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

Abstract

To provide a photosensitive resin composition that can form a cured product having high resolution even when cured at low temperatures of 200°C or lower, a method for producing a cured pattern, a cured product, an interlayer insulation film, a cover coat layer, a surface protection film and an electronic component.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor having a polymerizable unsaturated bond, (B1) a polymerizable monomer having an aliphatic cyclic skeleton, and (C) a compound having an acyl phosphine oxide structure.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Conventionally, polyimide and polybenzoxazole, which have excellent heat resistance as well as electrical and mechanical properties, have been used for the surface protection films and interlayer insulating films of semiconductor elements. In recent years, photosensitive resin compositions in which these resins themselves are given photosensitivity have been used, and their use can simplify the manufacturing process of patterned cured products and shorten complicated manufacturing processes (see, for example, Patent Document 1).

[0003] In recent years, the miniaturization of transistors, which has supported the high performance of computers, has reached the limit of scaling laws, and stacked device structures in which semiconductor elements are stacked three-dimensionally to achieve further improvements in performance and speed have been attracting attention.

[0004] Among stacked device structures, multi-die fanout wafer level packaging is a package manufactured by encapsulating multiple dies together in a single package. It is attracting a great deal of attention because it is expected to achieve lower costs and higher performance than the conventional fan-out wafer level packaging (manufactured by encapsulating a single die in a single package).

[0005] In the manufacture of multi-die fan-out wafer-level packages, low-temperature curing properties are strongly required from the viewpoints of protecting high-performance dies, protecting sealing materials with low heat resistance, and improving yields (see, for example, Patent Document 2).

[0006] A technique has been disclosed in which a negative type photosensitive resin composition is used as the photosensitive resin composition (for example, Patent Document 3). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2009-265520 A [Patent Document 2] International Publication No. 2008 / 111470 [Patent Document 3] International Publication No. 2019 / 087985 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having excellent resolution 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 layer, a surface protective film, and an electronic component. [Means for solving the problem]

[0009] According to the present invention, the following photosensitive resin composition and the like are provided. 1. (A) a polyimide precursor having a polymerizable unsaturated bond; (B1) a polymerizable monomer having an aliphatic cyclic skeleton, and (C) A photosensitive resin composition containing a compound having an acylphosphine oxide structure. 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): [ka] (In formula (1), X1 is a tetravalent group having one or more aromatic groups, -COOR1 group and -CONH- group are located at the ortho position relative to each other, and -COOR2 group and -CO- group are located at the ortho position relative 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 formula (2).) [ka] (In formula (2), R3 to R5 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m represents an integer of 1 to 10.) 3. The photosensitive resin composition according to 1 or 2, wherein the component (B1) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond and having an alicyclic skeleton. 4. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B1) contains a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds and having an alicyclic skeleton. 5. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B1) contains a polymerizable monomer represented by the following formula (3): [ka] (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 of 0 to 2, and n1+n2 is 1 or more. At least one of the n1 R6s and the n2 R7s is a group represented by the following formula (4).) [ka] (In formula (4), R9~R 11 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10. 6. The photosensitive resin composition according to 5, wherein n1+n2 is 2 or 3. 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (B1) contains a polymerizable monomer represented by the following formula (5): [ka] 8. The photosensitive resin composition according to any one of 1 to 7, further comprising (B2) a polymerizable monomer other than the component (B1). 9. The photosensitive resin composition according to any one of 1 to 8, further comprising (D) an ultraviolet absorber. 10. The photosensitive resin composition according to any one of 1 to 9, further comprising (E) a thermal polymerization initiator. 11. A step of applying the photosensitive resin composition according to any one of 1 to 10 onto a substrate and drying it to form a photosensitive resin film; a step of exposing the photosensitive resin film to a pattern to obtain a resin film; developing the resin film after the patterned exposure with an organic solvent to obtain a patterned resin film; and heat-treating the patterned resin film. 12. The method for producing a patterned cured product according to 11, wherein the heat treatment is carried out at a temperature of 200°C or lower. 13. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 10. 14. The cured product according to 13, which is a patterned cured product. 15. An interlayer insulating film, a cover coat layer or a surface protective film prepared using the cured product according to 13 or 14. An electronic component comprising an interlayer insulating film, a cover coat layer, or a surface protective film according to 16.15. Effect of the Invention

[0010] The present invention provides a photosensitive resin composition capable of forming a cured product having excellent resolution 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 layer, a surface protective film, and an electronic component. [Brief description of the drawings]

[0011] [Figure 1] 1A to 1C are diagrams illustrating a manufacturing process for an electronic component according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The photosensitive resin composition, the method for producing a patterned cured product, the cured product, the interlayer insulating film, the cover coat layer, the surface protective film, and the electronic component of the present invention will be described in detail below. Note that the present invention is not limited to the following embodiments.

[0013] In this specification, "A or B" may include either A or B, or may include both. In addition, in this specification, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the intended effect of the step is achieved. A numerical range indicated using "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. Furthermore, in this specification, the content of each component in the composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified. Furthermore, unless otherwise specified, the example materials may be used alone or in combination of two or more types. In this specification, the term "(meth)acrylic group" means an "acrylic group" and a "methacrylic group".

[0014] 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)”), (B1) a polymerizable monomer having an aliphatic cyclic skeleton (hereinafter also referred to as "component (B1)"), and (C) A compound containing an acylphosphine oxide structure (hereinafter also referred to as “component (C)”) is contained.

[0015] This makes it possible to form a cured product with excellent resolution even when cured at a low temperature of 200° C. or less. As an optional effect, a cured product having excellent film retention can be formed.

[0016] The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition. The photosensitive resin composition of the present invention is preferably a material for electronic parts.

[0017] The component (A) is not particularly limited, but is preferably a polyimide precursor that has high transmittance when i-line is used as a light source during patterning, and exhibits high cured product properties even when cured at low temperatures of 200° C. or less.

[0018] The polymerizable unsaturated bond may be a carbon-carbon double bond.

[0019] The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1): This provides high i-line transmittance and allows the formation of a good cured product even when cured at a low temperature of 200°C or less. 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, based on all structural units of the component (A). There is no particular upper limit, and it may be 100 mol%.

[0020] [ka] (In formula (1), X1 is a tetravalent group having one or more aromatic groups, -COOR1 group and -CONH- group are located at the ortho position relative to each other, and -COOR2 group and -CO- group are located at the ortho position relative 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 formula (2).)

[0021] [ka] (In formula (2), R3 to R5 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m represents an integer of 1 to 10 (preferably an integer of 2 to 5, more preferably 2 or 3).)

[0022] In the tetravalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups of 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.

[0023] Examples of the aromatic hydrocarbon group of 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.

[0024] Examples of the tetravalent group having one or more aromatic groups for X1 in formula (1) include, but are not limited to, the tetravalent group of the following formula (6). [ka] (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-) (-O- is preferred).)

[0025] In formula (6), the divalent groups of X and Y that are not conjugated with the benzene ring to which they are bonded are preferably -O-, -S-, a methylene group, a bis(trifluoromethyl)methylene group, or a difluoromethylene group, and more preferably -O-.

[0026] In the divalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups of 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.

[0027] Examples of the aromatic hydrocarbon group of Y1 in formula (1) include divalent to tetravalent groups formed from a benzene ring, divalent to tetravalent groups formed from naphthalene, and divalent to tetravalent groups formed from perylene.

[0028] Examples of the divalent group having one or more aromatic groups for Y1 in formula (1) include, but are not limited to, divalent groups in which two aromatic groups are bonded via an ether group (-O-).

[0029] Examples of the divalent group having one or more aromatic groups for Y1 in formula (1) include, but are not limited to, the group of the following formula (7). [ka] (In formula (7), R 12 ~R 19 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, or a monovalent organic group having a halogen atom.

[0030] R in Equation (7) 12 ~R 19 Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) include a methyl group. For example, R 12 and R 15 ~R 19 is a hydrogen atom, and R 13 and R 14 may be a monovalent aliphatic hydrocarbon group.

[0031] R in Equation (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 having 1 to 6 carbon atoms), such as a trifluoromethyl group.

[0032] Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) for R1 and R2 in formula (1) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group.

[0033] At least one of R1 and R2 in formula (1) is a group represented by formula (2), and it is preferred that both are groups represented by formula (2).

[0034] Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) for R3 to R5 in formula (2) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, etc. A methyl group is preferred.

[0035] 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 a polyamic acid, adding a compound represented by the following formula (10) and reacting the resulting mixture in an organic solvent to partially introduce ester groups. 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.

[0036] [ka] (In formula (8), X1 is a group corresponding to X1 in formula (1).)

[0037] [ka] (In formula (9), Y1 is as defined in formula (1).)

[0038] [ka] (In formula (10), R is a group represented by formula (2) above.)

[0039] The component (A) may have a structural unit other than the structural unit represented by formula (1). Examples of structural units other than the structural unit represented by formula (1) include a structural unit represented by formula (11). [ka] In formula (11), X2 is a tetravalent group having one or more aromatic groups, -COOR 51The -CONH- and -COOR- groups are in the ortho position relative to each other. 52 The -CO- group and the -CO- group are in the ortho position relative to each other. Y2 is a divalent group having one or more aromatic groups. R 51 and R 52 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0040] Examples of the tetravalent group having one or more aromatic groups for X2 in formula (11) include the same as the tetravalent group having one or more aromatic groups for X1 in formula (1). Examples of the divalent group having one or more aromatic groups for Y2 in formula (11) include the same as the divalent group having one or more aromatic groups for Y1 in formula (1). R in Equation (11) 51 and R 52 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include the same ones as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R1 and R2.

[0041] The structural units other than the structural unit represented by formula (1) may be used alone or in combination of two or more kinds.

[0042] 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).

[0043] In the component (A), the proportion of carboxy groups esterified with a group represented by formula (2) relative to all carboxy groups and all carboxy esters is preferably 50 mol % or more, more preferably 60 to 100 mol %, and even more preferably 70 to 90 mol %.

[0044] There are no particular limitations on the molecular weight of the component (A), but a weight average molecular weight of 10,000 to 200,000 is preferred. The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.

[0045] The photosensitive resin composition of the present invention contains (B1) a polymerizable monomer having an alicyclic skeleton (preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms), which can impart hydrophobicity to the cured product that can be formed, and can suppress a decrease in adhesion between the cured product and a substrate under high-temperature and high-humidity conditions.

[0046] From the viewpoint of improving the crosslink density with the component (A), the component (B1) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton and a group containing (preferably two or more) polymerizable unsaturated double bonds (preferably a (meth)acrylic group since it is polymerizable by a photopolymerization initiator), and preferably contains two to three groups containing polymerizable unsaturated double bonds in order to improve the crosslink density and photosensitivity and to suppress swelling of the pattern after development.

[0047] The component (B1) preferably contains a polymerizable monomer represented by the following formula (3). [ka] (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 of 0 to 2, and n1+n2 is 1 or more (preferably 2 or 3). At least one of the n1 R6s and the n2 R7s (preferably 2 or 3) is a group represented by the following formula (4).)

[0048] When there are two R7's, the two R7's may be the same or different.

[0049] [ka] (In formula (4), R9~R 11 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10 (preferably 0, 1, or 2).

[0050] The component (B1) more preferably contains a polymerizable monomer represented by the following formula (5): [ka]

[0051] Furthermore, for example, the following polymerizable monomers may be used as the component (B1).

[0052] [ka] In formula (12), R 21 ~R 24 are each independently 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 1 or more (preferably 2).

[0053] R 21 If there are two or more, there are two or more R 21 may be the same or different. R 22 If there are two or more, there are two or more R 22 may be the same or different.

[0054] n3 R 21 At least one of (preferably 2 or 3) is a group represented by the above formula (4). n4 R 22 At least one of (preferably 2 or 3) is a group represented by the above formula (4). n5 R 23 and n6 R 24 At least one of (preferably 2) is a group represented by the above formula (4).

[0055] R6 and R7 in formula (3) and R in formula (12) 21 ~R 24 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include the same ones as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms represented by R1 and R2 in formula (1).

[0056] R9 to R in formula (4)11 Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include the same as the aliphatic hydrocarbon groups having 1 to 3 carbon atoms represented by R3 to R5 in formula (2).

[0057] The component (B1) may use one type alone, or two or more types in combination.

[0058] The content of the (B1) component is preferably 1 to 50 parts by mass relative to 100 parts by mass of the (A) component, 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. When the exposure temperature is within the above range, a practical relief pattern is easily obtained, and post-development residues in unexposed areas are easily suppressed.

[0059] The photosensitive resin composition of the present invention contains (C) a compound containing an acylphosphine oxide structure (for example, one or more, preferably one or two). This makes it possible to reduce the amount of residue even in fine patterns, thereby improving the resolution.

[0060] Examples of component (C) include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (e.g., Irgacure 1700 manufactured by BASF Japan Ltd.).

[0061] As the component (C), for example, a compound represented by the following formula (15) is preferable. [ka] In formula (15), R 26 and R 27 are each independently an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms) (e.g., a methyl group), p and r are each independently an integer of 0 to 5, s is an integer of 0 to 2, t is an integer of 1 to 3, and the sum of s and t is 3. When p is an integer of 2 or more, R 26may be the same or different. When r is an integer of 2 or more, R 27 may be the same or different. When s is 2, the groups in the parentheses may be the same or different. When t is an integer of 2 or more, the groups in the parentheses may be the same or different.

[0062] p is preferably 0. 27 are preferably each independently an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group. r is preferably an integer of 2 to 4, and more preferably 3. The combination of s and t (s, t) is preferably (1,2) or (2,1).

[0063] Examples of the compound represented by formula (15) include a compound represented by the following formula (16) and a compound represented by the following formula (17). [ka]

[0064] The component (C) may use one type alone, or two or more types in combination.

[0065] The content of the component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the component (A). Within the above range, photocrosslinking tends to be uniform in the film thickness direction, making it easier to obtain a practical relief pattern.

[0066] The photosensitive resin composition of the present invention preferably further contains (B2) a polymerizable monomer other than the component (B1) (hereinafter also referred to as "component (B2)". This can improve the heat resistance, mechanical properties, and chemical resistance of the resulting cured product.

[0067] Examples of the component (B2) 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. Further examples thereof include trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tetrakisacrylate methane tetrayl tetrakis (methyleneoxyethylene), ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, and methacryloyloxyethyl isocyanurate.

[0068] Among these, tetraethylene glycol dimethacrylate, pentaerythritol tetraacrylate, and methanetetrayltetrakis(methyleneoxyethylene) tetrakisacrylate are preferable.

[0069] The component (B2) may be used alone or in combination of two or more types.

[0070] When the (B2) component is contained, the total content of the (B1) component and the (B2) component is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) component, 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. When the exposure temperature is within the above range, a practical relief pattern is easily obtained, and post-development residues in unexposed areas are easily suppressed.

[0071] Furthermore, when the (B2) component is contained, from the viewpoint of improving the properties of the cured product, the total content of the (B2) component is preferably 1 to 40 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of the (A) component.

[0072] The photosensitive resin composition of the present invention may further contain (D) an ultraviolet absorber (hereinafter also referred to as "component (D)"). This can suppress crosslinking of unexposed areas caused by diffuse reflection during irradiation with actinic rays, and can further improve the resolution. The component (D) preferably has an absorbance of 0.05 or more, more preferably 0.1 or more, at 365 nm at a concentration of 10 mg / L.

[0073] Examples of the component (D) include: 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2-(2-hydroxy-4-octyl benzotriazole-based compounds such as 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 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; Salicylic acid ester compounds such as phenyl salicylate and 4-tert-butylphenyl salicylate, 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; Diphenylacrylate compounds such as ethyl 2-cyano-3,3-diphenylacrylate, Cyanoacrylate compounds, Diphenyl cyanoacrylate compounds such as 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl), Benzothiazole compounds, Azobenzene compounds such as 4-[ethyl(2-hydroxyethyl)amino]-4′-nitroazobenzene, Polyphenol compounds such as pyrogallol, phloroglysine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagin, quercetagetin, gossypetin, pelargonidin, cyanidin, aurantidin, 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; Examples of nickel complex compounds include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylaminenickel(II).

[0074] It is particularly preferable to use benzotriazole-based compounds, benzophenone-based compounds, azobenzene-based compounds, and polyphenol-based compounds.

[0075] As the (D) component, 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 are preferably used from the viewpoint of resolution (resolution).

[0076] The component (D) may be used alone or in combination of two or more types.

[0077] When the (D) component is included, from the viewpoint of improving resolution, the content of the (D) component is preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, and even more preferably 0.2 part by mass or more, per 100 parts by mass of the (A) component. When the component (D) is contained, the amount of the 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, per 100 parts by mass of the component (A). This can prevent insufficient photocuring inside the photosensitive resin composition due to increased absorption at the surface of the photosensitive resin composition during irradiation with actinic rays.

[0078] From the viewpoint of promoting the polymerization reaction, the photosensitive resin composition of the present invention may further contain (E) a thermal polymerization initiator (hereinafter also referred to as "component (E)"). The component (E) is preferably a compound that does not decompose when heated (dried) to remove the solvent during film formation, but decomposes when heated during curing to generate radicals and promote a polymerization reaction between the components (B1) themselves, or between the components (A) and (B1). The component (E) is preferably a compound having a decomposition point of 110° C. or higher and 200° C. or lower, and from the viewpoint of promoting the polymerization reaction at a lower temperature, a compound having a decomposition point of 110° C. or higher and 175° C. or lower is more preferable.

[0079] Specific examples include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-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-t-butyl peroxide, and dilauroy peroxide. Examples of peroxyesters include diacyl peroxides such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and bis(1-phenyl-1-methylethyl)peroxide. Commercially available products include those under the trade names "Percumyl D", "Percumyl P", "Percumyl H", and "Perbutyl O" (all manufactured by NOF Corporation).

[0080] The component (E) may use one type alone, or two or more types in combination.

[0081] When the (E) component is contained, the content of the (E) component is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) component, more preferably 0.2 to 20 parts by mass in order to ensure good flux resistance, and even more preferably 0.3 to 10 parts by mass in order to suppress a decrease in solubility due to decomposition during drying.

[0082] The photosensitive resin composition of the present invention may further contain a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, and N-dimethylmorpholine. Generally, there are no particular limitations on the solvent as long as it can sufficiently dissolve other components. Among these, from the viewpoints of excellent solubility of each component and excellent coatability during photosensitive resin film formation, it is preferable to use N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0083] Furthermore, as the solvent, a compound represented by the following formula (21) may be used. [ka] (In the formula, R 41 ~R 43 are each independently an alkyl group having 1 to 10 carbon atoms.

[0084] 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The compound represented by formula (21) is preferably 3-methoxy-N,N-dimethylpropanamide (for example, trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).

[0085] The solvent may be used alone or in combination of two or more kinds. The content of the solvent is not particularly limited, but is generally 50 to 1000 parts by mass per 100 parts by mass of the component (A).

[0086] The photosensitive resin composition of the present invention may further contain a polymerization inhibitor, a rust inhibitor, a silane coupling agent (adhesive aid), a sensitizer, and a surfactant or a leveling agent.

[0087] By including a polymerization inhibitor, storage stability can be ensured. Examples of the polymerization inhibitor include a radical polymerization inhibitor and a radical polymerization suppressor.

[0088] Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, and dixoids such as 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dixoid.

[0089] The polymerization inhibitor may be used alone or in combination of two or more kinds.

[0090] 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, per 100 parts by mass of the component (A), from the viewpoints of the storage stability of the photosensitive resin composition and the heat resistance of the obtained cured product.

[0091] By including a rust inhibitor, corrosion of copper and copper alloys can be suppressed and discoloration can be prevented. Examples of the rust inhibitor 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, and 4-amino-3,5-dimethyl-1,2,4-triazole. triazole derivatives such as 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. The rust inhibitors may be used alone or in combination of two or more.

[0092] When a rust inhibitor 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, per 100 parts by mass of the component (A).

[0093] Usually, the silane coupling agent (adhesive aid) reacts with the component (A) during heat treatment after development to form a crosslink, or the silane coupling agent itself polymerizes during the heat treatment step, which can further improve the adhesion between the resulting cured product and the substrate.

[0094] A preferred silane coupling agent is a compound having a urea bond (-NH-CO-NH-), which can further increase the adhesion to the substrate even when curing is performed at a low temperature of 200° C. or less. The compound represented by the following formula (13) is more preferred because it exhibits excellent adhesiveness when cured at low temperatures. [ka] (In formula (13), R 31 and R 32 are each independently 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.

[0095] Specific examples of the compound represented by formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, and 4-ureidobutyltriethoxysilane, and preferably 3-ureidopropyltriethoxysilane.

[0096] The silane coupling agent may be a silane coupling agent having a hydroxyl group or a glycidyl group. By using a silane coupling agent having a hydroxyl group or a glycidyl group and a silane coupling agent having a urea bond in the molecule in combination, the adhesion of the cured product to the substrate during low-temperature curing can be further improved. Examples of the silane coupling agent having a hydroxy 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, and methyl n-propyldiphenylsilanol, ethyldiphenylsilanol, 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.

[0097] [ka] (In formula (14), R 33 is a monovalent organic group having a hydroxyl group or a glycidyl group, and R 34 and R 35are each independently 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.

[0098] 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. An example of a commercially available product is "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0099] The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a group having a nitrogen atom, and a silane coupling agent having an amino group or an amide bond is more preferable. Further, examples of silane coupling agents 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.

[0100] Further, examples of the silane coupling agent having an amide bond include compounds represented by the following formula. R 36 -(CH2) e -CO-NH-(CH2) f -Si(OR 37 )3 (R36 is a hydroxy group or a glycidyl group, e and f each independently represent an integer of 1 to 3, R 37 is a methyl group, an ethyl group, or a propyl group.

[0101] Moreover, the silane coupling agent may be triethoxysilylpropylethylcarbamate.

[0102] The silane coupling agents may be used alone or in combination of two or more.

[0103] When a silane coupling agent is used, the content of the silane coupling agent 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, per 100 parts by mass of the component (A).

[0104] By including a sensitizer, it is possible to maintain the remaining film rate over a wide range of exposure doses while also achieving good resolution.

[0105] Sensitizers include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-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-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetyl benzyl, benzil dimethyl ketal, and benzil. Diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutylate, 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(t-butylperoxycarbonyl)benzophenone, and the like.

[0106] The sensitizers may be used alone or in combination of two or more.

[0107] When a sensitizer is contained, the amount of the sensitizer is preferably 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1.5 parts by mass, per 100 parts by mass of the component (A).

[0108] By including a surfactant or a leveling agent, it is possible to improve the coatability (for example, suppression of striations (unevenness in film thickness)) and the developability.

[0109] Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Commercially available products include those sold under the trade names "Megafac F171", "F173", and "R-08" (all manufactured by DIC Corporation), those sold under the trade names "Fluorad FC430" and "FC431" (all manufactured by Sumitomo 3M Limited), and those sold under the trade name "Organosiloxane Polymer KP341" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0110] The surfactant and leveling agent may be used alone or in combination of two or more kinds.

[0111] When a surfactant or leveling agent is contained, the content of the surfactant or 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, per 100 parts by mass of the component (A).

[0112] The photosensitive resin composition of the present invention essentially consists of the components (A), (B1), and (C), and optionally the components (B2), (D), and (E), a polymerization inhibitor, a rust inhibitor, a silane coupling agent (adhesion aid), a sensitizer, a surfactant, and a leveling agent, excluding the solvent, and may contain other unavoidable impurities as long as the effects of the present invention are not impaired. 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 of the photosensitive resin composition of the present invention, excluding the solvent, Component (A), component (B1) and component (C), Component (A), component (B1), component (C), and component (B2), or It may consist of component (A), component (B1), and component (C), and optionally components (B2), (D), and (E), a polymerization inhibitor, a rust inhibitor, a silane coupling agent (adhesion aid), a sensitizer, a surfactant, and a leveling agent.

[0113] The cured product of the present invention can be obtained by curing the above-mentioned photosensitive resin composition. The cured product of the present invention may be used as a patterned cured product or as a non-patterned cured product. The film thickness of the cured product of the present invention is preferably from 5 to 20 μm.

[0114] In the above-mentioned patterned cured product, the pattern opening width is preferably 3 μm or less. The pattern opening width can be measured from an image of a cross section of the patterned cured product photographed with a scanning electron microscope (SEM).

[0115] The method for producing a patterned cured product of the present invention includes the steps of applying the above-mentioned photosensitive resin composition onto a substrate and drying to form a photosensitive resin film, exposing the photosensitive resin film to a pattern to obtain a resin film, developing the resin film after the pattern exposure using an organic solvent to obtain a patterned resin film, and heat-treating the patterned resin film. In this way, a patterned cured product can be obtained.

[0116] The method for producing a patternless cured product includes, for example, the steps of forming the above-mentioned photosensitive resin film and performing a heat treatment. It may further include a step of exposing the film to light.

[0117] Examples of the substrate include a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), a metal oxide insulator substrate such as a TiO2 substrate or a SiO2 substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

[0118] The coating method is not particularly limited, but may be carried out using a spinner or the like.

[0119] The drying can be carried out using a hot plate, an oven, or the like. The drying temperature is preferably 90 to 150°C, and from the viewpoint of ensuring the dissolution contrast, more preferably 90 to 120°C. The drying time is preferably from 30 seconds to 5 minutes. The drying may be carried out two or more times. In this way, a photosensitive resin film can be obtained in which the above-mentioned photosensitive resin composition is formed into a film shape.

[0120] The thickness of the photosensitive resin film is preferably from 5 to 100 μm, more preferably from 6 to 50 μm, and further preferably from 7 to 30 μm.

[0121] The pattern exposure is performed by exposing a predetermined pattern through a photomask, for example. The actinic rays to be irradiated include ultraviolet rays such as i-rays, visible light, and radiation, and are preferably i-rays. As the exposure device, a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, or the like can be used.

[0122] After the pattern exposure, post-exposure baking (PEB) may be performed before development, if necessary. The temperature of the post-exposure baking is preferably 60° C. to 160° C., and the time of the post-exposure baking is preferably 30 seconds to 5 minutes.

[0123] By developing, a resin film having a pattern formed thereon (patterned resin film) can be obtained. In general, when a negative type photosensitive resin composition is used, the unexposed areas are removed with a developer. The organic solvent used as the developer may be a good solvent for the photosensitive resin film, or a suitable mixture of a good solvent and a poor solvent. Examples of the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, and cyclohexanone. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0124] A surfactant may be added to the developer. The amount of surfactant added is preferably from 0.01 to 10 parts by mass, and more preferably from 0.1 to 5 parts by mass, relative to 100 parts by mass of the developer.

[0125] The development time can be set to, for example, twice the time required for the photosensitive resin film to be immersed and completely dissolved. The development time differs depending on the component (A) used, but is preferably from 10 seconds to 15 minutes, more preferably from 10 seconds to 5 minutes, and from the viewpoint of productivity, even more preferably from 20 seconds to 5 minutes.

[0126] After development, washing may be carried out with a rinsing solution. As the rinse liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in appropriate mixture, or in stepwise combination.

[0127] By subjecting the patterned resin film to a heat treatment, a patterned cured product can be obtained. The polyimide precursor of component (A) undergoes a dehydration ring-closing reaction during the heat treatment step, usually resulting in the corresponding polyimide.

[0128] The temperature of the heat treatment is preferably 250°C or lower, more preferably 120 to 250°C, and even more preferably 200°C or lower or 160 to 200°C. By keeping the amount within the above range, damage to the substrate and devices can be minimized, devices can be produced with a high yield, and energy savings can be achieved in the process.

[0129] The heat treatment time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. Within the above range, the crosslinking reaction or the dehydration ring-closing reaction can proceed sufficiently. The heat treatment may be performed in air or in an inert atmosphere such as nitrogen, but is preferably performed in a nitrogen atmosphere from the viewpoint of preventing oxidation of the patterned resin film.

[0130] Examples of equipment used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealer, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0131] The cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protective film, or the like. Using one or more selected from the group consisting of the above passivation films, buffer coat films, interlayer insulating films, cover coat layers, and surface protection films, etc., highly reliable electronic components such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (multi-die fan-out wafer-level packages, etc.) can be manufactured.

[0132] An example of a manufacturing process for a semiconductor device, which is an electronic component of the present invention, will be described with reference to the drawings. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure, which is an electronic component according to one embodiment of the present invention. 1, 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 conductor layer 3 is formed on the exposed circuit elements. Then, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0133] Next, a photosensitive resin layer 5 such as a chlorinated rubber or phenol novolak type is formed on the interlayer insulating film 4, and windows 6A are provided by a known photoetching technique so that predetermined portions of the interlayer insulating film 4 are exposed.

[0134] The interlayer insulating film 4 from which the window 6A is exposed is selectively etched to provide a window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.

[0135] Furthermore, a second conductor layer 7 is formed by using a known photolithography technique, and is electrically connected to the first conductor layer 3 . When forming a multi-layer wiring structure having three or more layers, the above steps can be repeated to form each layer.

[0136] Next, the above-mentioned photosensitive resin composition is used to open windows 6C by pattern exposure to form a surface protective film 8. The surface protective film 8 protects the second conductor layer 7 from external stress, α-rays, etc., and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film can also be formed using the photosensitive resin composition of the present invention. EXAMPLES

[0137] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0138] Synthesis Example 1 (Synthesis of A1) 47.1 g (152 mmol) of 3,3',4,4'-diphenylethertetracarboxylic 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) and stirred at 45°C for 1 hour, then cooled to 25°C. To this solution, 27.4 g (129 mmol) of 2,2'-dimethylbenzidine and 145 mL of dry N-methyl-2-pyrrolidone were added, and the mixture was stirred at 45°C for 150 minutes and then cooled to room temperature. To this solution, 59.7 g (284 mmol) of trifluoroacetic anhydride was added dropwise, and the mixture was stirred for 120 minutes. To this solution, a catalytic amount of benzoquinone was added, and then 40.4 g (310 mmol) of HEMA was added, and the mixture was stirred at 45° C. for 20 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A1. The weight-average molecular weight of the obtained polyimide precursor A1 was determined by gel permeation chromatography (GPC) using standard polystyrene standards under the following conditions: The weight-average molecular weight of A1 was 35,000.

[0139] The measurement was performed using 1 mL of a solution of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] for 0.5 mg of A1.

[0140] Measurement equipment: Detector: Hitachi L4000UV Pump: Hitachi L6000 Shimadzu Corporation C-R4A Chromatopac Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF=1 / 1 (volume ratio) LiBr(0.03mol / L), H3PO4(0.06mol / L) Flow rate: 1.0 mL / min, detector: UV 270 nm

[0141] The esterification rate of A1 (the reaction rate of the carboxyl groups of ODPA with HEMA) was calculated by NMR measurement under the following conditions: The esterification rate was 81 mol% relative to the total carboxyl groups (total carboxyl groups and total carboxy esters) (the remaining 19 mol% was carboxyl groups).

[0142] Measurement equipment: Bruker Biospin AV400M Magnetic field strength: 400MHz Reference material: Tetramethylsilane (TMS) Solvent: dimethyl sulfoxide (DMSO)

[0143] Synthesis Example 2 (Synthesis of A2) In a 1.0 liter flask equipped with a stirrer and a thermometer, 62.0 g (199.9 mmol) of 4,4'-oxydiphthalic dianhydride, 5.2 g (40.0 mmol) of 2-hydroxyethyl methacrylate, and a catalytic amount of 1,4-diazabicyclo[2.2.2.]octane triethylenediamine were dissolved in 250.0 g of N-methyl-2-pyrrolidone, and the solution 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 (118.9 mmol) of oxydianiline (4,4'-diaminodiphenyl ether), and 100 mL of dry N-methyl-2-pyrrolidone were added, and the mixture was stirred at 45°C for 150 minutes and then cooled to room temperature. 78.5g (373.8mmol) of trifluoroacetic anhydride was added dropwise to this solution, and the mixture was stirred for 20 minutes. Then, 53.1g (408.0mmol) of 2-hydroxyethyl methacrylate was added and stirred at 45°C for 20 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. This is designated as polyimide precursor A2. The weight average molecular weight was determined in the same manner as in Synthesis Example 1. The weight average molecular weight of A2 was 35,000.

[0144] The esterification rate of A2 was determined in the same manner as in Synthesis Example 1. The esterification rate of A2 was 70 mol % relative to all carboxy groups (total carboxy groups and all carboxy esters) (the remaining 30 mol % was carboxy groups).

[0145] Examples 1 to 3 and Comparative Examples 1 to 6 [Preparation of photosensitive resin composition] Photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 6 were prepared using the components and amounts shown in Table 1. The amounts shown in Table 1 are parts by mass of each component relative to 100 parts by mass of component (A).

[0146] The components used are as follows: As the component (A), the polyimide precursor A1 obtained in Synthesis Example 1 and the polyimide precursor A2 obtained in Synthesis Example 2 were used.

[0147] (B1) Component B1: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula) [ka]

[0148] (B2) Component B2: ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd., tetrakis(methyleneoxyethylene) tetrakisacrylate) B3: TEGDMA (Tetraethylene glycol dimethacrylate, manufactured by Sartomer)

[0149] B4: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., tetramethylolmethane tetraacrylate, a compound represented by the following formula) [ka]

[0150] B5: ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated pentaerythritol tetraacrylate, a compound represented by the following formula D2-6, n11+n12+n13+n14=35) [ka]

[0151] (C) Component C1: Irgacure TPO (BASF Japan, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide) C2: Irgacure 819 (BASF Japan, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide)

[0152] (C') component C3: IRGACURE OXE 02 (manufactured by BASF Japan Ltd., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)) C4: G-1820 (PDO) (Lambson Corporation, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime) C5: BTTB (NOF Corporation, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone)

[0153] (D) Component D1: Curcumin (manufactured by Sanwa Chemical Co., Ltd., (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione)

[0154] (E) Component E1: Percumyl D (NOF Corporation, bis(1-phenyl-1-methylethyl) peroxide)

[0155] Polymerization Inhibitor F1: Taobn (Hampford Research, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dixoid)

[0156] Sensitizer EMK (4,4′-bis(diethylamino)benzophenone, manufactured by Aldrich)

[0157] solvent KJCMPA-100 (KJ Chemicals Co., Ltd., 3-methoxy-N,N-dimethylpropanamide) NMP (N-methyl-2-pyrrolidone)

[0158] [Absorbance measurement of component (D)] The absorbance of D1 described above was measured. D1 was dissolved in chloroform to prepare a 10 mg / L sample for measurement. The measurement equipment and conditions are as follows. As a result, the absorbance of D1 was 0.25. Measuring equipment: U-3900H (manufactured by Hitachi High-Tech Science Corporation) Measurement conditions: Cell length: 10.0 mm

[0159] [Manufacturing patterned resin film] The obtained photosensitive resin composition was spin-coated onto a silicon wafer using a coating device Act8 (Tokyo Electron Limited), dried at 105°C for 2 minutes, and then dried at 115°C for 2 minutes to form a photosensitive resin film having a dry thickness of 7 to 10 μm. The resulting photosensitive resin film was immersed in cyclopentanone and the developing time was set to twice the time required for it to be completely dissolved. In addition, a photosensitive resin film was prepared in the same manner as described above, and the obtained photosensitive resin film was exposed to light using an i-line stepper FPA-3000iW (manufactured by Canon Inc.) at the exposure dose shown in Table 1 by irradiating a photomask for forming vias having a diameter of 1 μm to 100 μm. The exposed resin film was paddle-developed in cyclopentanone using Act8 for the above-mentioned developing time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

[0160] [Evaluation of remaining film rate] The thickness of the above-mentioned photosensitive resin film before exposure and the obtained patterned resin film were measured using an optical interference type film thickness measuring device VM-2210 (manufactured by SCREEN Co., Ltd.), and the remaining film ratio was calculated according to the following formula. Residual film rate (%) = (film thickness of patterned resin film) / (film thickness of photosensitive resin film) × 100 The results are shown in Table 1.

[0161] [Production of patterned cured product] The obtained patterned resin film was heated in a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere at 175° C. for 2 hours to obtain a patterned cured product (film thickness after curing: 6 to 7 μm).

[0162] [Evaluation of aperture mask dimensions] The obtained patterned cured product was observed using an optical microscope, and the smallest diameter at which an opening was formed that exposed 55% or more of the substrate surface relative to the area of ​​the via mask dimensions was evaluated as the opening mask dimension. The results are shown in Table 1.

[0163] [Opening width evaluation] For the patterned cured products of Examples 1 to 3 and Comparative Examples 2 to 5, which had a residual film rate of 80% or more, cross-sections were observed using focused ion beam processing and a scanning electron microscope combination instrument (FIB-SEM) SMI500 (manufactured by Hitachi High-Tech Science Corporation). For each pattern, a pattern with a smooth forward tapered cross section was selected from the obtained cross-sectional images. Among the selected patterns, the opening width on the substrate with the smallest mask dimension was measured. The results are shown in Table 1. "-" indicates that no measurement was performed.

[0164] [Table 1] [Industrial Applicability]

[0165] The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, a surface protective film, or the like, and the interlayer insulating film, cover coat layer, or surface protective film of the present invention can be used for electronic parts, etc. [Explanation of symbols]

[0166] 1. Semiconductor substrate 2 Protective film 3 First conductor layer 4 Interlayer insulating film 5 Photosensitive resin layer 6A, 6B, 6C Windows 7 Second Conductor Layer 8 Surface protective film

Claims

1. (A) a polyimide precursor having a polymerizable unsaturated bond; (B1) a polymerizable monomer having an aliphatic cyclic skeleton, (B2) 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, pentaerythritol triacrylate, pentaerythritol tetraacrylate, one or more selected from the group consisting of pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tetrakisacrylate methane tetrayl tetrakis (methyleneoxyethylene), ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, and methacryloyloxyethyl isocyanurate; and (C) containing a compound containing an acylphosphine oxide structure, The content of the component (B2) is 1 to 40 parts by mass per 100 parts by mass of the component (A).

2. 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 1】 (In formula (1), X １ is a tetravalent group having one or more aromatic groups, -COOR １ The -COOR group and the -CONH- group are in the ortho position relative to each other. ２ The Y group and the —CO— group are in the ortho position relative to each other. １ is a divalent group having one or more aromatic groups. １ and R ２ 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; R １ and R ２ At least one of the above is a group represented by formula (2). 【Chemistry 2】 (In formula (2), R ３ ~R ５ 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. 3. The photosensitive resin composition according to claim 1, wherein the component (B1) comprises a polymerizable monomer having a group containing a polymerizable unsaturated double bond and having an alicyclic skeleton.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B1) contains a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds and having an aliphatic cyclic skeleton.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B1) contains a polymerizable monomer represented by the following formula (3): 【Chemistry 3】 (In formula (3), R ６ and R ７ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4), where n1 is 0 or 1, n2 is an integer of 0 to 2, and n1+n2 is 1 or more. ６ and n2 R ７ At least one of the above is a group represented by the following formula (4): 【Chemistry 4】 (In formula (4), R ９ ~R １１ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10.

6. The photosensitive resin composition according to claim 5, wherein n1+n2 is 2 or 3.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (B1) contains a polymerizable monomer represented by the following formula (5): 【Chemistry 5】

8. A photosensitive resin composition according to any one of claims 1 to 7, wherein the (B2) component is one or more selected from the group consisting of triethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, and tetrakisacrylate methane tetrayl tetrakis (methyleneoxyethylene).

9. The photosensitive resin composition according to any one of claims 1 to 8, further comprising (D) an ultraviolet absorber.

10. The photosensitive resin composition according to any one of claims 1 to 9, further comprising (E) a thermal polymerization initiator.

11. A step of applying the photosensitive resin composition according to any one of claims 1 to 10 onto a substrate and drying the composition to form a photosensitive resin film; a step of exposing the photosensitive resin film to a pattern to obtain a resin film; developing the resin film after the patterned exposure with an organic solvent to obtain a patterned resin film; and heat-treating the patterned resin film.

12. The method for producing a patterned cured product according to claim 11, wherein the heat treatment is performed at a temperature of 200° C. or lower.

13. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 10.

14. The cured product according to claim 13, which is a patterned cured product.

15. An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured product according to claim 13 or 14.

16. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to claim 15.

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