°C, preferably 20 to 40°C.

After the treatment using the developer solution, further rinsing can be performed. In addition, a method such as supplying a rinse liquid while the developer in contact with the pattern is not completely dried can be used. Rinsing is preferably carried out in a solvent different from the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. When the developer is a developer containing an organic solvent, examples of the rinse liquid include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), etc., and PGMEA is preferred. In addition, as a rinse solution for development based on a developer containing an alkaline aqueous solution, water is preferable. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid during the rinsing is not particularly defined, but it is preferably possible to perform it at 10 to 45°C, more preferably 18 to 30°C.

Regarding the organic solvent in the case where the rinsing liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, and butyl propionate are preferably mentioned. Ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate Ester (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy Methyl ethyl acetate, ethyl ethoxy acetate, etc.), 3-alkoxy propionic acid alkyl esters (for example: 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. ( For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy Alkyl propionate (for example: 2-alkoxy methyl propionate, 2-alkoxy ethyl propionate, 2-alkoxy propionate propyl ester, etc. (for example, 2-methoxy propionate methyl Ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy- Methyl 2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutanoate, 2-oxobutanoic acid Ethyl esters, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celoxol acetate, ethyl Gieselux acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3- Heptanone, N-methyl-2-pyrrolidone, etc., and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably cited, and as the sulfenes, for example, more Preferably, dimethyl sulfoxide is cited, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, and methyl isobutyl can be cited. Base carbitol, triethylene glycol, etc., and examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, and the like.

When the rinsing liquid contains an organic solvent, one kind of organic solvent can be used or two or more kinds can be used in combination. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfene, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferred, and cyclopentanone, γ-butyrolactone Esters, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

When the rinsing liquid contains an organic solvent, in the rinsing liquid, 50% by mass or more is preferably an organic solvent, more preferably 70% by mass or more is an organic solvent, and more than 90% by mass is an organic solvent. In addition, in the rinse liquid, 100% by mass may be an organic solvent.

The rinsing liquid may further contain other ingredients. As other components, a well-known surfactant, a well-known defoamer, etc. are mentioned, for example.

〔Method of supplying rinsing fluid〕 The method of supplying the rinsing liquid is not particularly limited as long as it can form the desired pattern. There are a method of immersing the substrate in the rinsing liquid, a method of forming a liquid film of the rinsing liquid on the substrate, and a spray to the substrate. The method of supplying the rinsing liquid, the method of continuously supplying the rinsing liquid to the substrate using a mechanism such as a straight nozzle. From the perspective of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency of manufacturing, there are spray nozzles, straight nozzles, spray nozzles, etc. to supply the rinse liquid, and the spray nozzles to continuously supply the method are Preferably, from the viewpoint of the permeability of the rinsing liquid to the image portion, the method of supplying with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, spray nozzles, and the like. That is, it is better to use a straight nozzle to supply the film after exposure or to continuously supply the rinse liquid in the rinse process, and it is more preferable to use the spray nozzle to supply the rinse liquid. In addition, as a method of supplying the developer in the rinsing process, a process in which the rinsing fluid is continuously supplied to the substrate, a process in which the rinsing fluid is maintained on the substrate in a substantially stationary state, and ultrasonic waves are used to make the rinsing fluid. The process of vibrating on the substrate and the process of combining these.

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

The heating system is preferably performed from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1-12°C/min, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the heating rate to 1°C/min or more, productivity can be ensured while preventing excessive volatilization of amines, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be reduced. Furthermore, in the case of an oven capable of rapid heating, it is preferable to proceed from the temperature at the beginning of the heating to the maximum heating temperature at a heating rate of 1 to 8°C/sec, more preferably 2 to 7°C/sec, and 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 more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at which the process of heating to the highest heating temperature is started. For example, when the photosensitive resin composition is applied to the substrate and then dried, the temperature of the dried film (layer), for example, is higher than the boiling point of the solvent contained in the photosensitive resin composition It is better to start to increase gradually at a temperature lower than 30-200°C.

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

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

Heating can be carried out in stages. As an example, the following pretreatment process can be performed: heating from 25°C to 180°C at 3°C/min, holding at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C/min, at 200°C Keep it for 120 minutes. The heating temperature of the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and still more preferably 120-185°C. In this pretreatment process, as described in the specification of US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. Through this kind of pretreatment process, the characteristics of the film can be improved. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can also be a two-stage or more step. For example, the pretreatment process 1 can be performed within the range of 100-150°C, and then the pretreatment process 2 can be performed within the range of 150-200°C.

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

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

＜Metal layer forming process＞ The manufacturing method of the present invention preferably includes a metal layer forming process of forming a metal layer on the surface of the film (resin composition layer) after development.

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

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be applied. For example, methods such as photolithography, lift off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited.

As for the thickness of the metal layer, at the thickest part, 0.01 to 100 μm is preferable, 0.1 to 50 μm is more preferable, and 1 to 10 μm is still more preferable.

＜Layer Process＞ Preferably, the manufacturing method of the present invention further includes a build-up process.

The build-up process refers to the re-sequence of (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process on the surface of the cured film (resin layer) or metal layer. One of the series of manufacturing processes. However, it is also possible to perform only the film formation process of (a) repeatedly. In addition, it can also be set to a state in which the (d) heating process is collectively performed at the end or in the middle of the build-up. That is, it can be set as a state in which the processes of (a) to (c) are repeated a specified number of times, and then (d) heating is performed, whereby the laminated resin composition layer is cured collectively. In addition, (c) the development process may include (e) the metal layer forming process. In this case, the heating of (d) may be performed each time, or the heating of (d) may be performed collectively after a specified number of laminations. Of course, the above-mentioned drying process or heating process may be further appropriately included in the layering process.

When the layering process is further performed after the layering process, the surface activation treatment process may be further performed after the heating process, after the exposure process, or after the metal layer forming process. As the surface activation treatment, plasma treatment can be exemplified.

The above-mentioned layering process is preferably performed 2 to 20 times, more preferably 2 to 5 times, and more preferably 3 to 5 times. In addition, the layers in the build-up process can be layers with the same composition, shape, and film thickness, or they can be different layers.

For example, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, the resin layer is preferably two or more layers and 20 layers or less, and 3 layers or more and 7 layers or less is more preferable. Preferably, 3 layers or more and 5 layers or less are more preferable.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the photosensitive resin composition so as to cover the metal layer after the metal layer is provided. Specifically, there can be mentioned a state in which the steps of (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process are repeated in order, or by The sequence of (a) film formation process, (b) exposure process, (c) development process, and (e) metal layer formation process is repeated in sequence, and (d) heating process is set at the end or in the middle. By alternately performing the lamination process of the laminated resin composition layer (resin layer) and the metal layer formation process, the resin composition layer (resin layer) and the metal layer can be alternately laminated.

(Surface activation treatment process) The manufacturing method of the laminate of the present invention may include a surface activation treatment process of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment process is usually performed after the metal layer formation process, but after the above-mentioned exposure and development process, the photosensitive resin composition layer is subjected to the surface activation treatment process and then the metal layer formation process is performed. The surface activation treatment may be performed only on at least a part of the metal layer, or may be performed only on at least a part of the photosensitive resin composition layer after exposure, or both the metal layer and the photosensitive resin composition layer after exposure may be performed separately. At least part of the person. It is preferable to perform a surface activation treatment on at least a part of the metal layer, and it is preferable to perform a surface activation treatment on a part or all of the area where the photosensitive resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin layer provided on the surface can be improved. In addition, it is preferable to also perform surface activation treatment on part or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the photosensitive resin composition layer to surface activation treatment, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface subjected to the surface activation treatment. The surface activation treatment is specifically selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) plasma treatment, corona discharge treatment, based on CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ etching treatment, surface treatment based on ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, immersion in containing amine The treatment in the organic surface treatment agent of the compound of at least one of the thiol group and the thiol group, the mechanical roughening treatment using a brush, the plasma treatment is better, especially the oxygen plasma treatment using oxygen in the raw gas is better good. In the case of corona discharge treatment, the energy system ^{is preferably 500 to 200,000 J/m 2} , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used in the formation of an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and FIG. 1 Records, these contents are incorporated into this manual. [Example]

Hereinafter, examples are given to further specifically illustrate the present invention. The materials, usage amount, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. As long as there is no special description, "parts" and "%" are quality standards.

<Synthesis example 1: Synthesis of polymer A-1> 46.96 g of 4,4'-oxydiphthalic dianhydride (ODPA) was put into a separable flask, and 2-hydroxy methacrylic acid was put into it 39.69 g of ethyl ester (HEMA) and 136.83 g of γ-butyrolactone were stirred at room temperature, and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation based on the reaction was over, it was naturally cooled to room temperature and left at room temperature for 16 hours. Next, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone while stirring under ice cooling was added to the reaction mixture over 40 minutes, and then the solution was stirred while stirring. A suspension of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of γ-butyrolactone was added for 60 minutes. After further stirring for 30 minutes at room temperature, 7.17 g of ethanol was added and stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction liquid was added to 716.21 g of ethanol, and a precipitate composed of a crude polymer was formed. The produced crude polymer was filtered out and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered and dried under vacuum to obtain a powdery polymer (polyimide precursor) P-1 . The total molar content of the cyclic isoimine structure and the cyclic isoimine structure contained in 1 g of polymer P-1 was measured by the ¹ H-NMR (Nuclear Magnetic Resonance) method. The result is 0.086mmol/g.

<Synthesis example 2: Synthesis of polymer P-2> Except that 46.91 g of ODPA was changed to an equal molar amount of 4,4'-bisphthalic dianhydride (BPDA), it was the same as in Synthesis Example 1 The method, synthesized polymer (polyimide precursor) P-2. The total molar content of the cyclic imine structure and the cyclic isoimine structure contained in 1 g of the polymer P-2 was measured by the ¹ H-NMR method, and it was 0.080 mmol/g.

<Synthesis example 3: Synthesis of polymer P'-1> In a drying reactor equipped with a stirrer, a condenser, and a flat-bottomed joint with an internal thermometer, 4,4'-oxydiphthalene was removed while removing water. 20.2 g (65.0 millimoles) of dicarboxylic dianhydride was suspended in 140 mL of diglyme. 16.8 g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 millimoles) of pyridine were added, and the mixture was stirred at a temperature of 60°C for 18 hours. Then, after cooling the mixture to -20°C, 16.1 g (135.5 millimoles) of sulfite chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was heated to room temperature, and after stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, to the obtained transparent solution, a solution obtained by dissolving 11.8 g (58.7 millimoles) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 1 hour. Next, 5.6 g (17.5 millimoles) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimine precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45°C for 3 days to obtain polymer P'-1. The total molar content of the cyclic isoimide structure and the cyclic isoimine structure contained in 1 g of polymer P'-1 was measured by the ¹ H-NMR method and found to be 0.001 mmol/g .

<Synthesis example 4: Synthesis of polymer P'-2> 20.2 g (65.0 millimoles) of 4,4'-oxydiphthalic dianhydride was changed to equal molar amount of 4,4'-bis With the exception of phthalic dianhydride (BPDA), the polymer (polyimide precursor) P'-2 was synthesized in the same manner as in Synthesis Example 3. The total molar content of the cyclic imine structure and the cyclic isoimine structure contained in 1 g of polymer P'-2 was measured by the ¹ H-NMR method, and it was 0.001 mmol/g .

<Synthesis Example 5: Synthesis of Polymer P-3> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 65.56g (179mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was removed while removing water. ) And 1,3-bis(3-aminopropyl)tetramethyldisiloxane 2.48g (10mmol) are dissolved in 300g of N-methylpyrrolidone (NMP). Next, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 30°C for 2 hours. Next, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 30°C for 2 hours. After stirring, the temperature was increased to 190°C while flowing nitrogen at a flow rate of 200 ml/min, and stirring was carried out for 6 hours. After cooling the above-mentioned reaction liquid to 25°C, 0.005 g of p-methoxyphenol was added and dissolved. 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise to this solution, and after stirring at 25°C for 2 hours, it was further stirred at 60°C for 3 hours. This was cooled to 25°C, 10 g of acetic acid was added, and the mixture was stirred at 25°C for 1 hour. After stirring, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio), and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, rinsed with 1.5 liters of water, and the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again to obtain polyimide. The obtained polyimide was dried at 40°C for 1 day under reduced pressure, thereby obtaining P-3.

<Synthesis Example 6: Synthesis of Polymer P-4> In 400 g of N-methylpyrrolidone, 28.0 g (76.4 millimoles) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved. Subsequently, 12.1 g (153 millimoles) of pyridine was added, and while maintaining the temperature at -10 to 0°C, the 4,4'-oxydipyridine was dissolved in 100 g of N-methylpyrrolidone and was added dropwise over 1 hour. A solution of 20.7 g (70.1 millimoles) of benzyl chloride. After stirring for 30 minutes, 1.00 g (12.7 millimoles) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole precursor resin was obtained by filtration, stirred again for 30 minutes in 6 liters of water, and filtered again. Next, the obtained polybenzoxazole precursor was dried under reduced pressure at 45°C for 3 days to obtain polymer P-4.

<Synthesis Example 7: Synthesis of Polymer P-5> The polymer P-4 was dissolved in 300 g of N-methylpyrrolidone (NMP), and the temperature was increased to 190° C. while flowing nitrogen at a flow rate of 200 ml/min, followed by stirring for 6 hours. After stirring, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio), and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polybenzoxazole was obtained by filtration. After rinsing with 1.5 liters of water, the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes and filtered again to obtain polybenzoxazole. The obtained polybenzoxazole was dried under reduced pressure at 40°C for 1 day to obtain polymer P-5.

<Synthesis Example 8: Synthesis of Polymer P-6> In Synthesis Example 1, 39.69 g of 2-hydroxyethyl methacrylate (HEMA) was changed to 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 18.32 g of diethylene glycol monomethyl ether. Otherwise, Synthesis was carried out in the same manner as in Synthesis Example 1 to obtain polymer P-6.

<Examples and Comparative Examples> In each example, the components described in the following table were mixed to obtain each photosensitive resin composition. In addition, in each comparative example, the components described in the following table were mixed to obtain each comparative composition. Specifically, the content of each component other than the solvent described in the table shall be the amount (parts by mass) described in each column of the table. The content of the solvent is such that the solid content concentration of each composition becomes the “solid content concentration (%)”. The obtained photosensitive resin composition and the comparative composition were pressure-filtered using a polytetrafluoroethylene filter having a pore width of 0.8 μm. In addition, in the table, the description of "-" indicates that the composition does not contain the corresponding component.

[Table 1] type Example 1 2 3 4 5 6 7 8 9 Resin P-1 41.5 - - - - 40.0 40.3 41.5 41.4 P-2 41.5 - - - - 40.0 40.3 41.5 41.4 P'-1 - - - - 41.0 - - - - P'-2 - - - - 41.0 - - - - P-3 - 80.7 - - - - - - - P-4 - - 74.8 - - - - - - P-5 - - - 73.1 - - - - - P-6 - - - - - - - - - Polymerization inhibitor A-1 - - - - - - - 0.1 - A-2 - - - - - - - - 0.1 A-3 - - - - - - - - - A-4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Migration inhibitor B-1 0.1 - - - - - - 0.1 - B-2 - - 0.1 - - - - - - Silane coupling agent C-1 - - - - - - - 0.5 - C-2 1.5 1.5 1.5 1.5 1.5 1.2 1.2 1 1.5 C-3 - - - - - 0.3 - - - C-4 - - - - - - 0.3 - - C-5 - - - - - - - - - Polymerization initiator D-1 - - - - - 0.5 - - - D-2 1 1.3 1.1 0.9 2.5 1 1.4 0.8 1.2 D-3 - - - - - 0.5 - - - D-4 - - - - - - 2 - - D-5 - - - - - - - - - Crosslinking agent E-1 8 8 16 16 8 8 8 7 8 E-2 - - - - - - - 1 - Thermal alkali generator F-1 - - 3 - - - - - - F-2 - 2 - - - - - - - F-3 - - - 2 - - - - - F-4 - - - - - 2 - - - Basic compound G-1 6 6 3 6 6 6 6 6 5 G-2 - - - - - - - - 1 Other organometallic compounds H-1 - - - - - - - - - H-2 - - - - - - - - - H-3 - - - - - - - - - H-4 - - - - - - - - - H-5 - - - - - - - - - Solid content concentration (%) 44 44 44 44 44 44 44 44 44 Solvent S-1 80 80 80 80 80 80 80 80 80 S-2 20 20 20 20 20 20 20 20 20 Film thickness (μm) 15 15 15 15 15 15 15 15 15 Absorbance of film 0.312 0.335 0.301 0.277 0.223 0.304 0.345 0.292 0.331 Exposure conditions M M M M M M M M M Developing conditions A B A B A A A A A Pattern shape A A A A A A A A A Resolution A B B B A A A A A Adhesion A B B B B A A A A Mechanical properties A A A A A A A A A Chemical resistance A A A A A A A A A

[Table 2] type Example 10 11 12 13 14 15 16 17 18 Resin P-1 41.3 44.4 41.5 - 41.5 41.5 41.5 41.5 41.5 P-2 41.3 44.4 41.5 - 41.5 41.5 41.5 41.5 41.5 P'-1 - - - - - - - - - P'-2 - - - - - - - - - P-3 - - - - - - - - - P-4 - - - - - - - - - P-5 - - - - - - - - - P-6 - - - 82.9 - - - - - Polymerization inhibitor A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 0.1 - - - - - - - - A-4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Migration inhibitor B-1 - - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 B-2 - - - - - - - - - Silane coupling agent C-1 - - - - - - - - - C-2 1.5 1.5 1.5 1.5 - 1.5 1.5 1.5 1.5 C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 - - - - 1.5 - - - - Polymerization initiator D-1 - - - - - - - - - D-2 1.3 1.2 1 1 1 0.000 1 1 1 D-3 - - - - - - - - - D-4 - - - - - - - - - D-5 - - - - - 1 - - - Crosslinking agent E-1 8 8 8 8 8 8 8 8 8 E-2 - - - - - - - - - Thermal alkali generator F-1 - - - - - - - - - F-2 - - - - - - - - - F-3 - - - - - - - - - F-4 - - - - - - - - - Basic compound G-1 5 - 6 6 6 6 6 6 6 G-2 1 - - - - - - - - Other organometallic compounds H-1 - - - - - - 1 - - H-2 - - - - - - - 1 - H-3 - - - - - - - - 1 H-4 - - - - - - - - - H-5 - - - - - - - - - Solid content concentration (%) 44 44 44 44 44 44 44 44 44 Solvent S-1 80 80 80 80 80 80 80 80 80 S-2 20 20 20 20 20 20 20 20 20 Film thickness (μm) 15 15 15 15 15 15 15 15 15 Absorbance of film 0.325 0.309 0.278 0.290 0.302 0.240 0.314 0.290 0.302 Exposure conditions M M D M M M M M M Developing conditions A A A A A A A A A Pattern shape A A A A A A A A A Resolution A A A A A A A A A Adhesion A A A A A A A A A Mechanical properties A A A A A A A A A Chemical resistance A A A A A A A A A

[table 3] type Example Comparative example 19 20 twenty one twenty two twenty three 1 2 3 4 5 Resin P-1 41.5 41.5 41.5 41.5 41.4 39.8 - - 40.6 41.4 P-2 41.5 41.5 41.5 41.5 41.4 39.8 - - 40.6 41.4 P'-1 - - - - - - 39.8 40.1 - - P'-2 - - - - - - 39.8 40.1 - - P-3 - - - - - - - - - - P-4 - - - - - - - - - - P-5 - - - - - - - - - - P-6 - - - - - - - - - - Polymerization inhibitor A-1 - - - - - - - - - - A-2 - - - - 0.1 - - - - 0.1 A-3 - - - - - - - 0.1 - - A-4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - - 0.5 Migration inhibitor B-1 0.1 0.1 0.1 0.1 - 0.1 0.1 - 0.1 - B-2 - - - - - - - - - - Silane coupling agent C-1 - - - - - - - - - - C-2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 C-3 - - - - - - - - - - C-4 - - - - - - - - - - C-5 - - - - - - - - - - Polymerization initiator D-1 - - - - - - - - - - D-2 1 1 1 1 8.0 0 1 0 0 10.0 D-3 - - - - - 1 1 1 1 - D-4 - - - - - 3.3 3.3 3.3 3.3 - D-5 - - - - - - - - - - Crosslinking agent E-1 8 8 8 8 8 8 8 8 8 8 E-2 - - - - - - - - - - Thermal alkali generator F-1 - - - - - - - - - - F-2 - - - - - - - - - - F-3 - - - - - - - - - - F-4 - - - - - - - - - - Basic compound G-1 6 6 6 6 5 6 6 6 5 5 G-2 - - - - 1 - - - - 1 Other organometallic compounds H-1 - - - - - - - - - - H-2 - - - - - - - - - - H-3 - - - - - - - - - - H-4 1 - - - - - - - - - H-5 - 1 - - - - - - - - Solid content concentration (%) 44 44 44 44 44 44 44 44 44 44 Solvent S-1 80 80 80 80 80 80 80 80 80 80 S-2 20 20 20 20 20 20 20 20 20 20 Film thickness (μm) 15 15 20 30 15 15 15 15 15 15 Absorbance of film 0.290 0.314 0.278 0.278 0.586 0.276 0.170 0.120 0.276 0.663 Exposure conditions M M M M M M M M M M Developing conditions A A A A A A A A A A Pattern shape A A A A A C B B C B Resolution A A A A A B D E B C Adhesion A A A A A B C C B B Mechanical properties A A A A A C B B C C Chemical resistance A A A A A C B B D C

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

〔Resin〕 ・P-1～P-6, P’-1～P’-2: Polymers P-1～P-6, P’-1～P’-2 obtained from the above synthesis example

[Polymerization inhibitor] ・A-1～A-4: Compounds of the following structure [Chemical formula 64]

<Migration inhibitor> ・B-1～B-2: Compounds of the following structure [Chemical formula 65]

上述結構中，Me表示甲基，Et表示乙基。[Silane Coupling Agent (Metal Adhesion Improver)] ・C-1～C-5: Compounds of the following structure [Chemical formula 66]

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

D-2及D-5為具有光自由基聚合開始能之化合物。[Photo-radical polymerization initiator] ・D-1～D-4: Compounds of the following structure ・D-5: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6 -Difluorophenyl) Titanium [Chemical formula 67]

D-2 and D-5 are compounds with photo-radical polymerization initiation ability.

(Crosslinking agent) ・E-1～E-2: Compounds of the following structure [Chemical formula 68]

[Thermal alkali generator] ・F-1～F-4: Compounds of the following structure [Chemical formula 69]

[Basic compound] ・G-1～G-2: Compounds of the following structure [Chemical formula 70]

[Other organometallic compounds] ・H-1: Titanium tetraisopropoxide (manufactured by Matsumoto Fine Chemical Co. Ltd.) ・H-2: Diisopropoxybis(acetone) titanium (Matsumoto Fine Chemical Co.) Ltd.) ・H-3～H-5: Compounds of the following structure [Chemical formula 71]

〔Solvent〕 ・S-1: N-Methyl-2-pyrrolidone ・S-2: Ethyl lactate

＜Evaluation＞ 〔Measurement of absorbance〕 In each Example or Comparative Example, the prepared photosensitive resin composition or comparative composition was coated on a glass substrate by a spin coating method. The substrate was heated to 100°C at a temperature increase rate of 10°C/min on a hot plate under the atmosphere, and then maintained at 100°C for 5 minutes to form a film with a film thickness of 15 μm. The absorbance at a wavelength of 405 nm of the above-mentioned film was measured using an ultraviolet-visible spectrophotometer (UH-4150, manufactured by Hitachi High-Tech Science Corporation), and it was described in the "Absorbance of the film" column of the table.

[Evaluation of pattern shape] In each of the Examples and Comparative Examples, each photosensitive resin composition or comparative composition was applied (coated) in a layered form on a silicon wafer by a spin coating method, thereby forming a composition layer. In each of the Examples and Comparative Examples, the silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 100°C for 5 minutes, and the "film thickness (") in the table was formed on the silicon wafer. μm)" The resin layer of the thickness described in the column. In the example described as "M" in the exposure conditions, an h-ray stepper was used to expose the resin layer on the silicon wafer. Exposure was carried out through a mask (a binary mask with a pattern of 1:1 lines and spaces and a line width of 10 μm). In order to obtain a pattern of a resin layer with a line width of 10 μm after development described later, the exposure amount was appropriately set. In the example described as "D" in the exposure conditions, exposure was performed using a direct exposure device (AdTech DE-6UH III). The exposure wavelength was set to 405 nm. The laser direct imaging exposure was performed in which the exposed part became a 1:1 line with a width of 10μm and the line part in the space pattern. In order to obtain a pattern of a resin layer with a line width of 10 μm after development described later, the exposure amount was appropriately set. After the above exposure, in the example described as "A" in the column of "Development Conditions", cyclopentanone was used for 60 seconds of development, and propylene glycol monomethyl ether acetate (PGMEA) was used for 20 seconds of washing. Thus, the line and space pattern of the resin layer after exposure is obtained. In the example described as "B" in the column of "Development Conditions", as the developer, a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution was used for 5 minutes of development and rinsed with pure water to obtain Line and space pattern of the resin layer after exposure. The line and space pattern was heated in a nitrogen environment at a temperature increase rate of 10°C/min, and heated at 230°C for 3 hours to obtain a cured film. Regarding the silicon wafer on which the cured film is formed, the silicon wafer is cut perpendicular to the line and space pattern of the cured film to expose the pattern cross section. Using an optical microscope, the cross-section of the pattern of the line and space pattern was observed at a magnification of 200 times, and the cross-sectional shape of the pattern was evaluated. Specifically, in each of the Examples and Comparative Examples, the taper angle formed by the surface of the silicon wafer (substrate surface) and the side surface of the cured film was measured and evaluated in accordance with the following evaluation criteria. The evaluation results are described in the column of "pattern shape" in the table. In this evaluation, it can be said that the taper angle does not exceed 90°, and the cross-sectional shape of the pattern is not a constricted shape. The closer the taper angle is to 90°, the better the pattern shape. -Evaluation criteria- A: The taper angle is 85° or more and 90° or less. B: The taper angle is 80° or more and less than 85°. C: The cone angle is less than 80°, or the cross-sectional shape of the pattern is an inverted cone shape with a cone angle exceeding 90°, or the cross-sectional shape of the pattern is a constricted shape.

[Resolution evaluation] In each of the Examples and Comparative Examples, each photosensitive resin composition or comparative composition was applied (coated) in a layered form on a silicon wafer by a spin coating method, thereby forming a composition layer. In each of the Examples and Comparative Examples, the silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 100°C for 5 minutes, and the "film thickness (") in the table was formed on the silicon wafer. μm)" The resin layer of the thickness described in the column. In the example described as "M" in the exposure conditions, an h-ray stepper was used to expose the resin layer on the silicon wafer. Exposure was performed through a mask of a fuse box with a width of 5 μm to 25 μm and a scale of 1 μm. The exposure level is set to the minimum line width described later as the minimum exposure level. In the example described as "D" in the exposure condition, the direct exposure device (AdTech DE-6UH III) was used, and the exposed part became a 1:1 line and space pattern with a width of 5μm to a width of 25μm and a scale of 1μm. Laser direct imaging of the line is exposed. The exposure wavelength was set to 405 nm. The exposure level is set to the minimum line width described later as the minimum exposure level. After the above-mentioned exposure, in the example described as "A" in the column of "Development Conditions", development was carried out with cyclopentanone for 60 seconds, and washing was carried out with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds. Thus, the line and space pattern of the resin layer after exposure is obtained. In the example described as "B" in the column of "Development Conditions", as a developer, a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution was used for 5 minutes of development and rinsed with pure water to obtain Line and space pattern of the resin layer after exposure. Among the above-mentioned line and space patterns, the line width of the line pattern with the smallest line width in which the silicon wafer is exposed between the line patterns was regarded as the "minimum line width", and the evaluation was performed in accordance with the following evaluation criteria. It can be said that the smaller the line width, the better the resolution. For example, it means that the width of the metal wiring formed in the subsequent plating process can be made finer, which is a better result. The measurement limit is 5 μm. The evaluation results are described in the "resolution" column in the table. -Evaluation criteria- A: The minimum line width is 5 μm or more and less than 8 μm. B: The minimum line width is 8 μm or more and less than 10 μm. C: The minimum line width is 10 μm or more and less than 12 μm. D: The minimum line width is 12 μm or more and less than 15 μm. E: The minimum line width is 15 μm or more.

〔Evaluation of Adhesion〕 In each Example and Comparative Example, each photosensitive resin composition or each comparative composition was applied (coated) in a layer form on a copper substrate by a spin coating method to form a resin composition layer. In each of the Examples and Comparative Examples, the copper substrate to which the obtained composition layer was applied was dried on a hot plate at 100°C for 5 minutes, thereby forming the "film thickness (μm) in the table" on the copper substrate. )" The resin layer of the thickness described in the column. In the example described as "M" in the exposure conditions, an h-ray stepper was used to expose the resin layer on the copper substrate. Exposure was performed through a mask in which a 100 μm square non-masked part was formed. In order to obtain a pattern of a 100 μm square resin layer after development described later, the exposure amount was appropriately set. In the example described as "D" in the exposure conditions, exposure was performed using a direct exposure device (AdTech DE-6UH III). The exposure wavelength was set to 405 nm. Direct imaging exposure was performed with a laser in a square shape such as a 100μm square in the exposure area. In order to obtain a pattern of a 100 μm square resin layer after development described later, the exposure amount was appropriately set. After the above exposure, in the example described as "A" in the column of "Development Conditions", cyclopentanone was used for 60 seconds of development, and propylene glycol monomethyl ether acetate (PGMEA) was used for 20 seconds of washing. A pattern of a square-shaped resin layer of 100 μm square was obtained. In the example described as "B" in the column of "Development Conditions", as a developer, a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution was used for 5 minutes of development and rinsed with pure water to obtain 100μm A pattern of a square resin layer. The above pattern was heated in a nitrogen atmosphere at a temperature increase rate of 10°C/min, and heated at 230°C for 3 hours to obtain a cured film. In an environment of 25° C. and 65% relative humidity (RH), the shear force of the cured film was measured with an adhesion tester (manufactured by XYZTEC Corporation, CondorSigma), and evaluated according to the following evaluation criteria. The evaluation result is described in the column of "adhesion" in the table. The greater the shear force, the better the adhesiveness (copper adhesiveness) of the cured film.

-Evaluation criteria- A: The shear force exceeds 40gf. B: The shear force exceeds 30 gf and is 40 gf or less. C: The shear force is 30 gf or less. In addition, 1gf is 0.00980665N.

[Evaluation of mechanical properties] In each of the Examples and Comparative Examples, each photosensitive resin composition or comparative composition was applied (coated) in a layered form on a silicon wafer by a spin coating method, thereby The composition layer is formed. The silicon wafer applied with the obtained composition layer was dried on a hot plate at 100°C for 5 minutes, and the silicon wafer was formed on the silicon wafer in the column of "film thickness (μm)" in the table Thick photosensitive resin composition layer. A broadband exposure machine (manufactured by USHIO INC.: UX-1000SN-EH01) was used to expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of ^{400 mJ/cm 2.} Exposure was performed through a photomask, and the shape of the photomask was set to a shape that would give a pattern with a sample width of 2 mm and a sample length of 50 mm after development described later. After exposure, in the example described as "A" in the column of "Development Conditions", as a developer, cyclohexanone was used for development for 60 seconds, and it was rinsed with PGMEA. In the example described as "B" in the column of "Development Conditions", as a developer, a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution was used for 5 minutes of development and rinsed with pure water. The photosensitive resin composition layer (resin layer) after development was heated in a nitrogen atmosphere at a temperature increase rate of 5° C./min, and after reaching 230° C., heating was performed for 3 hours. The heated resin layer was immersed in a 3% by mass hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin film. A tensile strength test was performed on the resin film peeled from the silicon wafer. The test uses a tensile testing machine (Tensilon) with a crosshead speed of 300mm/min, a sample width of 2mm, and a sample length of 50mm. For the length of the film, under an environment of 25°C and 65%RH (relative humidity), Measured in accordance with JIS-K6251 (Japanese Industrial Standards). The elongation (elongation at break) of the sample when the sample was broken at the time of cutting was measured 10 times each, and the arithmetic mean of the elongation at break obtained in the 10 measurements was calculated. The results were evaluated in accordance with the following evaluation criteria. The evaluation results are described in the column of "mechanical properties" in the table. -Evaluation Criteria- A: The above arithmetic average is 60% or more. B: The above arithmetic average is 50% or more and less than 60%. C: The arithmetic average of the above is less than 50%.

[Evaluation of chemical resistance] The entire surface was exposed without using a photomask during exposure, and development was omitted for simplification of evaluation. Except for this, a cured film was formed on the silicon wafer by the same method as the above-mentioned evaluation of mechanical properties. Without peeling the cured film from the silicon wafer, the cured film and silicon wafer were immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: In the chemical solution, the resin layer was immersed at 75°C for 15 minutes, the film thickness before and after the immersion were compared, and the dissolution rate (nm/min) was calculated. The evaluation was performed in accordance with the following evaluation criteria, and the evaluation results were described in the column of "chemical resistance" in the table. The lower the dissolution rate, the better the chemical resistance. -Evaluation criteria- A: The dissolution rate is less than 200 nm/min. B: The dissolution rate is 200 nm/min or more and less than 300 nm/min. C: The dissolution rate is 300 nm/min or more and less than 400 nm/min. D: The dissolution rate is 400 nm/min or more.

From the above results, it can be seen that the photosensitive resin composition of the present invention has an excellent pattern shape of the obtained pattern.

<Example 101> The photosensitive resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate with the copper thin layer formed on the surface by the spin coating method, and dried at 100°C 5 After forming a photosensitive film with a film thickness of 20 μm in minutes, exposure was performed using a stepper (manufactured by Nikon Co., Ltd., NSR1505 i6). Through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10 μm), exposure was performed at a wavelength of 365 nm. After the exposure, it was heated at 100°C for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes, and washed with PGMEA for 30 seconds to obtain a layer pattern. Next, the temperature was raised at a temperature increase rate of 10° C./min under a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 3 hours, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, a semiconductor device was manufactured using these interlayer insulating films for rewiring layers. As a result, it was confirmed that there was no problem in the operation.

none.

Claims (17)

A photosensitive resin composition, which contains: A resin selected from the group consisting of at least one polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole; Organometallic complexes with photopolymerization initiation ability; and Hindered phenol compounds, In the case of forming a film composed of the photosensitive resin composition with a film thickness of 15 μm by heating at 100° C. for 5 minutes, the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6. A photosensitive resin composition, which contains: A resin selected from the group consisting of at least one polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole; Organometallic complexes with photo-radical polymerization initiation ability; and Hindered phenol compounds, For forming a film composed of the aforementioned photosensitive resin composition, The film thickness of the foregoing film is 15 μm or more, and the absorbance at a wavelength of 405 nm of the foregoing film is 0.2 to 0.6. The photosensitive resin composition according to claim 1 or 2, wherein The aforementioned organometallic complex has photoradical polymerization initiation ability. The photosensitive resin composition according to claim 1 or 2, wherein The metal in the aforementioned organometallic complex is titanium. The photosensitive resin composition according to claim 1 or 2, wherein The aforementioned organometallic complex is a metallocene compound. The photosensitive resin composition according to claim 1 or 2, wherein The content of the aforementioned organometallic complex is 0.5% by mass to 5.0% by mass with respect to the total solid content of the photosensitive resin composition. The photosensitive resin composition according to claim 1 or claim 2, which further contains a sensitizer. The photosensitive resin composition according to claim 1 or 2, wherein The aforementioned resin is a polyimide precursor containing at least one of a cyclic iminium structure and a cyclic isoiminium structure, and the cyclic iminium structure and the cyclic ring in 1g of the polyimide precursor The total molar content of the isoimide structure is 0.08 mmol/g to 1.68 mmol/g. The photosensitive resin composition according to claim 1 or claim 2, which is used to form a photosensitive film for negative development. The photosensitive resin composition according to claim 1 or claim 2, which is used to form an interlayer insulating film for a rewiring layer. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. A laminated body including two or more layers of the cured film according to claim 11, and including a metal layer between any of the foregoing cured films. A method for manufacturing a hardened film, which includes: The film forming process is to apply the photosensitive resin composition according to any one of claims 1 to 10 to a substrate to form a film. The method for manufacturing a cured film according to claim 13, which includes: an exposure process for exposing the aforementioned film; and a development process for developing the aforementioned film. The method of manufacturing a cured film according to claim 13, wherein The aforementioned exposure is based on the laser direct imaging method. The method of manufacturing a hardened film as described in claim 13, which includes: The heating process involves heating the aforementioned film at 50°C to 450°C. A semiconductor device comprising the cured film as described in claim 11.