Photosensitive resin composition, method for producing patterned cured product, cured product, interlayer insulating film, cover coat, surface protective film, and electronic component

Abstract

A photosensitive resin composition comprises: (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photopolymerization initiator, (D) a cyclization catalyst, and (E) a solvent.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a method for producing a patterned cured product, the cured product, an interlayer insulating film, a cover coat, a surface protective film, and an electronic component. Background Art

[0002] Conventionally, surface protection films and interlayer insulation films for semiconductor elements have used polyimide and polybenzothiophene, which have excellent heat resistance, electrical properties, and mechanical properties. In recent years, photosensitive resin compositions imparting photosensitivity to these resins themselves have been used. Use of such photosensitive resin compositions can simplify the production process of patterned cured products, shortening the complex production process (for example, see Patent Document 1).

[0003] Furthermore, in recent years, miniaturization of transistors, which supports the advancement of computer performance, has reached the limit of scaling laws. To further enhance performance and speed, stacked device structures in which semiconductor elements are stacked three-dimensionally have attracted attention.

[0004] In the stacked device structure, multi-die fan-out wafer level packaging (Multi-die Fanout Wafer Level Packaging) is a package manufactured by sealing multiple chips together in one package. Compared with the previously proposed fan-out wafer level packaging (manufactured by sealing one chip in one package), it can be expected to be low-cost and high-performance, and therefore has attracted much attention.

[0005] In the production of multi-chip fan-out wafer-level packages, low-temperature curing properties are strongly required from the perspectives of protecting high-performance chips, protecting heat-resistant sealing materials, and improving yield (for example, see Patent Document 2).

[0006] Furthermore, as a resin composition, a resin composition containing a polyimide precursor is disclosed (for example, refer to Patent Document 3).

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-265520

[0010] Patent Document 2: International Publication No. 2008 / 111470

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 2016-199662 Summary of the Invention

[0012] An object of the present invention is to provide a photosensitive resin composition, a method for producing a patterned cured product, an interlayer insulating film, a cover coat, a surface protective film, and an electronic component that can form a cured product having excellent mechanical properties even when cured at a low temperature of 230°C or less and has excellent storage stability.

[0013] According to the present invention, the following photosensitive resin composition and the like are provided.

[0014] 1. A photosensitive resin composition comprising:

[0015] (A) a polyimide precursor having a polymerizable unsaturated bond,

[0016] (B) polymerizable monomers,

[0017] (C) photopolymerization initiator,

[0018] (D) a cyclization catalyst, and

[0019] (E) Solvent.

[0020] 2. The photosensitive resin composition according to 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

[0021] [Chemistry 1]

[0022]

[0023] (In formula (1), X1 is a tetravalent group having one or more aromatic groups, the -COOR1 group and the -CONH- group are ortho-positioned to each other, and the -COOR2 group and the -CO- group are ortho-positioned to each other. Y1 is a divalent aromatic group. R1 and R2 are each independently a hydrogen atom, a group represented by the following formula (2), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R1 and R2 is a group represented by the above formula (2).)

[0024] [Chemistry 2]

[0025]

[0026] (In formula (2), R3 to R5 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)

[0027] 3. The photosensitive resin composition according to 1 or 2, wherein the component (D) is at least one selected from the group consisting of N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2′-(4-methylphenylimino)diethanol.

[0028] 4. The photosensitive resin composition according to 1 or 2, wherein the component (D) contains a compound represented by the following formula (17).

[0029] [Chemistry 3]

[0030]

[0031] (In formula (17), R 31A ~R 33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, and R 31A ~R 33A At least one of R is a monovalent aromatic group. 31A ~R 33A Adjacent groups may form a ring.)

[0032] 5. The photosensitive resin composition according to any one of 1 to 4, wherein the component (C) comprises (C1) a compound represented by the following formula (15) and (C2) a compound represented by the following formula (16).

[0033] [Chemistry 4]

[0034]

[0035] (In formula (15), R 11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. 12A R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 13A and R 14A Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. When a1 is an integer greater than or equal to 2, R 11A They can be the same or different.)

[0036] [Chemistry 5]

[0037]

[0038] (In formula (16), R 21A is an alkyl group with 1 to 12 carbon atoms, R 22A and R 23A Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and c1 is an integer from 0 to 5. When c1 is an integer greater than or equal to 2, R 21A They can be the same or different.)

[0039] 6. The photosensitive resin composition according to any one of 1 to 5, wherein the component (B) contains a polymerizable monomer having an aliphatic cyclic skeleton.

[0040] 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (B) has a group containing a polymerizable unsaturated double bond.

[0041] 8. The photosensitive resin composition according to 7, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds.

[0042] 9. The photosensitive resin composition according to any one of 1 to 7, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

[0043] [Chemistry 6]

[0044]

[0045] (In formula (3), R6 and R7 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4). n1 is 0 or 1, n2 is an integer from 0 to 2, and n1 + n2 is greater than or equal to 1. At least one of the n1 R6s and n2 R7s is a group represented by the following formula (4).)

[0046] [Chemistry 7]

[0047]

[0048] (In formula (4), R9~R 11 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l represents an integer from 0 to 10.

[0049] 10. The photosensitive resin composition according to 9, wherein n1+n2 is 2 or 3.

[0050] 11. The photosensitive resin composition according to any one of 1 to 10, wherein the component (B) contains a polymerizable monomer represented by the following formula (5).

[0051] [Chemistry 8]

[0052]

[0053] 12. The photosensitive resin composition according to any one of 1 to 11, further comprising (F) a thermal polymerization initiator.

[0054] 13. The photosensitive resin composition according to any one of 1 to 12, further comprising an antioxidant.

[0055] 14. A method for producing a patterned cured product, comprising the following steps:

[0056] A step of applying the photosensitive resin composition according to any one of items 1 to 13 onto a substrate and drying the composition to form a photosensitive resin film;

[0057] The process of pattern-exposing the photosensitive resin film to obtain a resin film;

[0058] A process of developing the pattern-exposed resin film using an organic solvent to obtain a patterned resin film; and

[0059] A step of heat-treating the patterned resin film.

[0060] 15. The method for producing a patterned cured product according to 14, wherein the temperature of the heat treatment is 230° C. or less.

[0061] 16. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 13.

[0062] 17. The cured product according to 16, which is a patterned cured product.

[0063] 18. An interlayer insulating film, a cover coat or a surface protective film produced using the cured product according to 16 or 17.

[0064] 19. An electronic component comprising the interlayer insulating film, cover coat or surface protection film according to 18.

[0065] According to the present invention, there can be provided a photosensitive resin composition capable of forming a cured product having excellent mechanical properties even when cured at a low temperature of 230°C or less and having excellent storage stability, a method for producing a patterned cured product, a cured product, an interlayer insulating film, a cover coat, a surface protective film, and an electronic component. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a diagram showing a manufacturing process of an electronic component according to one embodiment of the present invention. DETAILED DESCRIPTION

[0067] Hereinafter, embodiments of the photosensitive resin composition of the present invention, a method for producing a patterned cured product using the same, a cured product, an interlayer insulating film, a cover coat, a surface protective film, and an electronic component will be described in detail. However, the present invention is not limited to the following embodiments.

[0068] In this specification, the term "A or B" may include either A or B, or both. Furthermore, the term "process" in this specification encompasses not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.

[0069] Numerical ranges expressed using "to" indicate a range that includes the numerical values ​​listed before and after the "to" as the minimum and maximum values, respectively. Furthermore, in this specification, when multiple substances corresponding to each component are present in the composition, unless otherwise specified, the content of each component in the composition refers to the total amount of the multiple substances present in the composition. Furthermore, unless otherwise specified, exemplified materials may be used alone or in combination of two or more.

[0070] The "(meth)acryloyl group" in this specification refers to both "acryloyl group" and "methacryloyl group".

[0071] The photosensitive resin composition of the present invention comprises: (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as "component (A)"), (B) a polymerizable monomer (hereinafter also referred to as "crosslinking agent") (hereinafter also referred to as "component (B)"), (C) a photopolymerization initiator (hereinafter also referred to as "component (C)"), (D) a cyclization catalyst (hereinafter also referred to as "component (D)"), and

[0072] (E) Solvent (hereinafter also referred to as "component (E)").

[0073] Thus, even with low-temperature curing at 230° C. or lower, a cured product having excellent mechanical properties can be formed.

[0074] In addition, storage stability can be improved.

[0075] Furthermore, as an optional effect, even with low-temperature curing at 230° C. or lower, a cured product having an excellent cyclization rate can be formed.

[0076] As an optional effect, sensitivity can be improved.

[0077] The photosensitive resin composition of the present invention is preferably a negative-type photosensitive resin composition. The photosensitive resin composition of the present invention is preferably a material for electronic components.

[0078] The component (A) is not particularly limited, but is preferably a polyimide precursor having high transmittance when i-line is used as a light source for patterning and exhibiting high cured product properties even when cured at a low temperature of 230° C. or lower.

[0079] Examples of the polymerizable unsaturated bond include a carbon-carbon double bond.

[0080] The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1): This has a high i-line transmittance and can form a good cured product even at a low temperature of 230°C or lower.

[0081] The content of the structural unit represented by formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, relative to all the structural units of component (A). The upper limit is not particularly limited and may be 100 mol%.

[0082] [Chemistry 9]

[0083]

[0084] (In formula (1), X1 is a tetravalent group having one or more aromatic groups, the -COOR1 group and the -CONH- group are ortho-positioned to each other, and the -COOR2 group and the -CO- group are ortho-positioned to each other. Y1 is a divalent aromatic group. R1 and R2 are each independently a hydrogen atom, a group represented by the following formula (2), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R1 and R2 is a group represented by the above formula (2).)

[0085] [Chemistry 10]

[0086]

[0087] (In formula (2), R3 to R5 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10 (preferably an integer of 2 to 5, more preferably 2 or 3).)

[0088] In the tetravalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups represented by X1 in formula (1), the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group.

[0089] Examples of the aromatic hydrocarbon group represented by X1 in formula (1) include a divalent to tetravalent (divalent, trivalent, or tetravalent) group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and a divalent to tetravalent group formed from perylene.

[0090] Examples of the tetravalent group having one or more aromatic groups represented by X1 in formula (1) include, but are not limited to, the tetravalent groups represented by the following formula (6).

[0091] [Chemistry 11]

[0092]

[0093] (In formula (6), X and Y each independently represent a divalent group or a single bond that is not conjugated with the benzene ring to which they are bonded. Z is an ether group (—O—) or a sulfide group (—S—) (preferably —O—).)

[0094] In formula (6), the divalent group of X and Y that is not conjugated with the benzene ring to which each is bonded is preferably -O-, -S-, a methylene group, a bis(trifluoromethyl)methylene group or a difluoromethylene group, and more preferably -O-.

[0095] The divalent aromatic group represented by Y1 in formula (1) may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, and is preferably a divalent aromatic hydrocarbon group.

[0096] Examples of the divalent aromatic hydrocarbon group represented by Y1 in formula (1) include, but are not limited to, the group represented by the following formula (7).

[0097] [Chemistry 12]

[0098]

[0099] (In formula (7), R 12 ~R 19 Each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group, or a monovalent organic group having a halogen atom.)

[0100] As R in formula (7) 12 ~R 19 The monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) may include a methyl group. For example, R 12 and R 15 ~R 19 is a hydrogen atom, R 13 and R 14 It is a monovalent aliphatic hydrocarbon group.

[0101] R in formula (7) 12 ~R 19 The monovalent organic group having a halogen atom (preferably a fluorine atom) is preferably a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), and examples thereof include trifluoromethyl.

[0102] Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) for R1 and R2 in formula (1) include methyl, ethyl, n-propyl, 2-propyl, and n-butyl.

[0103] At least one of R1 and R2 in formula (1) is a group represented by formula (2), and preferably both are groups represented by formula (2).

[0104] Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) for R3 to R5 in formula (2) include methyl, ethyl, n-propyl, and 2-propyl groups, with methyl being preferred.

[0105] A polyimide precursor having a structural unit represented by formula (1) can be obtained, for example, by reacting a tetracarboxylic dianhydride represented by the following formula (8) with a diamino compound represented by the following formula (9) in an organic solvent such as N-methyl-2-pyrrolidone to obtain polyamic acid, adding a compound represented by the following formula (10), and reacting them in an organic solvent to partially introduce ester groups.

[0106] The tetracarboxylic dianhydride represented by formula (8) and the diamino compound represented by formula (9) may be used alone or in combination of two or more.

[0107] [Chemistry 13]

[0108]

[0109] (In formula (8), X1 is a group corresponding to X1 in formula (1).)

[0110] [Chemistry 14]

[0111] H2N-Y1-NH2···(9)

[0112] (In formula (9), Y1 is as defined in formula (1).)

[0113] [Chemistry 15]

[0114] R-OH···(10)

[0115] (In formula (10), R is a group represented by formula (2) above.)

[0116] The component (A) may have a structural unit other than the structural unit represented by formula (1).

[0117] Examples of structural units other than the structural unit represented by formula (1) include the structural unit represented by formula (11).

[0118] [Chemistry 16]

[0119]

[0120] (In formula (11), X2 is a tetravalent group having one or more aromatic groups, -COOR 51 The -CONH- group and the -COOR group are in the ortho position to each other. 52 The -CO- group and the -CO- group are in ortho position to each other. Y2 is a divalent aromatic group. 51 and R 52Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0121] Examples of the tetravalent group having one or more aromatic groups represented by X2 in formula (11) include the same groups as those mentioned for the tetravalent group having one or more aromatic groups represented by X1 in formula (1).

[0122] Examples of the divalent aromatic group represented by Y2 in formula (11) include the same groups as those mentioned for the divalent aromatic group represented by Y1 in formula (1).

[0123] R in formula (11) 51 and R 52 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include the same groups as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R1 and R2.

[0124] Structural units other than the structural unit represented by formula (1) may be used alone or in combination of two or more.

[0125] The content of structural units other than the structural unit represented by formula (1) is preferably less than 50 mol% based on all structural units of the component (A).

[0126] In component (A), the ratio of esterified carboxyl groups in the groups represented by formula (2) relative to all carboxyl groups and all carboxylic acid esters is preferably 50 mol% or more, more preferably 60 to 100 mol%, and even more preferably 70 to 90 mol%.

[0127] The molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in terms of number average molecular weight.

[0128] The number average molecular weight can be determined by, for example, measuring it by gel permeation chromatography and converting it using a standard polystyrene calibration curve.

[0129] Component (B) preferably has (preferably two or more) a group containing a polymerizable unsaturated double bond (preferably a (meth)acryloyl group from the perspective of polymerizability by a photopolymerization initiator). Component (B) is preferably a polymerizable monomer having two or more groups containing a polymerizable unsaturated double bond. To increase crosslinking density and sensitivity and suppress pattern swelling after development, it is preferred that the component contain two to three groups containing a polymerizable unsaturated double bond.

[0130] Furthermore, the component (B) may contain a polymerizable monomer having a functional group other than a group containing a polymerizable unsaturated double bond. Examples of the functional group include cyclic ether groups such as an epoxy group and an oxetane group.

[0131] Component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton (preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms). This imparts hydrophobicity to the resulting cured product and prevents degradation of adhesion between the cured product and the substrate under high-temperature and high-humidity conditions.

[0132] The component (B) preferably contains a polymerizable monomer represented by the following formula (3).

[0133] [Chemistry 17]

[0134]

[0135] (In formula (3), R6 and R7 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4). n1 is 0 or 1, n2 is an integer from 0 to 2, and n1 + n2 is greater than or equal to 1 (preferably 2 or 3). At least one of the n1 R6s and n2 R7s (preferably 2 or 3) is a group represented by the following formula (4).

[0136] When there are two R7s, the two R7s may be the same or different.

[0137] [Chemistry 18]

[0138]

[0139] (In formula (4), R9~R 11 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l represents an integer from 0 to 10 (preferably 0, 1 or 2).

[0140] More preferably, the component (B) contains a polymerizable monomer represented by the following formula (5).

[0141] [Chemistry 19]

[0142]

[0143] Moreover, as (B)component, the following polymerizable monomers can be used, for example.

[0144] [Chemistry 20]

[0145]

[0146] In formula (12), R 21 ~R 24 Each independently represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the above formula (4). n3 is an integer of 1 to 3 (preferably 2 or 3). n4 is an integer of 1 to 3 (preferably 2 or 3). n5 is 0 or 1, and n6 is 0 or 1. n5 + n6 is greater than or equal to 1 (preferably 2).

[0147] In R 21 If there are two or more, two or more R 21 It can be the same or different.

[0148] In R 22 If there are two or more, two or more R 22 It can be the same or different.

[0149] n3 R 21 At least one (preferably two or three) of the groups is a group represented by the above formula (4).

[0150] n4 R 22 At least one (preferably two or three) of the groups is a group represented by the above formula (4).

[0151] n5 R 23 and n6 R 24 At least one (preferably two) of the groups is a group represented by the above formula (4).

[0152] As R6 and R7 of formula (3) and R 21 ~R 24 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include the same groups as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R1 and R2 in formula (1).

[0153] As R9 to R 11 Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include the same groups as the aliphatic hydrocarbon groups having 1 to 3 carbon atoms for R3 to R5 in formula (2).

[0154] The component (B) may contain a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton. This allows for obtaining a cured product having excellent mechanical properties.

[0155] Examples of polymerizable monomers other than the polymerizable monomer having an aliphatic cyclic skeleton include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, and pentaerythritol. triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, ethylene oxide (EO)-modified bisphenol A diacrylate (for example, commercially available product FA324A (manufactured by Hitachi Chemical Co., Ltd.)), and the like.

[0156] The component (B) may be used alone or in combination of two or more.

[0157] From the viewpoint of obtaining good mechanical properties and photosensitivity, the component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton.

[0158] In the case of comprising a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer other than a polymerizable monomer having an aliphatic cyclic skeleton, the content of the polymerizable monomer having an aliphatic cyclic skeleton is preferably 1 to 40 parts by mass relative to 100 parts by mass of component (A). From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 5 to 35 parts by mass. Relative to 100 parts by mass of component (A), the content of the polymerizable monomer other than a polymerizable monomer having an aliphatic cyclic skeleton is preferably 1 to 20 parts by mass. From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 5 to 15 parts by mass.

[0159] The content of component (B) is preferably 1 to 50 parts by mass per 100 parts by mass of component (A), more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass from the viewpoint of improving the hydrophobicity of the cured product.

[0160] When the content is within the above range, a practical concavo-convex pattern can be easily obtained, and residues after development in unexposed portions can be easily suppressed.

[0161] (C) As component, for example, preferably, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone are mentioned;

[0162] Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone;

[0163] Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives;

[0164] Benzil derivatives such as benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal;

[0165] Benzoin, benzoin methyl ether and other benzoin derivatives; and

[0166] Oxime esters such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and compounds represented by the following formulas are not limited thereto.

[0167] [Chemistry 21]

[0168]

[0169] In particular, oxime esters are preferred from the viewpoint of sensitivity.

[0170] The component (C) preferably contains (C1) a compound represented by the following formula (15) (hereinafter also referred to as "component (C1)").

[0171] The component (C1) is preferably more sensitive to active light than the component (C2) described below, and is preferably a highly sensitive photosensitizer.

[0172] [Chemistry 22]

[0173]

[0174] In formula (15), R 11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. 12A R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 13A and R 14AEach independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a phenyl group, or a tolyl group. When a1 is an integer greater than or equal to 2, R 11A They can be the same or different.

[0175] R 11A It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1. 12A It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. 13A and R 14A Each independently is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0176] Examples of the compound represented by formula (15) include a compound represented by the following formula (15A), which is available as "IRGACURE OXE 02" manufactured by BASF Japan Ltd.

[0177] [Chemistry 23]

[0178]

[0179] Furthermore, the component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter also referred to as "component (C2)").

[0180] The component (C2) is preferably a photosensitizer having lower sensitivity to active light than the component (C1), and is preferably a photosensitizer having standard sensitivity.

[0181] [Chemistry 24]

[0182]

[0183] In formula (16), R 21A is an alkyl group with 1 to 12 carbon atoms, R 22A and R 23A Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and c1 is an integer from 0 to 5. When c1 is an integer greater than or equal to 2, R 21A They can be the same or different.

[0184] c1 is preferably 0. 22A It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. 23A An alkoxy group having 1 to 12 carbon atoms is preferred, an alkoxy group having 1 to 4 carbon atoms is more preferred, and a methoxy group or an ethoxy group is further preferred.

[0185] Examples of the compound represented by formula (16) include a compound represented by the following formula (16A), which is available as "G-1820 (PDO)" manufactured by Lambson.

[0186] [Chemistry 25]

[0187]

[0188] The component (C) may be used alone or in combination of two or more.

[0189] The component (C) preferably contains one or more selected from the group consisting of the component (C1) and the component (C2).

[0190] Furthermore, the component (C) preferably contains the component (C1) and the component (C2).

[0191] The content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the component (A).

[0192] When the amount is within the above range, photocrosslinking tends to become uniform in the film thickness direction, and a practical concavo-convex pattern tends to be obtained.

[0193] When the component (C1) is contained, the content of the component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.07 to 2.5 parts by mass, and more preferably 0.09 to 1.0 parts by mass, relative to 100 parts by mass of the component (A).

[0194] When the component (C2) is contained, the content of the component (C2) is usually 0.5 to 15.0 parts by mass, preferably 1.0 to 15.0 parts by mass, relative to 100 parts by mass of the component (A).

[0195] When the components (C1) and (C2) are contained, the content of the component (C1) is preferably 0.05 to 5.0 parts by mass relative to 100 parts by mass of the component (A), and the content of the component (C2) is preferably 0.5 to 15.0 parts by mass relative to 100 parts by mass of the component (A).

[0196] When the component (C1) and the component (C2) are contained, the mass ratio of the content of the component (C1) to the content of the component (C2) is preferably 1:2 to 1:15, more preferably 1:3 to 1:10.

[0197] The photosensitive resin composition of the present invention contains (D) a cyclization catalyst.

[0198] The component (D) is preferably at least one selected from the group consisting of 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2′-(4-methylphenylimino)diethanol, and more preferably at least one selected from the group consisting of N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2′-(4-methylphenylimino)diethanol.

[0199] The component (D) preferably contains a compound represented by the following formula (17).

[0200] [Chemistry 26]

[0201]

[0202] (In formula (17), R 31A ~R 33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, and R 31A ~R 33A At least one (preferably one) of is a monovalent aromatic group. 31A ~R 33A Adjacent groups may form a ring (for example, a 5-membered ring or a 6-membered ring which may have a substituent (for example, a methyl group or a phenyl group)).

[0203] Preferably further R 31A ~R 33A At least one of them is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group.

[0204] As R in formula (17) 31A ~R 33A The monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) includes a methyl group, an ethyl group, and the like.

[0205] As R in formula (17) 31A ~R 33A The monovalent aliphatic hydrocarbon group having a hydroxyl group includes 31A ~R 33A A group in which one or more (preferably 1 to 3) hydroxyl groups are bonded to a monovalent aliphatic hydrocarbon group. Specific examples include hydroxymethyl and hydroxyethyl. A hydroxyethyl group is preferred.

[0206] As R in formula (17) 31A ~R 33AThe monovalent aromatic group may be a monovalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms), or a monovalent aromatic heterocyclic group.

[0207] Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a naphthyl group.

[0208] R in formula (17) 31A ~R 33A The monovalent aromatic group may have a substituent. As the substituent, there can be mentioned the same group as R in the above formula (17): 31A ~R 33A The monovalent aliphatic hydrocarbon group and R 31A ~R 33A The same group as the monovalent aliphatic hydrocarbon group having a hydroxyl group.

[0209] (D) Component may be used alone or in combination of two or more.

[0210] The content of component (D) is preferably 0.1 to 20 parts by mass per 100 parts by mass of component (A) from the viewpoint of improving the imidization rate and sensitivity, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass from the viewpoint of storage stability.

[0211] The photosensitive resin composition of the present invention contains (E) a solvent.

[0212] Component (E) includes N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethyl ethoxypropionate, methyl 3-methoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-dimethylmorpholine, and the like. Generally, there are no particular limitations as long as the other components can be sufficiently dissolved.

[0213] Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and N,N-dimethylacetamide are preferably used from the viewpoint of the solubility of each component and excellent coating properties when forming a photosensitive resin film.

[0214] Furthermore, as the component (E), a compound represented by the following formula (21) can be used.

[0215] [Chemistry 27]

[0216]

[0217] (Where R41 ~R 43 Each independently represents an alkyl group having 1 to 10 carbon atoms.)

[0218] As R in formula (21) 41 ~R 43 Examples of the alkyl group having 1 to 10 carbon atoms (preferably 1 to 3, more preferably 1 or 3) include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl.

[0219] The compound represented by formula (21) is preferably 3-methoxy-N,N-dimethylpropionamide (for example, trade name "KJ CMPA-100" (manufactured by KJ Chemical Co., Ltd.)).

[0220] (E) Components may be used alone or in combination of two or more.

[0221] (E) The content of the component is not particularly limited, but is generally 50 to 1000 parts by mass based on 100 parts by mass of the component (A).

[0222] The photosensitive resin composition of the present invention may further contain (F) a thermal polymerization initiator (hereinafter also referred to as "component (F)") from the viewpoint of promoting the polymerization reaction.

[0223] Component (F) is preferably a compound that does not decompose during heating (drying) for removing the solvent during film formation, but decomposes during heating during curing to generate free radicals, thereby promoting the polymerization reaction between components (B) or between component (A) and component (B).

[0224] The component (F) is preferably a compound having a decomposition point of 110°C or higher and 200°C or lower, and more preferably 110°C or higher and 175°C or lower from the viewpoint of promoting the polymerization reaction at a lower temperature.

[0225] Specific examples include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, and 1,1-di(tert-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide; and peroxides such as butyl peroxide. Examples of the present invention include diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-tert-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; peroxyesters such as tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; and bis(1-phenyl-1-methylethyl)peroxide. Commercially available products include those sold under the trade names "Percumyl D," "Percumyl P," and "Percumyl H" (all manufactured by NOF Corporation).

[0226] When the component (F) is contained, the content of the component (F) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the component (A). In order to ensure good flux resistance, the content is more preferably 0.2 to 20 parts by mass. From the viewpoint of suppressing a decrease in solubility due to decomposition during drying, the content is still more preferably 0.3 to 10 parts by mass.

[0227] The photosensitive resin composition of the present invention may further contain an antioxidant. The antioxidant replenishes oxygen and peroxide radicals generated during high-temperature storage or reflow processing, further suppressing the reduction in adhesion. Furthermore, it can inhibit electrode oxidation during insulation reliability testing and suppress diffusion from the electrodes into the resin film or patterned resin film.

[0228] Examples of the antioxidant include N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxalamide, N,N'-bis-3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione,

[0229] 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol),

[0230] Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

[0231] Pentaerythritol [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, ,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

[0232] 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and

[0233] 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, etc.

[0234] The antioxidants may be used alone or in combination of two or more.

[0235] When an antioxidant is contained, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the component (A).

[0236] The photosensitive resin composition of the present invention may further contain a coupling agent (adhesion aid), a surfactant or a leveling agent, a rust preventive, a polymerization inhibitor, and the like.

[0237] Typically, the coupling agent reacts with component (A) during the heat treatment after development to cause crosslinking, or the coupling agent itself polymerizes during the heat treatment step. This can further improve the adhesion between the resulting cured product and the substrate.

[0238] Preferred silane coupling agents include compounds having a urea bond (—NH—CO—NH—), which can further enhance adhesion to the substrate even when curing at a low temperature of 230° C. or lower.

[0239] Since the adhesiveness is excellent when curing at a low temperature, the compound represented by the following formula (13) is more preferable.

[0240] [Chemistry 28]

[0241]

[0242] (In formula (13), R 31 and R 32 Each independently represents an alkyl group having 1 to 5 carbon atoms. a is an integer of 1 to 10, and b is an integer of 1 to 3.

[0243] Specific examples of the compound represented by formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc., preferably 3-ureidopropyltriethoxysilane.

[0244] As the silane coupling agent, a silane coupling agent having a hydroxyl group or a glycidyl group can also be used. If a silane coupling agent having a hydroxyl group or a glycidyl group is used in combination with a silane coupling agent having a urea bond in the molecule, the adhesion of the cured product to the substrate during low-temperature curing can be further improved.

[0245] Examples of the silane coupling agent having a hydroxyl group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, and ethyldiphenylsilane. Alcohol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis(trihydroxysilyl)benzene, 1,4-bis(methyldihydroxysilyl)benzene, 1,4-bis(ethyldihydroxysilyl)benzene, 1,4-bis(propyldihydroxysilyl)benzene, 1,4-bis(butyldihydroxysilyl)benzene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis(diethylhydroxysilyl)benzene, 1,4-bis(dipropylhydroxysilyl)benzene, 1,4-bis(dibutylhydroxysilyl)benzene, and the compound represented by the following formula (14). Among them, the compound represented by formula (14) is particularly preferred in order to further improve the adhesion to the substrate.

[0246] [Chemistry 29]

[0247]

[0248] (In formula (14), R 33 is a monovalent organic group having a hydroxyl group or a glycidyl group, R 34 and R 35 Each independently represents an alkyl group having 1 to 5 carbon atoms. c is an integer of 1 to 10, and d is an integer of 1 to 3.

[0249] Examples of the compound represented by formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, and 4-glycidoxybutyltriethoxysilane.

[0250] The silane coupling agent having a hydroxyl group or a glycidyl group preferably further includes a group having a nitrogen atom, and is preferably a silane coupling agent further having an amino group or an amide bond.

[0251] Examples of the silane coupling agent further having an amino group include bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, bis(2-glycidoxymethyl)-3-aminopropyltriethoxysilane, and bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane.

[0252] Examples of the silane coupling agent further having an amide bond include: R 36 -(CH2) e -CO-NH-(CH2) f -Si(OR 37 )3(R 36 is a hydroxyl group or a glycidyl group, e and f are each independently an integer of 1 to 3, R 37 is a methyl group, an ethyl group or a propyl group).

[0253] The silane coupling agents may be used alone or in combination of two or more.

[0254] When using a silane coupling agent, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0255] By including a surfactant or a leveling agent, coating properties (for example, suppression of streaks (uneven film thickness)) and developability can be improved.

[0256] Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include those with the trade names “MEGAFAX F171,” “F173,” and “R-08” (all manufactured by DIC Corporation); those with the trade names “FLUORAD FC430” and “FC431” (all manufactured by Sumitomo 3M Co., Ltd.); and those with the trade names “Organosiloxane Polymer KP341,” “KBM303,” “KBM403,” and “KBM803” (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0257] The surfactant and the leveling agent may be used alone or in combination of two or more.

[0258] When a surfactant or a leveling agent is contained, the content of the surfactant or the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the component (A).

[0259] By including a rust inhibitor, corrosion of copper and copper alloys can be suppressed and discoloration can be prevented.

[0260] Examples of the rust preventive agent include triazole derivatives and tetrazole derivatives.

[0261] The rust preventive agents may be used alone or in combination of two or more.

[0262] When using a rust preventive agent, the content of the rust preventive agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the component (A).

[0263] By containing a polymerization inhibitor, good storage stability can be ensured.

[0264] Examples of the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.

[0265] Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluoquinone, tannic acid, p-benzylaminophenol, and nitrosamines.

[0266] The polymerization inhibitors may be used alone or in combination of two or more.

[0267] When a polymerization inhibitor is contained, the content of the polymerization inhibitor is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the component (A), from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the obtained cured product.

[0268] The photosensitive resin composition of the present invention is essentially composed of components (A) to (E), and optionally component (F), a coupling agent, a surfactant, a leveling agent, a rust inhibitor, and a polymerization inhibitor, and may contain unavoidable impurities within a range that does not impair the effects of the present invention.

[0269] For example, 80% or more, 90% or more, 95% or more, 98% or more, or 100% by mass of the photosensitive resin composition of the present invention can be made of

[0270] (A) to (E) ingredients,

[0271] (A) to (F) ingredients, or

[0272] The composition comprises the components (A) to (E), and optionally the component (F), a coupling agent, a surfactant, a leveling agent, a rust preventive, and a polymerization inhibitor.

[0273] The cured product of the present invention can be obtained by curing the above-mentioned photosensitive resin composition.

[0274] The cured product of the present invention can be used as a patterned cured product or as a non-patterned cured product.

[0275] The film thickness of the cured product of the present invention is preferably 5 to 20 μm.

[0276] The method for producing a patterned cured product of the present invention includes the following steps: applying the above-mentioned photosensitive resin composition on a substrate and drying it to form a photosensitive resin film; exposing the photosensitive resin film to a pattern to obtain a resin film; developing the pattern-exposed resin film using an organic solvent to obtain a patterned resin film; and heating the patterned resin film.

[0277] Thereby, a patterned cured product can be obtained.

[0278] The method for producing a non-patterned cured product comprises, for example, a step of forming the above-mentioned photosensitive resin film and a step of performing a heat treatment, and may further comprise a step of exposing the film.

[0279] Examples of the substrate include semiconductor substrates such as glass substrates and Si substrates (silicon wafers); metal oxide insulator substrates such as TiO2 substrates and SiO2 substrates; silicon nitride substrates, copper substrates, and copper alloy substrates.

[0280] The coating method is not particularly limited, and the coating can be performed using a spin coater or the like.

[0281] Drying can be performed using a hot plate, an oven, or the like.

[0282] The drying temperature is preferably 90 to 150°C, and more preferably 90 to 120°C from the viewpoint of ensuring the dissolution contrast.

[0283] The drying time is preferably 30 seconds to 5 minutes.

[0284] Drying may be performed two or more times.

[0285] Thereby, the photosensitive resin film which formed the said photosensitive resin composition into a film shape can be obtained.

[0286] The film thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 6 to 50 μm, and even more preferably 7 to 30 μm.

[0287] The pattern exposure is performed through a photomask, for example, to expose a predetermined pattern.

[0288] Examples of the active light to be irradiated include ultraviolet rays such as i-ray and broadband (BB) rays, visible rays, and radiation, and i-ray is preferred.

[0289] As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper exposure machine, a scanner exposure machine, or the like can be used.

[0290] By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, unexposed portions are removed using a developer.

[0291] As the organic solvent used as the developer, a good solvent for the photosensitive resin film may be used alone, or a good solvent and a poor solvent may be appropriately mixed and used as the developer.

[0292] Examples of the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, and cyclohexanone.

[0293] Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0294] A surfactant may be added to the developer in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the developer.

[0295] The development time can be set to, for example, twice the time required for immersing the photosensitive resin film and for it to be completely dissolved.

[0296] The development time varies depending on the component (A) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0297] After development, the film can be washed using a rinse solution.

[0298] As the rinse liquid, distilled water, methanol, ethanol, isopropyl alcohol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in appropriate mixtures, and can also be used in combination in stages.

[0299] By heat-treating the patterned resin film, a patterned cured product can be obtained.

[0300] The polyimide precursor of the component (A) undergoes a dehydration ring-closure reaction in the heat treatment step, and generally forms a corresponding polyimide.

[0301] The temperature of the heat treatment is preferably 250°C or lower, more preferably 120 to 250°C, further preferably 230°C or lower or 180 to 230°C.

[0302] By setting it within the above range, damage to the substrate and the device can be minimized, the device can be produced with a high yield, and energy saving of the process can be achieved.

[0303] The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.

[0304] By setting it as the said range, a crosslinking reaction or a dehydration ring-closure reaction can fully proceed.

[0305] The atmosphere for the heat treatment may be air or an inert atmosphere such as nitrogen. However, a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the patterned resin film.

[0306] Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0307] The cured product of the present invention can be used as a passivation film, a buffer coating film, an interlayer insulating film, a cover coating film, a surface protective film, or the like.

[0308] By using one or more of the group consisting of the above-mentioned passivation film, buffer coating, interlayer insulating film, covering coating and surface protection film, it is possible to manufacture highly reliable semiconductor devices, multi-layer wiring boards, various electronic devices, stacked devices (multi-chip fan-out wafer-level packaging, etc.) and other electronic components.

[0309] An example of a manufacturing process of a semiconductor device as an electronic component of the present invention will be described with reference to the drawings.

[0310] Figure 1 This is a diagram showing the manufacturing process of a semiconductor device having a multilayer wiring structure as an electronic component according to one embodiment of the present invention.

[0311] exist Figure 1 In the present invention, a semiconductor substrate 1 such as a Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit elements, and a first conductive layer 3 is formed on the exposed circuit elements. Then, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0312] Next, a photosensitive resin layer 5 of a chlorinated rubber-based, phenol novolac-based, or other resin is formed on the interlayer insulating film 4 , and a window 6A is provided by a known photolithography technique to expose a predetermined portion of the interlayer insulating film 4 .

[0313] The interlayer insulating film 4 exposed by the window 6A is selectively etched to form a window 6B.

[0314] Next, the photosensitive resin layer 5 is completely removed using an etching solution that does not corrode the first conductive layer 3 exposed from the window 6B but corrodes only the photosensitive resin layer 5 .

[0315] Furthermore, a second conductive layer 7 is formed using a known photolithography technique to be electrically connected to the first conductive layer 3 .

[0316] When forming a multilayer wiring structure having three or more layers, the above-mentioned steps may be repeated to form each layer.

[0317] Next, the photosensitive resin composition is used to open windows 6C by pattern exposure to form surface protection film 8. Surface protection film 8 protects second conductive layer 7 from external stress, α rays, etc., and the resulting semiconductor device has excellent reliability.

[0318] In the above examples, an interlayer insulating film can also be formed using the photosensitive resin composition of the present invention.

[0319] Example

[0320] Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

[0321] Synthesis Example 1 (Synthesis of A1)

[0322] 7.07 g of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 30 g of N-methyl-2-pyrrolidone (NMP), stirred at 30°C for 4 hours, and then stirred at room temperature overnight to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added to the mixture under water cooling, and the mixture was stirred at 45°C for 3 hours. 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was then added. The reaction mixture was added dropwise to distilled water, and the precipitate was separated by filtration, collected, and dried under reduced pressure to obtain polyimide precursor A1.

[0323] The number average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene: The number average molecular weight of A1 was 40,000.

[0324] The measurement was performed using 1 mL of a solution containing 0.5 mg of A1 and 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)].

[0325] Measuring device: L4000UV detector manufactured by Hitachi, Ltd.

[0326] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.

[0327] C-R4A Chromatopac manufactured by Shimadzu Corporation

[0328] Measurement conditions: Gelpack GL-S300MDT-5 x 2 columns

[0329] Eluent: THF / DMF = 1 / 1 (volume ratio)

[0330] LiBr(0.03mol / L), H3PO4(0.06mol / L)

[0331] Flow rate: 1.0 mL / min, detector: UV 270 nm

[0332] Furthermore, NMR measurement was performed under the following conditions to calculate the esterification rate of A1 (reaction rate between the carboxyl groups of ODPA and HEMA). The esterification rate was 80 mol% relative to all carboxyl groups of the polyamic acid (the remaining 20 mol% were carboxyl groups).

[0333] Measurement equipment: AV400M manufactured by Bruker BioSpin

[0334] Magnetic field strength: 400MHz

[0335] Reference substance: Tetramethylsilane (TMS)

[0336] Solvent: dimethyl sulfoxide (DMSO)

[0337] Examples 1 to 3 and Comparative Examples 1 to 5

[0338] (Preparation of Photosensitive Resin Composition)

[0339] The photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared according to the components and blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of each component relative to 100 parts by mass of A1.

[0340] The components used are as follows: A1 obtained in Synthesis Example 1 was used as the component (A).

[0341] Component (B): polymerizable monomer

[0342] B1: A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula B1)

[0343] [Chemistry 30]

[0344]

[0345] B2: ATM-4E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated pentaerythritol tetraacrylate, a compound represented by the following formula (n11+n12+n13+n14 is 4))

[0346] [Chemistry 31]

[0347]

[0348] B3: FA-324A (manufactured by Hitachi Chemical Co., Ltd., EO-modified bisphenol A diacrylate, a compound represented by the following formula B3)

[0349] [Chemistry 32]

[0350]

[0351] Component (C): Photopolymerization initiator

[0352] C1: IRUGCURE OXE 02 (manufactured by BASF Japan Ltd., ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime))

[0353] C2: G-1820 (PDO) (manufactured by Lambson Corporation, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime)

[0354] Component (D): Cyclization catalyst

[0355] D1: 2HE (Made by Morin Chemical Industry Co., Ltd., N-phenyldiethanolamine)

[0356] (D') component

[0357] D2: U-CAT SA810 (manufactured by San-Apro Co., Ltd., a compound represented by the following formula D2)

[0358] [Chemistry 33]

[0359]

[0360] D3: U-CAT SA1 (manufactured by San-Apro Co., Ltd., a compound represented by the following formula D3)

[0361] [Chemistry 34]

[0362]

[0363] D4: 4-Hydroxypyridine

[0364] (E) Component: Solvent

[0365] E1: KJCMPA-100 (manufactured by KJ Chemical Co., Ltd., a compound represented by the following formula E1)

[0366] [Chemistry 35]

[0367]

[0368] Component (F): Thermal polymerization initiator

[0369] F1: Percumyl D (manufactured by NOF Corporation, bis(1-phenyl-1-methylethyl)peroxide, a compound represented by the following formula F1)

[0370] [Chemistry 36]

[0371]

[0372] (Evaluation of sensitivity)

[0373] The obtained photosensitive resin composition was spin-coated on a silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electron Co., Ltd.), dried at 105° C. for 120 seconds, and then dried at 115° C. for 120 seconds to form a photosensitive resin film having a dry film thickness of 13 μm.

[0374] The development time was set to twice the time required for immersing the obtained photosensitive resin film in cyclopentanone and dissolving it completely.

[0375] A photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was exposed to light using an i-line stepper FPA-3000iW (manufactured by Canon Inc.) at a rate of 100 mJ / cm 2 The irradiation dose of the scale is 100~1100mJ / cm according to the predetermined pattern. 2 The i-line is used for exposure.

[0376] The exposed resin film was developed in cyclopentanone for the above-mentioned development time using Act 8, and then rinsed and washed using propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

[0377] The lower limit of the exposure amount at which the film thickness of the obtained pattern resin film becomes 80% or more of the film thickness of the photosensitive resin film before exposure is defined as sensitivity.

[0378] (Manufacturing 1 of Patterned Cured Product)

[0379] The patterned resin film obtained in the sensitivity evaluation was heated at 200° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.) to obtain a patterned cured product (film thickness after curing: 10 μm).

[0380] (Production of Patterned Cured Product 2)

[0381] The patterned resin film obtained in the sensitivity evaluation was heated at 400° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF to obtain a patterned cured product.

[0382] (Evaluation of cyclization rate)

[0383] The IR (infrared spectroscopy) spectrum of the patterned resin film obtained in the sensitivity evaluation was measured under the following conditions using FT-IR IRAffinity-1S (manufactured by Shimadzu Corporation). This value is referred to as IR1.

[0384] Regarding the measurement conditions of IR spectrum, the measurement range is 400-4000cm by transmission method. -1 , cumulative number of times is 16 times.

[0385] IR spectra were measured using a silicon wafer as a substrate. First, a substrate not coated with the photosensitive resin composition was measured as a background. Next, the resin film portion of the patterned resin film was measured using the background to obtain an IR spectrum.

[0386] Furthermore, IR was measured for the patterned cured product obtained in Production 1 of Patterned Cured Product in the same manner as above. This value was defined as IR2.

[0387] The IR of the patterned cured product obtained in Production 2 of Patterned Cured Product was measured in the same manner as above. This value was defined as IR3.

[0388] The cyclization rate was determined by dividing the value obtained by subtracting IR1 from IR2 by the value obtained by subtracting IR1 from IR3 and calculating the percentage. A was designated as 65% or more, and B was designated as less than 65%. The results are shown in Table 1.

[0389] (Evaluation of storage stability)

[0390] Within 24 hours after conditioning, the photosensitive resin composition was spin-coated onto a Si substrate at a rotational speed to achieve a film thickness of 13 μm after drying. The film was then dried on a hot plate at 105°C for 120 seconds and then at 115°C for 120 seconds to form a photosensitive resin film. A portion of the film was scraped to expose the silicon wafer, and the height from the exposed silicon wafer surface to the film surface was measured using a probe profilometer, Dektak 150 (manufactured by Bruker). (The film thickness was measured in the same manner as above and below.) This was designated as film thickness 1.

[0391] After conditioning, the photosensitive resin composition was allowed to stand at room temperature (25°C) for 14 days. After standing, it was spin-coated onto a Si substrate at the same rotational speed as used to form the photosensitive resin film for thickness 1. The film was then dried on a hot plate at 105°C for 120 seconds and then at 115°C for 120 seconds to form a photosensitive resin film. The film thickness was measured in the same manner as above. This was designated as thickness 2.

[0392] The case where the percentage obtained by subtracting the absolute value of the film thickness 1 from the film thickness 2 and dividing it by the film thickness 1 was less than or equal to 5% was designated as A. The case where it exceeded 5% was designated as B. The results are shown in Table 1.

[0393] (Production of Patterned Cured Product 3)

[0394] The photosensitive resin composition was spin-coated on a Si substrate, and dried by heating at 105° C. for 120 seconds and then at 115° C. for 120 seconds on a hot plate to form a photosensitive resin film having a thickness of 12.0 to 13.0 μm.

[0395] The obtained photosensitive resin film was subjected to broadband (BB) exposure using a mask aligner MA-8 (manufactured by Suss MicroTec), and the exposed resin film was developed using cyclopentanone to obtain a 10 mm wide strip-shaped patterned resin film.

[0396] The obtained patterned resin film was cured at 200° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF to obtain a patterned cured product having a film thickness of 10 μm.

[0397] (Evaluation of elongation)

[0398] The patterned cured product obtained in Production 3 of Patterned Cured Product was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and a 10 mm wide cured product was peeled off from the wafer.

[0399] A tensile test was performed on a 10 mm wide section of the peeled cured product using an Autograph AGS-X 100N (manufactured by Shimadzu Corporation). The distance between the grips was set to 20 mm, the tensile speed was set to 5 mm / min, and the measurement temperature was set to 18-25°C. Three measurements were performed on each cured product in each Example and Comparative Example, and the average elongation was calculated.

[0400] The case where the average elongation exceeded 50% was designated A, the case where it exceeded 45% and was 50% or less was designated B, and the case where it was 45% or less was designated C. Table 1 shows the results before PCT (pressure cooker test).

[0401] Furthermore, the pattern cured product obtained in Preparation 3 of the Pattern Cured Product was treated at 121° C., 100 RH (Relative Humidity) %, and 2 atm for 100 hours using a PCT tester HASTEST (manufactured by Hirayama Seisakusho Co., Ltd., PC-R8D).

[0402] The patterned cured product was taken out from the PCT tester, peeled off and subjected to a tensile test in the same manner as above, and the average value of the elongation was determined.

[0403] The case where the average elongation exceeded 50% was designated A, the case where it exceeded 45% and was 50% or less was designated B, and the case where it was 45% or less was designated C. The results after PCT are shown in Table 1. "-" indicates that no measurement was made.

[0404] [Table 1]

[0405]

[0406] Industrial applicability

[0407] The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat, a surface protective film, and the like. The interlayer insulating film, the cover coat, or the surface protective film of the present invention can be used for electronic components and the like.

[0408] While several embodiments and / or examples of the present invention have been described in detail above, it is readily apparent to those skilled in the art that numerous modifications may be made to these illustrative embodiments and / or examples without departing substantially from the novel teachings and effects of the present invention. Therefore, these numerous modifications are also encompassed within the scope of the present invention.

[0409] The entire contents of the documents described in this specification and the application on which the present application claims priority based on the Paris Convention are incorporated herein by reference.

Claims

1. A photosensitive resin composition comprising: (A) a polyimide precursor having a polymerizable unsaturated bond, (B) polymerizable monomers, (C1) a compound represented by the following formula (15), (C2) a compound represented by the following formula (16), (D) a compound represented by the following formula (17), and (E) a solvent, In formula (15), R 11A is an alkyl group having 1 to 12 carbon atoms, a1 is an integer from 0 to 5, R 12A is a hydrogen atom or an alkyl group with 1 to 12 carbon atoms, R 13A and R 14A Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, and when a1 is an integer greater than or equal to 2, R 11A They can be the same or different. In formula (16), R 21A is an alkyl group with 1 to 12 carbon atoms, R 22A and R 23A are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, wherein c1 is an integer from 0 to 5. When c1 is an integer greater than or equal to 2, R 21A They can be the same or different. In formula (17), R 31A ~R 33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, and R 31A ~R 33A At least one of R is a monovalent aromatic group, 31A ~R 33A Adjacent groups may or may not form a ring.

2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1): In formula (1), X1 is a tetravalent group having one or more aromatic groups, the -COOR1 group and the -CONH- group are ortho-positioned to each other, the -COOR2 group and the -CO- group are ortho-positioned to each other, Y1 is a divalent aromatic group, R1 and R2 are each independently a hydrogen atom, a group represented by the following formula (2), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R1 and R2 is a group represented by the above formula (2). In formula (2), R3 to R5 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.

3. The photosensitive resin composition according to claim 1, wherein the component (D) is at least one selected from the group consisting of N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol.

4. The photosensitive resin composition according to claim 1, wherein R 31A ~R 33A At least one of them is phenyl.

5. The photosensitive resin composition according to claim 1, wherein R 11A It is an alkyl group having 1 to 4 carbon atoms. 6 . The photosensitive resin composition according to claim 1 , wherein the component (B) comprises a polymerizable monomer having an aliphatic cyclic skeleton. 7 . The photosensitive resin composition according to claim 1 , wherein the component (B) has a group containing a polymerizable unsaturated double bond. 8 . The photosensitive resin composition according to claim 7 , wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds.

9. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a polymerizable monomer represented by the following formula (3): In formula (3), R6 and R7 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4), n1 is 0 or 1, n2 is an integer from 0 to 2, n1+n2 is greater than or equal to 1, and at least one of n1 R6 and n2 R7 is a group represented by the following formula (4), In formula (4), R9~R 11 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l represents an integer of 0 to 10. 10 . The photosensitive resin composition according to claim 9 , wherein n1+n2 is 2 or 3.

11. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a polymerizable monomer represented by the following formula (5): 12 . The photosensitive resin composition according to claim 1 , further comprising (F) a thermal polymerization initiator. The photosensitive resin composition according to claim 1 , further comprising an antioxidant.

14. A method for producing a patterned cured product, comprising the following steps: A step of applying the photosensitive resin composition according to any one of claims 1 to 13 on a substrate and drying the resulting film to form a photosensitive resin film; The process of pattern-exposing the photosensitive resin film to obtain a resin film; The process of developing the resin film after the pattern exposure using an organic solvent to obtain a patterned resin film; as well as a step of heating the patterned resin film. 15 . The method for producing a patterned cured product according to claim 14 , wherein the temperature of the heat treatment is less than or equal to 230° C. 16 . A cured product obtained by curing the photosensitive resin composition according to claim 1 . The cured product according to claim 16 , which is a patterned cured product.

18. An interlayer insulating film, a cover coat or a surface protective film produced using the cured product according to claim 16 or 17. 19 . An electronic component comprising the interlayer insulating film, cover coat or surface protection film according to claim 18 .

Images