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

Abstract

To provide a photosensitive resin composition having excellent sensitivity, a method for producing a patterned cured film using the same, a cured film, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.SOLUTION: The photosensitive resin composition comprises: (A) a polyimide precursor having a polymerizable unsaturated bond; (B) one or more of compounds represented by the formulas (1) to (4) in the figure; and (C) a photopolymerization initiator represented by a specific formula.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, a cured film, 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 protective film and interlayer insulating film 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 films and shorten the complicated manufacturing process (see, for example, Patent Document 1).

[0003] In recent years, miniaturization of transistors, which has supported the high performance of computers, is facing the limits of scaling laws, and stacked device structures in which semiconductor elements are stacked three-dimensionally to achieve further high performance and speed have been attracting attention (for example, see Non-Patent Document 1). Among stacked device structures, multi-die fanout wafer level packaging is a package manufactured by collectively sealing multiple dies in one package, and is attracting attention because it is expected to reduce costs and improve performance compared to the conventional fan-out wafer level packaging (manufactured by sealing one die in one package).

[0004] In the fabrication of multi-die fan-out wafer-level packages, the exposure time of steppers is becoming longer as the wafer size becomes larger, and this requires photosensitive materials with higher sensitivity to make the exposure process more efficient. For example, Patent Document 2 discloses a negative-type photosensitive resin composition containing a specific amide compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2009-265520 A [Patent Document 2] JP 2016-79340 A [Non-patent literature]

[0006] [Non-Patent Document 1] "Semiconductor Technology Yearbook 2013 Packaging / Mounting Edition", Nikkei BP, December 2012, pp.41-50 Summary of the Invention [Problem to be solved by the invention]

[0007] However, conventional photosensitive resin compositions do not have sufficiently high photosensitivity. An object of the present invention is to provide a photosensitive resin composition having excellent sensitivity, a method for producing a patterned cured film using the same, a cured film, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research in view of the above problems and have found that a photosensitive resin composition having high photosensitivity can be obtained by combining a polyimide precursor having a polymerizable unsaturated bond with a specific photopolymerization initiator and a compound having a specific structure, thereby completing the present invention.

[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; (B) one or more compounds represented by the following formulas (1) to (4): (C) a photopolymerization initiator represented by the following formula (11), A photosensitive resin composition comprising: [ka] (In formulas (1) to (4), R 1 , R2 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms; R 3 ~R 7 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, s is an integer of 0 to 8, t is an integer of 0 to 4, and r is an integer of 0 to 4. [ka] (In formula (11), R 11 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group; R 12 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group; R 13 is a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group. 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 (21): [ka] (In formula (21), X 1 is a tetravalent aromatic group. Y 1 is a divalent aromatic group. 21 and R 22 are each independently a hydrogen atom, a group represented by the following formula (22) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 21 and R 22 At least one of the groups is a group represented by the following formula (22): 21 The -COOR group and the -CO- group are in the ortho position relative to each other. 22 The -CONH- group and the -CONH- group are in the ortho position to each other. [ka] (In formula (22), R 23 ~R 25are 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 1 or 2, which contains, as the component (B), at least a compound represented by the formula (3). 4. The photosensitive resin composition according to any one of 1 to 3, comprising 10 to 10,000 parts by mass of the component (B) per 100 parts by mass of the component (A). 5. The photosensitive resin composition according to any one of 1 to 4, further comprising (D) a crosslinking agent. 6. The photosensitive resin composition according to any one of 1 to 5, further comprising (E) a thermal polymerization initiator. 7. A step of applying the photosensitive resin composition according to any one of 1 to 6 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; a step of heat treating the patterned resin film; A method for producing a patterned cured film comprising the steps of: 8. The method for producing a patterned cured film according to 7, wherein the heat treatment is carried out at a temperature of 200° C. or lower. 9. A cured film obtained by curing the photosensitive resin composition according to any one of 1 to 6. 10. The cured film according to 9, which is a patterned cured film. 11. An interlayer insulating film, a cover coat layer or a surface protective film prepared using the cured film according to 9 or 10. An electronic component comprising an interlayer insulating film, a cover coat layer, or a surface protective film according to 12.11. Effect of the Invention

[0010] According to the present invention, there can be provided a photosensitive resin composition having excellent sensitivity, a method for producing a patterned cured film using the same, a cured film, 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 schematic 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 film, the cured film, the interlayer insulating film, the cover coat layer, the surface protective film, and the electronic component according to 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 this specification, the term "process" includes 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. In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. 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. In this specification, the exemplified materials may be used alone or in combination of two or more types, unless otherwise specified. In this specification, "(meth)acrylic group" means "acrylic group" and "methacrylic group".

[0014] [Photosensitive resin composition] 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) one or more compounds represented by the following formulas (1) to (4) (hereinafter also referred to as "component (B)"), and (C) a photopolymerization initiator represented by the following formula (11) (hereinafter also referred to as "component (C)"). The photosensitive resin composition of the present invention is preferably a negative type photosensitive resin composition. [ka] (In formulas (1) to (4), R 1 , R 2 and R 8are each independently an alkyl group having 1 to 4 carbon atoms; R 3 ~R 7 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, s is an integer of 0 to 8, t is an integer of 0 to 4, and r is an integer of 0 to 4. [ka] (In formula (11), R 11 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group; R 12 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group; R 13 is a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group.

[0015] The photosensitive resin composition of the present invention contains the above-mentioned components, and thus has higher photosensitivity than conventional photosensitive resin compositions, i.e., a pattern with a high residual film rate can be obtained with a small amount of exposure. Each component will be described below.

[0016] (Component (A): Polyimide precursor having a polymerizable unsaturated bond) The component (A) is not particularly limited as long as it is a polyimide precursor having a polymerizable unsaturated bond, but a polyimide precursor that has high transmittance when i-line is used as a light source for patternwise exposure and that exhibits high cured film properties even when cured at a low temperature of 200°C or less is preferred. The polymerizable unsaturated bond may be a double bond between carbon atoms.

[0017] The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (21): This provides high i-line transmittance and allows the formation of a good cured film even when curing is performed at a low temperature of 200°C or less. [ka] (In formula (21), X 1 is a tetravalent aromatic group. Y 1 is a divalent aromatic group. 21 and R 22 are each independently a hydrogen atom, a group represented by the following formula (22) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 21 and R 22 At least one of the groups is a group represented by the following formula (22): 21 The -COOR group and the -CO- group are in the ortho position relative to each other. 22 The -CONH- group and the -CONH- group are in the ortho position to each other. [ka] (In formula (22), R 23 ~R 25 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 10, more preferably an integer of 2 to 5, and even more preferably 2 or 3).

[0018] X 1 The tetravalent aromatic group may be a tetravalent group containing an aromatic hydrocarbon structure (having, for example, 6 to 20 carbon atoms) or a tetravalent group containing an aromatic heterocyclic structure (having, for example, 5 to 20 atoms). X 1 is preferably a tetravalent group containing an aromatic hydrocarbon structure.

[0019] X 1 Examples of the tetravalent group containing an aromatic hydrocarbon structure include, but are not limited to, the groups shown below. [ka] (In the formula, Z 1 and Z 2 are each independently a divalent group or a single bond that is not conjugated with the benzene ring to which it is attached. 3 is an ether bond (-O-) or a sulfide bond (-S-).

[0020] Z 1 and Z2 The divalent group is preferably -O-, -S-, a methylene group, a bis(trifluoromethyl)methylene group, or a difluoromethylene group, and more preferably -O-. Z 3 is preferably -O-.

[0021] Y 1 The divalent aromatic group may be a divalent aromatic hydrocarbon group (having, for example, 6 to 20 carbon atoms) or a divalent aromatic heterocyclic group (having, for example, 5 to 20 atoms). 1 is preferably a divalent aromatic hydrocarbon group.

[0022] Y 1 Examples of the divalent aromatic hydrocarbon group include, but are not limited to, groups represented by the following formula (23): [ka] (In formula (23), R 31 ~R 38 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, or a monovalent organic group having a halogen atom.

[0023] R 31 ~R 38 The monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) is preferably a methyl group.

[0024] R 31 ~R 38 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), and more preferably a trifluoromethyl group.

[0025] In formula (23), for example, R 32 and R 33 is a monovalent aliphatic hydrocarbon group (e.g., a methyl group), and R 31 and R 34 ~R 38may be a hydrogen atom.

[0026] R in Equation (21) 21 and R 22 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group.

[0027] In formula (21), R 21 and R 22 At least one of R is a group represented by formula (22), and preferably R 21 and R 22 are both groups represented by formula (22).

[0028] R in Equation (22) 23 ~R 25 Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, etc. A methyl group is preferred.

[0029] A polyimide precursor having a structural unit represented by formula (21) can be produced, for example, by reacting a tetracarboxylic dianhydride represented by the following formula (24) with a diamino compound represented by the following formula (25) in an organic solvent such as N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") to produce a polyamic acid, adding a compound represented by the following formula (26) and reacting in an organic solvent to introduce ester groups entirely or partially. [ka] (In formula (24), X 1 is as defined in formula (21). In formula (25), Y 1 is as defined in formula (21). In formula (26), R 23 ~R 25 and m are as defined in equation (22).

[0030] The tetracarboxylic dianhydride represented by the formula (24) and the diamino compound represented by the formula (25) may be used alone or in combination of two or more kinds.

[0031] The content of the structural unit represented by formula (21) is preferably 50% by mole or more, and more preferably 80% by mole or more, based on all structural units in the component (A). There is no particular upper limit, and it may be 100% by mole.

[0032] The component (A) may have a structural unit other than the structural unit represented by formula (21). Examples of the structural unit other than the structural unit represented by formula (21) include a structural unit represented by the following formula (27). [ka] (In formula (27), X 2 is a tetravalent aromatic group. Y 2 is a divalent aromatic group. 41 and R 42 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. 42 The -CONH- and -COOR- groups are in the ortho position relative to each other. 41 The -CO- group and the -CO- group are in the ortho position relative to each other.

[0033] X in equation (27) 2 As the tetravalent aromatic group, X in the formula (21) 1 The tetravalent aromatic group Y 2 As the divalent aromatic group, Y in formula (21) 1 The divalent aromatic group R 41 and R 42 As the aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 21 and R 22 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include the same groups as those listed above.

[0034] The content of structural units other than the structural unit represented by formula (21) is preferably less than 50 mol % based on all structural units in the component (A). The structural unit other than the structural unit represented by formula (21) may be of one type alone or of two or more types.

[0035] In the component (A), the proportion of carboxy groups esterified with the group represented by formula (22) relative to all carboxy groups and all carboxy esters in the polyimide precursor is preferably 50 mol % or more, more preferably 60 to 100 mol %, and still more preferably 70 to 90 mol %.

[0036] There are no particular limitations on the molecular weight of the component (A), but a number average molecular weight of 10,000 to 200,000 is preferred. The number average molecular weight is determined by measuring by gel permeation chromatography (GPC) and converting the result using a standard polystyrene calibration curve. Specifically, the number average molecular weight is measured by the method described in the Examples.

[0037] (Component (B): one or more of the compounds represented by formulas (1) to (4)) The photosensitive resin composition of the present invention has high photosensitivity by containing one or more of the compounds represented by formulas (1) to (4) as the component (B). [ka] (In formulas (1) to (4), R 1 , R 2 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms; R 3 ~R 7 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, s is an integer of 0 to 8, t is an integer of 0 to 4, and r is an integer of 0 to 4.

[0038] In formula (1), s is preferably 0. In formula (2), R 2 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2 (more preferably 1). In formula (3), R 3The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, or a butyl group. 4 and R 5 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. In formula (4), R 6 ~R 8 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. r is preferably 0 or 1 (more preferably 0).

[0039] The component (B) may be, for example, one or more of the compounds represented by formulas (1), (3), and (4), or may be a compound represented by formula (3).

[0040] As the component (B), for example, the following compounds can be used. [ka]

[0041] The content of the component (B) is usually 10 to 10,000 parts by mass, preferably 10 to 1,000 parts by mass, and more preferably 10 to 500 parts by mass, per 100 parts by mass of the component (A).

[0042] (solvent) The photosensitive resin composition of the present invention may contain a solvent (e.g., an organic solvent). There are no particular limitations on such a solvent, and any solvent that is commonly used can be used. Specific examples of the solvent include the following solvents. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)). ethyl propionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and NMP. Examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene. The sulfoxides include dimethyl sulfoxide and the like.

[0043] As the solvent, preferably, γ-butyrolactone, cyclopentanone, ethyl lactate, or the like is used.

[0044] The content of NMP in the photosensitive resin composition of the present invention may be, for example, 1% by mass or less (or 3 parts by mass or less per 100 parts by mass of the component (A)). The content of NMP may be 0% by mass (no NMP is included). This can reduce toxicity such as reproductive toxicity.

[0045] Since the (B) component can usually dissolve other components of the photosensitive resin composition of the present invention to form a varnish, the above-mentioned solvent may or may not be used. When the above-mentioned solvent is used, the content of the (B) component is, for example, 5 to 100% by mass relative to the total of the (B) component and the solvent, and may be 5 to 50% by mass relative to the total of the (B) component and the solvent. When the above-mentioned solvent is used, the content of the (B) component is, for example, 10 to 1000 parts by mass relative to 100 parts by mass of the (A) component, and may be 10 to 100 parts by mass relative to 100 parts by mass of the (A) component, or 10 to 50 parts by mass relative to 100 parts by mass of the (A) component. Even if the content of the (B) component is small (for example, 5 to 50% by mass relative to the total of the (B) component and the solvent, or 10 to 50 parts by mass relative to 100 parts by mass of the (A) component), the sensitivity of the photosensitive resin composition of the present invention can be improved.

[0046] (Component (C): Photopolymerization initiator represented by formula (11)) The photosensitive resin composition of the present invention contains the photopolymerization initiator represented by formula (11), and as a result of the synergistic effect with the component (B), the composition has higher photosensitivity. [ka] (In formula (11), R 11 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group; R 12 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group; R 13 is a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group.

[0047] R 11 and R 12 are each independently preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group, or a tolyl group, more preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group, or a tolyl group, and further preferably a methyl group, a cyclopentyl group, a phenyl group, or a tolyl group. R 13 R in formula (11) in the compounds represented by formulas (14) to (20) described later. 13 It is preferred that the group corresponds to:

[0048] Examples of the substituent (hereinafter also referred to as an arbitrary substituent) of the substituted or unsubstituted benzoyl group, the substituted or unsubstituted fluorenyl group, or the substituted or unsubstituted carbazolyl group include a phenylthio group, an ethyloloxy group, an alkyl group having 1 to 20 carbon atoms (e.g., a methyl group, an ethyl group, an n-propyl group), an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 8) which may be halogenated (preferably fluorinated), a 2,2-dimethyl-1,3-dioxolan-4-yl)methoxy group, a benzoyl group, and the like. The optional substituents may further have the optional substituents described above.

[0049] From the viewpoint of improving photocurability, the component (C) is preferably a compound represented by the following formula (12) or formula (13). [ka] In formula (12), R 61 and R 62 is R in the above formula (11). 11 and R 12 is the same as: R 64 is -H, -OH, -COOH, -O(CH2)OH, -O(CH2)2OH, -COO(CH2)OH, or -COO(CH2)2OH, preferably -H, -O(CH2)OH, -O(CH2)2OH, -COO(CH2)OH, or -COO(CH2)2OH, and more preferably -H, -O(CH2)2OH, or -COO(CH2)2OH.

[0050] [ka] In formula (13), R 61 and R 62 is R in the above formula (11). 11 and R 12 is the same as: R 65 R is an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group. 66 is an alkyl group having 1 to 12 carbon atoms or an organic group having an acetal bond, and R 66 Preferably, i is a substituent corresponding to the following formula: where i is an integer of 1 to 3, and preferably 1 or 2.

[0051] Examples of the compound represented by formula (12) include compounds represented by formulas (14) and (15). The compound represented by formula (14) is available as IRGACURE OXE-01 (manufactured by BASF Japan Ltd.). [ka]

[0052] Examples of the compound represented by formula (13) include compounds represented by formula (16) or (17) below, which are available as IRGACURE OXE-02 (manufactured by BASF Japan Ltd.) and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation), respectively. [ka]

[0053] Furthermore, as the photopolymerization initiator of the component (C), compounds represented by the following formulas (18) to (20) can also be used. [ka]

[0054] The content of the (C) component is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 6 parts by mass, relative to 100 parts by mass of the (A) component. When the content is within the above range, photocrosslinking tends to be uniform in the film thickness direction, making it easier to obtain a practical relief pattern.

[0055] (Component (D): Crosslinking agent) The photosensitive resin composition of the present invention may further contain a crosslinking agent (hereinafter also referred to as "component (D)"). The component (D) preferably has a polymerizable unsaturated double bond-containing group, and in order to improve the crosslink density and photosensitivity and to suppress swelling of the pattern after development, the component (D) preferably has 2 to 6 polymerizable unsaturated double bond-containing groups, and more preferably has 2 to 4. The component (D) is preferably a compound having a (meth)acrylic group polymerizable by a photopolymerization initiator.

[0056] Specific examples of the (D) component include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth)acrylate, 1,3-(meth)acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, and tricyclodecane dimethanol diacrylate.

[0057] The component (D) preferably has a polymerizable unsaturated double bond-containing group and further has an aliphatic cyclic 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.

[0058] The component (D) preferably contains a crosslinking agent represented by the following formula (31). [ka] (In formula (31), R 51 and R 52 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (32), where n1 is 0 or 1, n2 is an integer of 0 to 2, and n1+n2 is 1 or more (preferably 2 or 3). 51 and n2 R 52 At least one of (preferably 2 or 3) is a group represented by the following formula (32).

[0059] R 52 If there are two, then there are two R52 may be the same or different.

[0060] [ka] (In formula (32), R 53 ~R 55 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).

[0061] R in Equation (31) 51 and R 52 As the aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 21 and R 22 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include the same groups as those listed above.

[0062] The amount of component (D), when present, is preferably 1 to 100 parts by mass, more preferably 1 to 75 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of component (A).

[0063] (Component (E): Thermal polymerization initiator) The photosensitive resin composition of the present invention may further contain 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 the formation of the photosensitive resin film, but decomposes when heated during curing to generate radicals and promote the polymerization reaction between the components (D) themselves or between the components (A) and (D). Therefore, the component (E) is preferably a compound with 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 with a decomposition point of 110° C. or higher and 175° C. or lower is more preferable. Examples of the component (E) include bis(1-phenyl-1-methylethyl) peroxide.

[0064] When component (E) is contained, the content thereof is preferably 0.5 to 20 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). From the viewpoint of suppressing a decrease in solubility due to decomposition during drying, the content is further preferably 1 to 10 parts by mass.

[0065] (Other ingredients) The photosensitive resin composition of the present invention may contain, in addition to the above components, a coupling agent, a surfactant or leveling agent, a rust inhibitor, a polymerization inhibitor, and the like.

[0066] (Coupling Agent) The coupling agent reacts with component (A) during heat treatment after development to form crosslinks, or the coupling agent itself polymerizes during the heat treatment step, thereby further improving the adhesion between the resulting cured film and the substrate.

[0067] The coupling agent is preferably a silane coupling agent. A preferred silane coupling agent is a compound having a urea bond (-NH-CO-NH-), which can further increase the adhesion between the resulting cured film and the substrate even when curing is performed at a low temperature of 200° C. or less. The compound represented by the following formula (41) is more preferred in that it exhibits excellent adhesiveness when cured at a low temperature. [ka] (In formula (41), R 71 and R 72 are each independently an alkyl group having 1 to 5 carbon atoms, j is an integer of 1 to 10, and k is an integer of 1 to 3.

[0068] Specific examples of the compound represented by formula (41) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, and 4-ureidobutyltriethoxysilane, and preferably 3-ureidopropyltriethoxysilane.

[0069] 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 film to the substrate during low-temperature curing can be further improved.

[0070] 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 (42). Among them, the compound represented by formula (42) is particularly preferred in order to further improve the adhesion to the substrate.

[0071] [ka] (In formula (42), R 73 is a monovalent organic group having a hydroxyl group or a glycidyl group, and R 74 and R 75are each independently an alkyl group having 1 to 5 carbon atoms, o is an integer of 1 to 10, and p is an integer of 1 to 3.

[0072] Examples of the compound represented by formula (42) 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.

[0073] The silane coupling agent having a hydroxy group or a glycidyl group is preferably a silane coupling agent further containing a group having a nitrogen atom (for example, an amino group or an amide bond). 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.

[0074] Further, examples of the silane coupling agent having an amide bond include the compound represented by the following formula (43). R 76 -(CH2) q -CO-NH-(CH2) u -Si(OR 77 )3(43) (In formula (43), R 76is a hydroxy group or a glycidyl group, q and u are each independently an integer of 1 to 3, R 77 is a methyl group, an ethyl group, or a propyl group.

[0075] 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 0.3 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A).

[0076] (Surfactant or leveling agent) 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.

[0077] 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 trade names "Megafax F171", "F173", and "R-08" (all manufactured by DIC Corporation), trade names "Fluorad FC430" and "FC431" (all manufactured by 3M Japan Ltd.), and trade names "Organosiloxane Polymer KP341", "KBM303", "KBM403", and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0078] 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).

[0079] (rust inhibitor) 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 triazole derivatives and tetrazole derivatives. 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 3 parts by mass, per 100 parts by mass of the component (A).

[0080] (Polymerization inhibitor) By including a polymerization inhibitor, good storage stability can be ensured. Examples of the polymerization inhibitor include a radical polymerization inhibitor and a radical polymerization suppressor. 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, and nitrosamines.

[0081] 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 film.

[0082] The photosensitive resin composition of the present invention may essentially consist of the components (A) to (C), as well as one or more components selected from the group consisting of a solvent, a component (D), a component (E), a coupling agent, a surfactant, a leveling agent, a rust inhibitor, and a polymerization inhibitor, and may also contain other unavoidable impurities within a range that does not impair the effects of the present invention. For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or 100% by mass of the photosensitive resin composition of the present invention is (A) ~ (C) ingredients, Components (A) to (C) and a solvent, Components (A) to (D) and a solvent, Components (A) to (E) and a solvent, or The composition may be composed of components (A) to (C), as well as one or more components selected from the group consisting of a solvent, component (D), component (E), a coupling agent, a surfactant, a leveling agent, a rust inhibitor, and a polymerization inhibitor.

[0083] [Cured film] The cured film of the present invention can be obtained by curing the above-mentioned photosensitive resin composition. The cured film of the present invention may be used as a patterned cured film or a patternless cured film. The thickness of the cured film of the present invention is preferably 5 to 20 μm.

[0084] [Method of manufacturing patterned cured film] The method for producing a patterned cured film 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. This allows the patterned cured film to be obtained.

[0085] The method for producing a patternless cured film 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.

[0086] Examples of the substrate include a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), a metal oxide insulating substrate such as a TiO2 substrate or a SiO2 substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

[0087] The coating method is not particularly limited, but may be carried out using a spinner or the like.

[0088] 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 when component (D) is contained, the drying temperature is more preferably 90 to 120° C. in order to ensure dissolution contrast and to inhibit the reaction between components (A) and (D). 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.

[0089] The thickness of the photosensitive resin film is preferably from 5 to 100 μm, more preferably from 8 to 50 μm, and further preferably from 10 to 30 μm.

[0090] 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.

[0091] 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, either alone or in the form of a suitable mixture of a good solvent and a poor solvent. Examples of the good solvent include N-methylpyrrolidone, 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.

[0092] 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.

[0093] The development time can be set to, for example, twice the time it takes for the photosensitive resin film to be immersed and 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.

[0094] After development, washing may be carried out with a rinsing liquid. 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.

[0095] A patterned cured film can be obtained by heat treating the patterned resin film. The polyimide precursor of component (A) may undergo a dehydration ring-closing reaction in a heat treatment step to become the corresponding polyimide.

[0096] 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 150 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.

[0097] The heat treatment time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the time 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.

[0098] Examples of the apparatus 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.

[0099] [Interlayer insulating film, cover coat layer, surface protection film, electronic components] The cured film 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. By using one or more selected from the group consisting of the above passivation films, buffer coat films, interlayer insulating films, cover coat layers, surface protection films, etc., highly reliable electronic components such as semiconductor devices, multilayer wiring boards, and various electronic devices can be manufactured.

[0100] 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.

[0101] 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.

[0102] 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 removed using an etching solution that corrodes the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed through the window 6B.

[0103] 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.

[0104] 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 4 can also be formed using the photosensitive resin composition of the present invention. EXAMPLES

[0105] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0106] Synthesis Example 1 (Synthesis of Polymer I) 7.07g of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (ODPA) and 4.12g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 30g of NMP, stirred at 30°C for 4 hours, and then stirred at room temperature overnight to obtain polyamic acid. 9.45g of trifluoroacetic anhydride was added thereto under water cooling, stirred at 45°C for 3 hours, and 7.08g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as "Polymer I"). The number average molecular weight of Polymer I was determined using a GPC method in terms of standard polystyrene under the following conditions: The number average molecular weight of Polymer I was 40,000. The number average molecular weight was measured using 0.5 mg of polymer I in 1 mL of a solution of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF)=1 / 1 (volume ratio)].

[0107] Measurement equipment: Detector: Hitachi L4000UV Pump: Hitachi L6000 Data processor: Shimadzu Corporation C-R4A Chromatopac Column: Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF=1 / 1 (volume ratio) LiBr(0.03mol / L), H3PO4(0.06mol / L) Flow rate: 1.0mL / min Detector: UV270nm

[0108] The esterification rate of polymer I (the reaction rate of the carboxyl groups of ODPA with HEMA) was calculated by NMR measurement under the following conditions: The esterification rate was 80 mol% based on the total carboxyl groups and total carboxy esters (the remaining 20 mol% was carboxyl groups). Measurement equipment: Bruker Biospin AV400M Magnetic field strength: 400MHz Reference material: Tetramethylsilane (TMS) Solvent: dimethyl sulfoxide (DMSO)

[0109] The components used in the examples and comparative examples are as follows.

[0110] (Component (A): Polyimide precursor having a polymerizable unsaturated bond) Polymer I: Polymer I obtained in Synthesis Example 1

[0111] (Component (B): one or more of the compounds represented by formulas (1) to (4)) B1: N-formylmorpholine B2: Propylene carbonate B3: 3-Methoxy-N,N-dimethylpropionamide B4: 1,3-Dimethyl-2-imidazolidinone ((B') component) B5: γ-butyrolactone B6:NMP The component (B') means a component different from the component (B) used in the present invention. [ka]

[0112] (Component (C): Photopolymerization initiator) C1: "IRGACURE OXE 02" (manufactured by BASF Japan Ltd., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), a compound represented by the following formula) [ka] C2: "PDO" (1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, manufactured by Lambson, a compound represented by the following formula) [ka] C3: NCI-930 (manufactured by ADEKA Corporation, O-acyloxime compound, compound represented by the following formula) [ka]

[0113] (Component (D): Crosslinking agent) D1: "A-DCP" (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula) [ka] D2: CYMEL 300 (manufactured by Allnex, a compound represented by the following formula) [ka]

[0114] (Component (E): Thermal polymerization initiator) E1: Percumyl D (manufactured by Nippon Oil & Fats Co., Ltd., bis(1-phenyl-1-methylethyl) peroxide, a compound represented by the following formula) [ka]

[0115] Examples 1 to 3 and Comparative Example 1 [Preparation of photosensitive resin composition] Photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 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).

[0116] [Sensitivity evaluation] The obtained photosensitive resin composition was spin-coated on a silicon wafer using a coating device "Act8" (Tokyo Electron Ltd.), dried at 100°C for 2 minutes, and then dried at 110°C for 2 minutes to form a photosensitive resin film with a dry thickness of 13 μm. The developing time was set to twice the time it took for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved. A photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was irradiated with 100 to 600 mJ / cm using an i-line stepper "FPA-3000iW" (Canon Inc.). 2 of i-line, 50mJ / cm 2 The exposure was performed by irradiating a predetermined pattern with a stepwise dose. The exposed resin film was paddle-developed with cyclopentanone using "Act8" for the above-mentioned development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film. The thickness of the resulting patterned resin film was divided by the thickness of the photosensitive resin film before exposure to calculate the remaining film ratio as a percentage. The exposure amount capable of forming a patterned resin film with a remaining film ratio of 80% or more was evaluated as the sensitivity.

[0117] [Table 1]

[0118] Examples 4 and 5 and Comparative Example 2 [Preparation of photosensitive resin composition] Photosensitive resin compositions were prepared and evaluated in the same manner as in Example 1, except that the amount of crosslinking agent (component (D)) was changed to 25 parts by mass per 100 parts by mass of component (A), and the type and amount of component (B) or (B') was changed as shown in Table 2. The results are shown in Table 2.

[0119] [Table 2]

[0120] From Tables 1 and 2, it can be seen that the photosensitive resin composition of the present invention using a specific component (B) can produce a pattern with good sensitivity even at a low exposure dose. Moreover, from Examples 4 and 5, it can be seen that the effect of improving sensitivity can be obtained even at a small content of component (B).

[0121] Examples 6 and 7 [Preparation of photosensitive resin composition and evaluation of sensitivity] Photosensitive resin compositions of Examples 6 and 7 were prepared using the components and amounts shown in Table 3. The amounts shown in Table 3 are parts by mass of each component relative to 100 parts by mass of component (A). Using the obtained photosensitive resin composition, a patterned resin film was obtained in the same manner as in Examples 1 to 3 and Comparative Example 1. The obtained patterned resin film was evaluated in the same manner as in Examples 1 to 3 and Comparative Example 1. The sensitivity is shown in Table 3.

[0122] [Production of cured film] The above-mentioned patterned resin film was heated in a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere at 200° C. for 1 hour to obtain a patterned cured product (film thickness after curing: 10 μm).

[0123] [Evaluation of the appearance of the cured film] The appearance of the above-mentioned patterned cured product was visually evaluated in a 5 cm square area at the center of the wafer. Compared to the above-mentioned patterned resin film, those that did not change or had less than 30 bubbles were rated as A. Those that had 30 or more bubbles were rated as B. The results are shown in Table 3.

[0124] [Evaluation of mechanical properties] The obtained patterned cured product was immersed in a 4.9 mass % aqueous solution of hydrofluoric acid, and a 10 mm wide cured product was peeled off from the wafer. A tensile test was carried out on the peeled cured product with a width of 10 mm using an autograph AGS-X 100 N (manufactured by Shimadzu Corporation). The chuck distance was 20 mm, the tensile speed was 5 mm / min, and the measurement temperature was 18 to 25°C. The measurement was carried out three times for each cured product of each example, and the average value was calculated. If the average value was 30% or more, it was rated as A, and if it was less than 30%, it was rated as B. The results are shown in Table 3.

[0125] [Table 3] [Industrial Applicability]

[0126] 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.

Claims

1. (A) a polyimide precursor having a polymerizable unsaturated bond; (B) a compound represented by the following formula (3), (C) a photopolymerization initiator represented by the following formula (13), and A photopolymerization initiator represented by the following formula (18), (D) one or more crosslinking agents selected from the group consisting of diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and tricyclodecane dimethanol diacrylate; A photosensitive resin composition comprising: 【Chemistry 1】 (In formula (3), R ３ R to R5 are each independently an alkyl group having 1 to 4 carbon atoms. 【Chemistry 2】 In formula (13), R 61 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R 62 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group. R 65 is an alkyl group having 1 to 6 carbon atoms. R 66 is an alkyl group having 1 to 12 carbon atoms or an organic group having an acetal bond. i is an integer of 1 to 3. 【Chemistry 3】

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 (21): 【Chemistry 4】 (In formula (21), X １ is a group represented by the following formula (28). １ R is a group represented by the following formula (23). ２１ and R ２２ are each independently a hydrogen atom, a group represented by the following formula (22) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R ２１ and R ２２ At least one of the groups is a group represented by the following formula (22): ２１ The -COOR group and the -CO- group are in the ortho position relative to each other. ２２ The -CONH- group and the -CONH- group are in the ortho position relative to each other. 【Chemistry 5】 (In formula (28), Z 3 is an ether bond (—O—) or a sulfide bond (—S—).) 【Chemistry 6】 (In formula (23), R 31 and R to R are hydrogen atoms. R 32 and R 33 are each independently a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.) 【Chemistry 7】 (In formula (22), R ２３ ~R ２５ 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 2, wherein Z 3 is an ether bond (—O—), and R 32 and R 33 are methyl groups.

4. 4. The photosensitive resin composition according to claim 1, wherein the component (B) is contained in an amount of 10 to 10,000 parts by mass per 100 parts by mass of the component (A).

5. A photosensitive resin composition described in any one of claims 1 to 4, wherein the (D) component is one or more crosslinking agents selected from the group consisting of triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tricyclodecane dimethanol diacrylate.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising (E) a thermal polymerization initiator.

7. A step of applying the photosensitive resin composition according to any one of claims 1 to 6 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; a step of heat treating the patterned resin film; A method for producing a patterned cured film comprising the steps of:

8. The method for producing a patterned cured film according to claim 7, wherein the heat treatment is performed at a temperature of 200°C or less.

9. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6.

10. The cured film according to claim 9, which is a patterned cured film.

11. An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured film according to claim 9 or 10.

12. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to claim 11.

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