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 containing: (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photopolymerization initiator, and (D) a UV absorber.

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 been made of 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 (see, for example, Patent Documents 2 to 4).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-265520

[0009] Patent Document 2: International Publication No. 2008 / 111470

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2016-199662

[0011] Patent Document 4: International Publication No. 2015 / 052885 Summary of the Invention

[0012] An object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having excellent resolution and aspect ratio even when cured at a low temperature of 200°C or less, 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.

[0013] Electronic devices are being required to be smaller and more highly integrated. Therefore, the present inventors have discovered that achieving a high resolution of a patterned cured film formed by heat-curing a patterned resin film is a problem.

[0014] The present inventors have conducted extensive studies in view of the above-mentioned problems and have found that a cured product of a patterned cured film having excellent resolution can be formed by using a combination of specific components in a photosensitive resin composition, thereby completing the present invention.

[0015] According to the present invention, the following photosensitive resin composition and the like are provided.

[0016] 1. A photosensitive resin composition comprising: (A) a polyimide precursor having a polymerizable unsaturated bond,

[0017] (B) polymerizable monomers,

[0018] (C) a photopolymerization initiator, and

[0019] (D) Ultraviolet absorber.

[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 group having one or more aromatic groups, 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 (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond.

[0028] 4. The photosensitive resin composition according to 3, wherein the number of the group containing a polymerizable unsaturated double bond is 2 or more.

[0029] 5. The photosensitive resin composition according to any one of 1 to 4, wherein the polymerizable monomer has an aliphatic cyclic skeleton.

[0030] 6. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

[0031] [Chemistry 3]

[0032]

[0033] (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).)

[0034] [Chemistry 4]

[0035]

[0036] (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.

[0037] 7. The photosensitive resin composition according to 6, wherein n1+n2 is 2 or 3.

[0038] 8. 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 (5).

[0039] [Chemistry 5]

[0040]

[0041] 9. The photosensitive resin composition according to any one of 1 to 8, wherein the component (D) has an absorbance of 0.1 or more at 365 nm at a concentration of 10 mg / L.

[0042] 10. The photosensitive resin composition according to any one of 1 to 9, wherein the component (D) is at least one selected from the group consisting of benzotriazole compounds, benzophenone compounds, azobenzene compounds, and polyphenol compounds.

[0043] 11. The photosensitive resin composition according to any one of items 1 to 10, wherein the component (D) is at least one selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4′-nitroazobenzene, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione.

[0044] 12. The photosensitive resin composition according to any one of 1 to 11, further comprising (I) a thermal polymerization initiator.

[0045] 13. A method for producing a patterned cured product, comprising the following steps:

[0046] A step of applying the photosensitive resin composition according to any one of items 1 to 12 on a substrate and drying the composition to form a photosensitive resin film;

[0047] The process of pattern-exposing the photosensitive resin film to obtain a resin film;

[0048] A process of developing the pattern-exposed resin film using an organic solvent to obtain a patterned resin film; and

[0049] A step of heat-treating the patterned resin film.

[0050] 14. The method for producing a patterned cured product according to 13, wherein the temperature of the heat treatment is 200° C. or less.

[0051] 15. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 12.

[0052] 16. The cured product according to 15, which is a patterned cured product.

[0053] 17. An interlayer insulating film, a cover coat or a surface protective film produced using the cured product according to 15 or 16.

[0054] 18. An electronic component comprising the interlayer insulating film, cover coat or surface protection film according to 17.

[0055] According to the present invention, there can be provided a photosensitive resin composition capable of forming a cured product having excellent resolution and aspect ratio even when cured at a low temperature of 200°C or less, 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

[0056] Figure 1 This is a diagram showing a manufacturing process of an electronic component according to one embodiment of the present invention. DETAILED DESCRIPTION

[0057] 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.

[0058] 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.

[0059] 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.

[0060] The "(meth)acryloyl group" in this specification refers to both "acryloyl group" and "methacryloyl group".

[0061] The photosensitive resin composition of the present invention contains: (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 "component (B)"), (C) a photopolymerization initiator (hereinafter also referred to as "component (C)"), and (D) an ultraviolet absorber (hereinafter also referred to as "component (D)").

[0062] Thus, even with low-temperature curing at 200° C. or lower, a cured product having excellent resolution and aspect ratio can be formed.

[0063] The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

[0064] Moreover, the photosensitive resin composition of the present invention is preferably a material for electronic components.

[0065] 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 pattern formation and exhibiting high cured product properties even when cured at a low temperature of 200° C. or lower.

[0066] Examples of the polymerizable unsaturated bond include a carbon-carbon double bond.

[0067] The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1): This has high i-line transmittance and can form a good cured product even when cured at a low temperature of 200°C or lower.

[0068] 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%.

[0069] [Chemistry 6]

[0070]

[0071] (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 group having one or more aromatic groups. 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 (preferably 1 or 2), and at least one of R1 and R2 is a group represented by the above formula (2).)

[0072] [Chemistry 7]

[0073]

[0074] (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).)

[0075] 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.

[0076] 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.

[0077] 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).

[0078] [Chemistry 8]

[0079]

[0080] (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—).)

[0081] 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-.

[0082] In the divalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups represented by Y1 in formula (1), the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group.

[0083] Examples of the aromatic hydrocarbon group represented by Y<1 > in formula (1) include a divalent to tetravalent group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and a divalent to tetravalent group formed from perylene.

[0084] Examples of the divalent group having one or more aromatic groups represented by Y1 in formula (1) include, but are not limited to, a divalent group in which two aromatic groups are bonded via an ether group (—O—).

[0085] Examples of the divalent group having one or more aromatic groups represented by Y1 in formula (1) include, but are not limited to, groups represented by the following formula (7).

[0086] [Chemistry 9]

[0087]

[0088] (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.)

[0089] As R in formula (7) 12 ~R 19The 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.

[0090] 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.

[0091] 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.

[0092] 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).

[0093] 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.

[0094] 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.

[0095] 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.

[0096] [Chemistry 10]

[0097]

[0098] (In formula (8), X1 is a group corresponding to X1 in formula (1).)

[0099] [Chemistry 11]

[0100] H2N-Y1-NH2...(9)

[0101] (In formula (9), Y1 is as defined in formula (1).)

[0102] [Chemistry 12]

[0103] R-OH...(10)

[0104] (In formula (10), R is a group represented by formula (2) above.)

[0105] The component (A) may have a structural unit other than the structural unit represented by formula (1).

[0106] Examples of structural units other than the structural unit represented by formula (1) include the structural unit represented by formula (11).

[0107] [Chemistry 13]

[0108]

[0109] (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 positions. Y2 is a divalent group having one or more aromatic groups. 51 and R 52 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

[0110] 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).

[0111] Examples of the divalent group having one or more aromatic groups represented by Y2 in formula (11) include the same groups as those mentioned for the divalent group having one or more aromatic groups represented by Y1 in formula (1).

[0112] 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.

[0113] Structural units other than the structural unit represented by formula (1) may be used alone or in combination of two or more.

[0114] 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).

[0115] 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%.

[0116] The molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in terms of weight average molecular weight.

[0117] The weight average molecular weight can be determined by, for example, measuring it by gel permeation chromatography and converting it using a standard polystyrene calibration curve.

[0118] The photosensitive resin composition of the present invention contains (B) a polymerizable monomer, thereby improving the heat resistance, mechanical properties, and chemical resistance of the resulting cured product.

[0119] From the viewpoint of increasing the crosslinking density with the component (A), the component (B) preferably contains a polymerizable monomer having (preferably two or more) a group containing a polymerizable unsaturated double bond (preferably a (meth)acryloyl group from the perspective of being polymerizable by a photopolymerization initiator).

[0120] The polymerizable monomer preferably has 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.

[0121] In order to increase the crosslinking density and sensitivity and suppress pattern swelling after development, the polymerizable monomer preferably has 2 to 3 groups containing a polymerizable unsaturated double bond.

[0122] The component (B) preferably contains a polymerizable monomer represented by the following formula (3).

[0123] [Chemistry 14]

[0124]

[0125] (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).)

[0126] When there are two R7s, the two R7s may be the same or different.

[0127] [Chemistry 15]

[0128]

[0129] (In formula (4), R9~R 11Each 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).

[0130] The component (B) more preferably contains a polymerizable monomer represented by the following formula (5):

[0131] [Chemistry 16]

[0132]

[0133] Moreover, as (B)component, the following polymerizable monomers can be used, for example.

[0134] [Chemistry 17]

[0135]

[0136] 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).

[0137] In R 21 If there are two or more, two or more R 21 It can be the same or different.

[0138] In R 22 If there are two or more, two or more R 22 It can be the same or different.

[0139] n3 R 21 At least one (preferably two or three) of the groups is a group represented by the above formula (4).

[0140] n4 R 22 At least one (preferably two or three) of the groups is a group represented by the above formula (4).

[0141] n5 R 23 and n6 R 24 At least one (preferably two) of the groups is a group represented by the above formula (4).

[0142] 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).

[0143] 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).

[0144] As component (B), a polymerizable monomer other than a polymerizable monomer having an aliphatic cyclic skeleton may be used. Examples of polymerizable monomers other than a 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, and 1,6-hexanediol dimethacrylate.

[0145] In addition, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate,

[0146] Tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methanetetrayltetra(methyleneoxyethylene) tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, and the like.

[0147] Among them, tetraethylene glycol dimethacrylate, pentaerythritol tetraacrylate, and methanetetrayltetra(methyleneoxyethylene)tetraacrylate are preferred.

[0148] The component (B) may be used alone or in combination of two or more.

[0149] 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.

[0150] 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.

[0151] Preferred examples of the component (C) include benzophenone derivatives such as benzophenone, methyl 2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone;

[0152] Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone;

[0153] Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives;

[0154] Benzil derivatives such as benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal;

[0155] Benzoin, benzoin methyl ether and other benzoin derivatives; and

[0156] 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.

[0157] [Chemistry 18]

[0158]

[0159] In particular, oxime esters are preferred from the viewpoint of sensitivity.

[0160] The component (C) preferably contains (C1) one or more compounds selected from the group consisting of compounds represented by the following formula (15-1) and compounds represented by the following formula (15-2) (hereinafter also referred to as "component (C1)").

[0161] The component (C1) is preferably more sensitive to active light than the component (C2) described below, and is preferably a highly sensitive photosensitizer.

[0162] [Chemistry 19]

[0163]

[0164] In formula (15-1), R 11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer from 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.

[0165] 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.

[0166] Examples of the compound represented by formula (15-1) include a compound represented by the following formula (15A), which is available as "IRGACURE OXE 02" manufactured by BASF Japan Ltd.

[0167] [Chemistry 20]

[0168]

[0169] [Chemistry 21]

[0170]

[0171] In formula (15-2), R 15A is -OH, -COOH, -O(CH2)OH, -O(CH2)2OH, -COO(CH2)OH or -COO(CH2)2OH, R 16A and R 17A Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group. b1 represents an integer from 0 to 5. When b1 represents an integer greater than or equal to 2, R 15 They can be the same or different.

[0172] R 15A Preferably, it is -O(CH2)2OH. b1 is preferably 0 or 1. R 16A It is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or a hexyl group. 17A It is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and more preferably a methyl group or a phenyl group.

[0173] Examples of the compound represented by formula (15-2) include a compound represented by the following formula (15B), which is available as "NCI-930" manufactured by ADEKA Corporation.

[0174] [Chemistry 22]

[0175]

[0176] Furthermore, the component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter also referred to as "component (C2)").

[0177] The component (C2) is preferably a photosensitizer having lower sensitivity to active light than the component (C1), and preferably a photosensitizer having standard sensitivity.

[0178] [Chemistry 23]

[0179]

[0180] 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.

[0181] 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.

[0182] 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.

[0183] [Chemistry 24]

[0184]

[0185] The component (C) may be used alone or in combination of two or more.

[0186] The component (C) preferably contains one or more selected from the group consisting of the component (C1) and the component (C2).

[0187] Furthermore, from the viewpoint of adjusting transmittance, the component (C) preferably contains the component (C1) and the component (C2).

[0188] The content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0189] 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.

[0190] When the component (C1) is contained, the content of the component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.1 to 2.5 parts by mass, and more preferably 0.2 to 2.0 parts by mass, relative to 100 parts by mass of the component (A).

[0191] 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 10.0 parts by mass, relative to 100 parts by mass of the component (A).

[0192] 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).

[0193] 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 1:3 to 1:70, more preferably 1:5 to 1:50.

[0194] The photosensitive resin composition of the present invention contains (D) an ultraviolet absorber.

[0195] This can suppress crosslinking of unexposed areas due to diffuse reflection during irradiation with active light. Component (D) preferably has an absorbance of 0.05 or greater, more preferably 0.1 or greater, at 365 nm at a concentration of 10 mg / L.

[0196] As (D)component, for example, there can be mentioned:

[0197] 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidomethyl)phenol, 2-(2-hydroxy-4 Benzotriazole compounds such as benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazol-2-yl)-p-cresol;

[0198] Salicylate compounds such as phenyl salicylate and 4-tert-butylphenyl salicylate;

[0199] Benzophenone compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2,2′,4,4′-tetrahydroxybenzophenone, and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone;

[0200] Diphenylacrylate compounds such as ethyl 2-cyano-3,3-diphenylacrylate;

[0201] Cyanoacrylate compounds;

[0202] Diphenylcyanoacrylate compounds such as 2-cyano-3,3-diphenylacrylate (2′-ethylhexyl);

[0203] Benzothiazole compounds;

[0204] Azobenzene compounds such as 4-[ethyl(2-hydroxyethyl)amino]-4′-nitroazobenzene;

[0205] Polyphenolic compounds such as pyrogallol, fluoroglycine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagin, quercetagetin, pelargonidin, cyanidin, aurantinidin, luteolinidin, peonidin, rosinidin, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione;

[0206] Nickel complex salt compounds such as [2,2′-thiobis(4-tert-octylphenol)]-2-ethylhexylamine nickel(II) and the like.

[0207] In particular, benzotriazole-based compounds, benzophenone-based compounds, azobenzene-based compounds, and polyphenol-based compounds are preferably used.

[0208] As the component (D), from the viewpoint of resolution (resolution), preferably used are 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol), 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4′-nitroazobenzene, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione.

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

[0210] From the viewpoint of excellent resolution, the content of component (D) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.2 parts by mass or more, relative to 100 parts by mass of component (A).

[0211] The content of component (D) is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, relative to 100 parts by mass of component (A). This can prevent increased absorption on the surface of the composition during irradiation with active light, which can lead to insufficient internal photocuring.

[0212] The photosensitive resin composition of the present invention may further contain (E) a polymerization inhibitor (hereinafter also referred to as "component (E)") from the viewpoint of ensuring storage stability.

[0213] (E) As a component, a radical polymerization inhibitor, a radical polymerization inhibitor, etc. are mentioned.

[0214] Examples of the component (E) 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-toluquinone, tannic acid, p-benzylaminophenol, nitrosamines, and dioxides such as 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dioxide.

[0215] (E) Components may be used alone or in combination of two or more.

[0216] When the component (E) is contained, the content of the component (E) 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 resulting cured product.

[0217] The photosensitive resin composition of the present invention may further contain (F) a rust inhibitor (hereinafter also referred to as "component (F)") from the viewpoint of suppressing corrosion of copper and copper alloys and preventing discoloration.

[0218] Examples of the component (F) include 1,2,4-triazole, 1,2,3-triazole, 1,2,5-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazole, 4-amino-3,5-dimethyl ... Triazole derivatives such as 5-dimethyl-1,2,4-triazole, 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, 5-methyl-1H-benzotriazole, 5,6-dimethylbenzotriazole, 5-amino-1H-benzotriazole, benzotriazole-4-sulfonic acid, and 1,2,3-benzotriazole; and tetrazole derivatives such as 1H-tetrazole, 5-methyl-1H-tetrazole, 5-(methylthio)-1H-tetrazole, 5-(ethylthio)-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-nitro-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5'-bis-1H-tetrazole, and 5-amino-1H-tetrazole.

[0219] The component (F) may be used alone or in combination of two or more.

[0220] When the component (F) is used, the content of the rust inhibitor 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 4 parts by mass, relative to 100 parts by mass of the component (A).

[0221] The photosensitive resin composition of the present invention may further contain (G) a silane coupling agent (adhesion aid) (hereinafter also referred to as "component (G)") from the viewpoint of improving the adhesion of the obtained cured film to the substrate.

[0222] Typically, component (G) reacts with component (A) during the heat treatment after development to cause crosslinking, or component (G) itself polymerizes during the heat treatment step. This can further improve the adhesion between the resulting cured product and the substrate.

[0223] Component (G) includes a compound having a urea bond (—NH—CO—NH—). This allows for further improved adhesion to the substrate even when curing is performed at a low temperature of 200° C. or lower.

[0224] From the viewpoint of excellent adhesiveness during curing at low temperatures, the compound represented by the following formula (13) is more preferred.

[0225] [Chemistry 25]

[0226]

[0227] (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.

[0228] 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.

[0229] As component (G), a silane coupling agent having a hydroxyl group or a glycidyl group can 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.

[0230] 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.

[0231] [Chemistry 26]

[0232]

[0233] (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.

[0234] 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.

[0235] Examples of commercially available products include "KBM403" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0236] The silane coupling agent having a hydroxyl group or a glycidyl group preferably further includes a group having a nitrogen atom, and more preferably further has an amino group or an amide bond.

[0237] 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.

[0238] Examples of the silane coupling agent further having an amide bond include compounds represented by the following formula.

[0239] R 36 -(CH2) e -CO-NH-(CH2) f -Si(OR 37 )3

[0240] (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 methyl, ethyl or propyl)

[0241] Moreover, as the component (G), triethoxysilylpropylethylcarbamate can also be used.

[0242] The component (G) may be used alone or in combination of two or more.

[0243] When the component (G) is used, the content of the component (G) is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0244] From the viewpoint of achieving both maintaining a residual film rate in a wide range of exposure doses and good resolution, the photosensitive resin composition of the present invention may further contain a sensitizer (H) (hereinafter also referred to as "component (H)").

[0245] Examples of the component (H) include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-tert-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4′-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzil, and benzyldimethyl acetal. Ketone, benzil diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, biscoumarin compounds, N-phenylglycine, N-phenyldiethanolamine, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, etc.

[0246] The component (H) may be used alone or in combination of two or more.

[0247] When the component (H) is contained, the amount of the component (H) is preferably 0.1 to 2.0 parts by mass, more preferably 0.2 to 1.5 parts by mass, relative to 100 parts by mass of the component (A).

[0248] The photosensitive resin composition of the present invention may further contain (I) a thermal polymerization initiator (hereinafter also referred to as "component (I)") from the viewpoint of promoting the polymerization reaction.

[0249] Component (I) is preferably a compound that does not decompose during heating (drying) for removing the solvent during film formation, but decomposes by heating during curing to generate free radicals, thereby promoting the polymerization reaction between components (B) or between component (A) and component (B).

[0250] The component (I) preferably has a decomposition point of 110°C or higher and 200°C or lower. From the viewpoint of promoting the polymerization reaction at a lower temperature, the decomposition point is more preferably 110°C or higher and 175°C or lower.

[0251] 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; Diacyl peroxides such as dilauroyl oxide 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," "Percumyl H," and "Perbutyl O" (all manufactured by NOF Corporation).

[0252] The component (I) may be used alone or in combination of two or more.

[0253] When component (I) is contained, the content of component (I) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of 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.

[0254] The photosensitive resin composition of the present invention may further contain (J) a solvent (hereinafter also referred to as "component (J)").

[0255] Component (J) 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.

[0256] 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.

[0257] Furthermore, as the component (J), a compound represented by the following formula (21) can also be used.

[0258] [Chemistry 27]

[0259]

[0260] (Where R 41 ~R 43 Each independently represents an alkyl group having 1 to 10 carbon atoms.)

[0261] 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.

[0262] 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.)).

[0263] The component (J) may be used alone or in combination of two or more.

[0264] The content of the component (J) is not particularly limited, but is generally 50 to 1000 parts by mass based on 100 parts by mass of the component (A).

[0265] The photosensitive resin composition of the present invention may further contain a surfactant, a leveling agent, and the like.

[0266] By including a surfactant or a leveling agent, coating properties (for example, suppression of streaks (uneven film thickness)) and developability can be improved.

[0267] 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 name “Organosiloxane Polymer KP341” (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0268] The surfactant and the leveling agent may be used alone or in combination of two or more.

[0269] 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).

[0270] The photosensitive resin composition of the present invention consists essentially of components (A) to (D), and optionally components (E) to (I), a surfactant, and a leveling agent, excluding component (J), and may contain unavoidable impurities within a range that does not impair the effects of the present invention.

[0271] The photosensitive resin composition of the present invention may be composed of, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass, in addition to the component (J).

[0272] (A) to (D) ingredients,

[0273] (A) to (I) components, or

[0274] The composition comprises the components (A) to (D), and optionally the components (E) to (I), a surfactant, and a leveling agent.

[0275] The cured product of the present invention can be obtained by curing the above-mentioned photosensitive resin composition.

[0276] The cured product of the present invention can be used as a patterned cured product or as a non-patterned cured product.

[0277] The film thickness of the cured product of the present invention is preferably 5 to 20 μm.

[0278] The cured product of the present invention preferably has a pattern with an aspect ratio of 1 or greater, more preferably 1.2 or greater, and particularly preferably 1.5 or greater.

[0279] The aspect ratio can be calculated according to the following formula by, for example, photographing a cross section of a patterned cured product using a scanning electron microscope (SEM), measuring the film thickness and opening width from the image.

[0280] Aspect ratio = (film thickness after curing / opening width on substrate)

[0281] 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.

[0282] Thereby, a patterned cured product can be obtained.

[0283] 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 performing an exposure.

[0284] 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.

[0285] The coating method is not particularly limited, and the coating can be performed using a spin coater or the like.

[0286] Drying can be performed using a hot plate, an oven, or the like.

[0287] The drying temperature is preferably 90 to 150°C, and more preferably 90 to 120°C from the viewpoint of ensuring the dissolution contrast.

[0288] The drying time is preferably 30 seconds to 5 minutes.

[0289] Drying may be performed two or more times.

[0290] Thereby, the photosensitive resin film which formed the said photosensitive resin composition into a film shape can be obtained.

[0291] 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.

[0292] The pattern exposure is performed through a photomask to expose a predetermined pattern, for example.

[0293] Examples of the active light to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, and i-rays are preferred.

[0294] 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.

[0295] If necessary, post-exposure baking (PEB) may be performed after exposure and before development. The temperature of the post-exposure baking is preferably 60° C. to 160° C., and the time of the post-exposure baking is preferably 0.5 minute to 5 minutes.

[0296] 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.

[0297] 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.

[0298] 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.

[0299] Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0300] 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.

[0301] 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.

[0302] 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.

[0303] After development, the film can be washed using a rinse solution.

[0304] 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.

[0305] By heat-treating the patterned resin film, a patterned cured product can be obtained.

[0306] The polyimide precursor of the component (A) undergoes a dehydration ring-closure reaction in the heat treatment step, and generally forms a corresponding polyimide.

[0307] The temperature of the heat treatment is preferably 250°C or lower, more preferably 120 to 250°C, further preferably 200°C or lower or 160 to 200°C.

[0308] 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.

[0309] The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.

[0310] By setting it as the said range, a crosslinking reaction or a dehydration ring-closure reaction can fully proceed.

[0311] 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.

[0312] 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.

[0313] 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.

[0314] 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.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] 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 .

[0319] The interlayer insulating film 4 exposed by the window 6A is selectively etched to form a window 6B.

[0320] 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 .

[0321] Furthermore, a second conductive layer 7 is formed using a known photolithography technique to be electrically connected to the first conductive layer 3 .

[0322] When forming a multilayer wiring structure having three or more layers, the above-mentioned steps may be repeated to form each layer.

[0323] 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.

[0324] In the above examples, an interlayer insulating film can also be formed using the photosensitive resin composition of the present invention.

[0325] Example

[0326] 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.

[0327] The components used in Examples and Comparative Examples are as follows.

[0328] Component (A): Polyimide precursor having a polymerizable unsaturated bond

[0329] A1: Compound obtained in Synthesis Example 1 described later

[0330] A2: Compound obtained in Synthesis Example 2 described later

[0331] A3: Compound obtained in Synthesis Example 3 described later

[0332] A4: Compound obtained in Synthesis Example 4 described later

[0333] Component (B): polymerizable monomer

[0334] B1: A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula)

[0335] [Chemistry 28]

[0336]

[0337] B2: ATM-4E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methanetetrayltetra(methyleneoxyethylene)tetraacrylate)

[0338] B3: TEGDMA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tetraethylene glycol dimethacrylate)

[0339] B4: A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., pentaerythritol tetraacrylate)

[0340] Component (C): Photopolymerization initiator

[0341] C1: IRUGCURE OXE 02 (manufactured by BASF Japan Ltd., ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime))

[0342] C2: G-1820 (PDO) (manufactured by Lambson Corporation, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime)

[0343] C3: NCI-930 (manufactured by ADEKA Co., Ltd., 2-(acetoxyimino)-1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]propan-1-one)

[0344] (D) Ingredient: UV absorber

[0345] D1: ADEKASTAB LA-29 (manufactured by ADEKA Co., Ltd., 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)

[0346] D2: ADEKASTAB LA-24 (manufactured by ADEKA Co., Ltd., 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol)

[0347] D3: ADEKASTAB LA-32 (manufactured by ADEKA Co., Ltd., 2-(2H-benzotriazol-2-yl)-p-cresol)

[0348] D4: SEESORB106 (manufactured by SHIPRO Chemicals Co., Ltd., 2,2′,4,4′-tetrahydroxybenzophenone)

[0349] D5: SEESORB107 (manufactured by SHIPRO Chemicals Co., Ltd., 2,2′-dihydroxy-4,4′-dimethoxybenzophenone)

[0350] D6: Disperse Red 1 (manufactured by Hitachi Chemical Techno-Service Co., Ltd., 4-[ethyl(2-hydroxyethyl)amino]-4′-nitroazobenzene)

[0351] D7: Curcumin (manufactured by Sanwa Chemical Co., Ltd., (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione)

[0352] D8: HPH (manufactured by Sanwa Chemical Co., Ltd., 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione)

[0353] (E) ingredient: polymerization inhibitor

[0354] E1: Taobn (manufactured by Hampford Research, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dioxide)

[0355] E2: Hydroquinone

[0356] (H) Component: Sensitizer

[0357] H1: EMK (manufactured by Aldrich, 4,4′-bis(diethylamino)benzophenone)

[0358] (I) Component: Thermal polymerization initiator

[0359] I1: Percumyl D (manufactured by NOF Corporation, bis(1-phenyl-1-methylethyl)peroxide)

[0360] (J) Ingredient: Solvent

[0361] J1: N-methyl-2-pyrrolidone

[0362] J2: γ-butyrolactone

[0363] J3: KJCMPA-100 (manufactured by KJ Chemical Co., Ltd., 3-methoxy-N,N-dimethylpropionamide)

[0364] [Absorbance measurement]

[0365] The absorbance of D1 to D8 was measured under the following conditions. The results are shown in Table 1.

[0366] D1 to D8 were dissolved in chloroform to adjust to 10 mg / L, respectively, and used as measurement samples.

[0367] Measuring equipment: U-3900H (manufactured by Hitachi High-Technologies Corporation)

[0368] Measurement conditions: Sample cell length: 10.0 mm

[0369] [Table 1]

[0370] absorbance D1 0.23 D2 0.25 D3 0.38 D4 0.40 D5 0.64 D6 0.21 D7 0.25 D8 0.26

[0371] Synthesis Example 1 (Synthesis of A1)

[0372] 47.1 g (152 mmol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA), 5.54 g (43 mmol) of 2-hydroxyethyl methacrylate (HEMA), and a catalytic amount of 1,4-diazabicyclo[2.2.2.]octanetriethylenediamine were dissolved in 380 g of N-methyl-2-pyrrolidone (NMP). The mixture was stirred at 45°C for 1 hour and then cooled to 25°C. 27.4 g (129 mmol) of 2,2'-dimethylbenzidine and 145 mL of dried N-methyl-2-pyrrolidone were added, followed by stirring at 45°C for 150 minutes and then cooling to room temperature. 59.7 g (284 mmol) of trifluoroacetic anhydride was added dropwise to the solution, followed by stirring for 120 minutes. A catalytic amount of benzoquinone was then added, followed by 40.4 g (310 mmol) of HEMA, and stirring at 45°C for 20 hours. This reaction liquid was added dropwise to distilled water, and the precipitate was separated and collected by filtration, and dried under reduced pressure to obtain a polyimide precursor A1.

[0373] The weight average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene: The weight average molecular weight of A1 was 35,000.

[0374] 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)].

[0375] Measuring device: L4000UV detector manufactured by Hitachi, Ltd.

[0376] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.

[0377] C-R4A Chromatopac manufactured by Shimadzu Corporation

[0378] Measurement conditions: Gelpack GL-S300MDT-5 x 2 columns

[0379] Eluent: THF / DMF = 1 / 1 (volume ratio)

[0380] LiBr(0.03mol / L), H3PO4(0.06mol / L)

[0381] Flow rate: 1.0 mL / min, detector: UV 270 nm

[0382] 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 81 mol% (the remaining 19 mol% was carboxyl groups) relative to all carboxyl groups of the polyamic acid (relative to all carboxyl groups and all carboxylic acid esters).

[0383] Measurement equipment: AV400M manufactured by Bruker BioSpin

[0384] Magnetic field strength: 400MHz

[0385] Reference substance: Tetramethylsilane (TMS)

[0386] Solvent: dimethyl sulfoxide (DMSO)

[0387] Synthesis Example 2 (Synthesis of A2)

[0388] 47.1 g (152 mmol) of ODPA, 2.77 g (21 mmol) of HEMA, and a catalytic amount of 1,4-diazabicyclo[2.2.2.]octanetriethylenediamine were dissolved in 500 g of NMP, stirred at 45°C for 1 hour, and then cooled to 25°C. 30.0 g (141 mmol) of 2,2'-dimethylbenzidine and 145 mL of dried NMP were added, followed by stirring at 45°C for 150 minutes and then cooling to room temperature. 65.2 g (311 mmol) of trifluoroacetic anhydride was added dropwise to this solution, followed by stirring for 180 minutes. A catalytic amount of benzoquinone was then added, followed by 43.1 g (331 mmol) of HEMA, and stirring at 45°C for 20 hours. The reaction solution was added dropwise to distilled water, and the precipitate was separated by filtration, collected, and dried under reduced pressure to obtain polyimide precursor A2.

[0389] The weight average molecular weight was determined by gel permeation chromatography (GPC) in terms of standard polystyrene under the same conditions as in Synthesis Example 1. The weight average molecular weight of A2 was 70,000.

[0390] The esterification rate of A2 was calculated by NMR measurement under the same conditions as in Synthesis Example 1. The esterification rate was 73 mol% (the remaining 27 mol% was carboxyl groups) relative to all carboxyl groups in the polyamic acid (relative to all carboxyl groups and all carboxylic acid esters).

[0391] Synthesis Example 3 (Synthesis of A3)

[0392] 62.0 g (200 mmol) of ODPA, 5.2 g (40.0 mmol) of HEMA, and a catalytic amount of 1,4-diazabicyclo[2.2.2]octanetriethylenediamine were dissolved in 250 g of NMP. The mixture was stirred at 45°C for 1 hour and then cooled to 25°C. 5.5 g (50.9 mmol) of m-phenylenediamine, 23.8 g (119 mmol) of oxydianiline (4,4′-diaminodiphenyl ether), and 100 mL of dried NMP were added. The mixture was stirred at 45°C for 150 minutes and then cooled to room temperature. 78.5 g (374 mmol) of trifluoroacetic anhydride was added dropwise to the solution. After stirring for 20 minutes, 53.1 g (408 mmol) of HEMA was added and stirred at 45°C for 20 hours. The reaction mixture was added dropwise to distilled water, and the precipitate was separated by filtration and collected, then dried under reduced pressure to obtain polyimide precursor A3.

[0393] The weight average molecular weight was determined using the GPC method under the same conditions as in Synthesis Example 1. The weight average molecular weight of A3 was 35,000.

[0394] The esterification rate of A3 was calculated by NMR measurement under the same conditions as in Synthesis Example 1. The esterification rate was 70 mol% (the remaining 30 mol% was carboxyl groups) relative to all carboxyl groups in the polyamic acid (relative to all carboxyl groups and all carboxylic acid esters).

[0395] Synthesis Example 4 (Synthesis of A4)

[0396] 43.6 g (200 mmol) of pyromellitic dianhydride (PMDA), 54.9 g (401 mmol) of HEMA, and 0.220 g of hydroquinone were dissolved in 394 g of NMP. A catalytic amount of 1,8-diazabicycloundecene was added, and the mixture was stirred at 25°C for 24 hours for esterification to obtain a pyromellitic acid-hydroxyethyl methacrylate diester solution. This solution was designated the PMDA-HEMA solution.

[0397] 49.6 g (160 mmol) of ODPA, 4.98 g (328 mmol) of HEMA, and 0.176 g of hydroquinone were dissolved in 378 g of NMP. A catalytic amount of 1,8-diazabicycloundecene was added, and the mixture was stirred at 25°C for 48 hours for esterification to obtain a 3,3′,4,4′-diphenylethertetracarboxylic acid-hydroxyethyl methacrylate diester solution. This solution was designated the ODPA-HEMA solution.

[0398] 196 g of PMDA-HEMA solution and 58.7 g of ODPA-HEMA solution were mixed, and then 25.9 g (218 mmol) of thionyl chloride was added dropwise using a dropping funnel under ice-cooling, maintaining the reaction solution temperature at 10°C or lower. After the addition of thionyl chloride, the mixture was allowed to react for 2 hours under ice-cooling to obtain a solution of PMDA and ODPA chloride. Next, a solution of 31.7 g (99.0 mmol) of 2,2′-bis(trifluoromethyl)benzidine, 34.5 g (436 mmol) of pyridine, and 0.076 g (693 mmol) of hydroquinone in 90.2 g of NMP was added dropwise using a dropping funnel under ice-cooling, ensuring that the reaction solution temperature did not exceed 10°C. The reaction solution was added dropwise to distilled water, and the precipitate was separated by filtration, collected, and dried under reduced pressure to obtain polyimide precursor A4.

[0399] The weight average molecular weight was determined using the GPC method under the same conditions as in Synthesis Example 1. The weight average molecular weight of A4 was 34,000.

[0400] The esterification rate of A4 was calculated by NMR measurement under the same conditions as in Synthesis Example 1. The esterification rate was 97 mol% (the remaining 3 mol% was carboxyl groups) relative to all carboxyl groups in the polyamic acid (relative to all carboxyl groups and all carboxylic acid esters).

[0401] Examples 1 to 24 and Comparative Examples 1 to 7

[0402] [Preparation of Photosensitive Resin Composition]

[0403] The photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were prepared according to the components and blending amounts shown in Tables 2 and 3. The blending amounts in Tables 2 and 3 are parts by mass of each component relative to 100 parts by mass of component (A).

[0404] [Manufacturing of patterned resin film]

[0405] 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 100°C for 2 minutes, and then dried at 110°C for 2 minutes to form a photosensitive resin film having a dry film thickness of 7 to 10 μm.

[0406] The development time was set to twice the time required for immersing the obtained photosensitive resin film in cyclopentanone until the film was completely dissolved.

[0407] In addition, a photosensitive resin film was prepared in the same manner as described above, and the obtained photosensitive resin film was exposed using an i-line stepper exposure machine FPA-3000iW (manufactured by Canon Inc.) on a photomask for forming through holes having a diameter of 1 μm to 100 μm at the exposure amounts shown in Tables 2 and 3.

[0408] Using Act 8, post-exposure heating was performed at 120° C. for 3 minutes in the atmosphere.

[0409] The resin film after exposure and heating was subjected to spin immersion development in cyclopentanone for the above-mentioned development time using Act 8, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

[0410] [Manufacturing of Patterned Cured Product]

[0411] The obtained patterned resin film was heated at 175° C. for 1 hour 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: 5 μm).

[0412] [Resolution Evaluation]

[0413] The obtained patterned cured product was observed using an optical microscope and evaluated according to the following criteria, with the resolution being the minimum diameter of the opening that exposed 55% or more of the substrate surface relative to the mask size of the through hole.

[0414] A: Pattern opening smaller than 4 μm.

[0415] B: Pattern opening greater than or equal to 4 μm and less than 6 μm.

[0416] C: Pattern opening greater than or equal to 6 μm and less than 8 μm.

[0417] D: Pattern opening greater than or equal to 8 μm.

[0418] The results are shown in Tables 2 and 3.

[0419] [Evaluation of aspect ratio]

[0420] The obtained patterned cured product was subjected to focused ion beam processing, and its cross section was observed using a scanning electron microscope (FIB-SEM) SMI500 (manufactured by Hitachi High-Technologies Corporation).

[0421] The film thickness after curing and the width of the opening on the substrate were measured from the obtained cross-sectional image, and the aspect ratio was calculated according to the following formula.

[0422] Aspect ratio = (film thickness after curing / opening width on substrate)

[0423] The results are shown in Tables 2 and 3.

[0424] [Table 2]

[0425]

[0426] [Table 3]

[0427]

[0428] Examples 5a, 6a, 10a, 20a to 23a and Comparative Examples 1a to 4a, 7a, and 8a

[0429] [Preparation of Photosensitive Resin Composition]

[0430] The photosensitive resin compositions of Examples 5a, 6a, 10a, 20a to 23a and Comparative Examples 1a to 4a, 7a, and 8a were prepared according to the components and amounts shown in Table 4. The amounts shown in Table 4 are parts by mass of each component per 100 parts by mass of component (A).

[0431] [Manufacturing of patterned resin film]

[0432] Using the obtained photosensitive resin composition, a photosensitive resin film was formed in the same manner as in Examples 1 to 24 and Comparative Examples 1 to 7.

[0433] The development time was set to twice the time required for immersing the obtained photosensitive resin film in cyclopentanone until the film was completely dissolved.

[0434] Furthermore, a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was exposed to a photomask for forming a via hole having a diameter of 1 μm to 100 μm using FPA-3000iW at an exposure dose shown in Table 4.

[0435] The exposed resin film was subjected to spin immersion development in cyclopentanone for the above-mentioned development time using Act 8, and then rinsed with PGMEA to obtain a patterned resin film.

[0436] [Manufacturing of Patterned Cured Product]

[0437] The obtained patterned resin film was heated at 175° C. for 1 hour in a nitrogen atmosphere using μ-TF to obtain a patterned cured product (film thickness after curing: 5 μm).

[0438] [Resolution Evaluation]

[0439] The obtained pattern cured products were evaluated for resolution in the same manner as in Examples 1 to 24 and Comparative Examples 1 to 7.

[0440] The results are shown in Table 4.

[0441] [Evaluation of aspect ratio]

[0442] About the obtained pattern cured product, the aspect ratio was calculated similarly to Examples 1 to 24 and Comparative Examples 1 to 7.

[0443] The results are shown in Table 4.

[0444] [Table 4]

[0445]

[0446] Examples 25 to 27 and Comparative Examples 8 to 10

[0447] [Preparation of Photosensitive Resin Composition]

[0448] The photosensitive resin compositions of Examples 25 to 27 and Comparative Examples 8 to 10 were prepared according to the components and blending amounts shown in Table 5. The blending amounts in Table 5 are parts by mass of each component relative to 100 parts by mass of the component (A).

[0449] [Manufacturing of patterned resin film]

[0450] The obtained photosensitive resin composition was spin-coated on a silicon wafer using Act 8, dried at 100° C. for 2 minutes, and then dried at 110° C. for 2 minutes to form a photosensitive resin film having a dry film thickness of 12 to 15 μm.

[0451] The development time was set to twice the time required for immersing the obtained photosensitive resin film in cyclopentanone until the film was completely dissolved.

[0452] Furthermore, a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was exposed to a photomask for forming a through-hole having a diameter of 1 μm to 100 μm using FPA-3000iW at an exposure dose shown in Table 5.

[0453] The exposed resin film was subjected to spin immersion development in cyclopentanone for the above-mentioned development time using Act 8, and then rinsed with PGMEA to obtain a patterned resin film.

[0454] [Manufacturing of Patterned Cured Product]

[0455] The obtained patterned resin film was heated at 175° C. for 1 hour in a nitrogen atmosphere using μ-TF to obtain a patterned cured product (film thickness after curing: 10 μm).

[0456] [Resolution Evaluation]

[0457] The obtained patterned cured product was observed using an optical microscope and evaluated according to the following criteria, with the resolution being the minimum diameter of the opening that exposed 55% or more of the substrate surface relative to the mask size of the through hole.

[0458] A: Pattern opening smaller than 8 μm.

[0459] B: Pattern opening greater than or equal to 8 μm and less than 10 μm.

[0460] C: Pattern opening greater than or equal to 10 μm and less than 15 μm.

[0461] D: Pattern opening greater than or equal to 15 μm.

[0462] The results are shown in Table 5.

[0463] [Evaluation of aspect ratio]

[0464] About the obtained pattern cured product, the aspect ratio was calculated similarly to Examples 1 to 24 and Comparative Examples 1 to 7.

[0465] The results are shown in Table 5.

[0466] [Table 5]

[0467]

[0468] Examples 28, 29 and Comparative Examples 11, 12

[0469] [Preparation of Photosensitive Resin Composition]

[0470] The photosensitive resin compositions of Examples 28 and 29 and Comparative Examples 11 and 12 were prepared according to the components and blending amounts shown in Table 6. The blending amounts in Table 6 are parts by mass of each component relative to 100 parts by mass of the component (A).

[0471] [Manufacturing of patterned resin film]

[0472] The obtained photosensitive resin composition was spin-coated on a silicon wafer using Act 8, dried at 100° C. for 2 minutes, and then dried at 110° C. for 2 minutes to form a photosensitive resin film having a dry film thickness of 12 to 15 μm.

[0473] The development time was set to twice the time required for immersing the obtained photosensitive resin film in cyclopentanone until the film was completely dissolved.

[0474] Furthermore, a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was exposed to a photomask for forming a through-hole having a diameter of 1 μm to 100 μm using FPA-3000iW at an exposure dose shown in Table 6.

[0475] Using Act 8, post-exposure heating was performed at 120° C. for 3 minutes in the atmosphere.

[0476] The resin film after exposure and heating was subjected to spin immersion development in cyclopentanone for the above-mentioned development time using Act 8, and then rinsed with PGMEA to obtain a patterned resin film.

[0477] [Manufacturing of Patterned Cured Product]

[0478] The obtained patterned resin film was heated at 175° C. for 1 hour in a nitrogen atmosphere using μ-TF to obtain a patterned cured product (film thickness after curing: 10 μm).

[0479] [Resolution Evaluation]

[0480] The obtained pattern cured products were evaluated for resolution in the same manner as in Examples 25 to 27 and Comparative Examples 8 to 10.

[0481] The results are shown in Table 6.

[0482] [Evaluation of aspect ratio]

[0483] About the obtained pattern cured product, the aspect ratio was calculated similarly to Examples 1 to 24 and Comparative Examples 1 to 7.

[0484] The results are shown in Table 6.

[0485] [Table 6]

[0486]

[0487] Industrial applicability

[0488] 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.

[0489] 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.

[0490] The entire contents of the documents described in this specification and the application based 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, (C) a photopolymerization initiator, and (D) one or more selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol, 4-[ethyl(2-hydroxyethyl)amino]-4′-nitroazobenzene, and (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione.

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): [Chemistry 29] 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 group having one or more aromatic groups, 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). [Chemistry 30] 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 (B) comprises a polymerizable monomer having a group containing a polymerizable unsaturated double bond. The photosensitive resin composition according to claim 3 , wherein the number of the groups containing polymerizable unsaturated double bonds is greater than or equal to 2. The photosensitive resin composition according to claim 1 , wherein the polymerizable monomer has an aliphatic cyclic skeleton.

6. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a polymerizable monomer represented by the following formula (3): [Chemistry 31] 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), [Chemistry 32] 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. The photosensitive resin composition according to claim 6 , wherein n1+n2 is 2 or 3.

8. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a polymerizable monomer represented by the following formula (5): [Chemistry 33] 9 . The photosensitive resin composition according to claim 1 , wherein the component (D) has an absorbance of 0.1 or more at 365 nm at a concentration of 10 mg / L.

10. The photosensitive resin composition according to claim 1, wherein the component (D) is one or more selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol, and (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione.

11. The photosensitive resin composition according to claim 1, wherein the component (D) is at least one selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazol-2-yl)-p-cresol. 12 . The photosensitive resin composition according to claim 1 , further comprising (I) a thermal polymerization initiator.

13. 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 12 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. 14 . The method for producing a patterned cured product according to claim 13 , wherein the temperature of the heat treatment is less than or equal to 200° C. 15 . A cured product obtained by curing the photosensitive resin composition according to claim 1 . The cured product according to claim 15 , which is a patterned cured product.

17. An interlayer insulating film, a cover coat or a surface protective film produced using the cured product according to claim 15 or 16. 18 . An electronic component comprising the interlayer insulating film, cover coat or surface protection film according to claim 17 .

Images