WO2020071437A1

WO2020071437A1 - Photosensitive resin composition, method for manufacturing pattern-cured product, cured product, interlayer insulation film, cover coat layer, surface protection film, and electronic component

Info

Publication number: WO2020071437A1
Application number: PCT/JP2019/038959
Authority: WO
Inventors: 米田　聡; 皓朝田; 和也副島; 則孝松家; 榎本　哲也
Original assignee: 日立化成デュポンマイクロシステムズ株式会社
Priority date: 2018-10-03
Filing date: 2019-10-02
Publication date: 2020-04-09
Also published as: TWI816900B; JPWO2020071437A1; KR20210068418A; TW202028863A; JP7405088B2; CN113168092A

Abstract

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

Description

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

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

Conventionally, a polyimide or polybenzoxazole having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. In recent years, photosensitive resin compositions in which photosensitive properties are imparted to these resins themselves have been used, and the use of such resins can simplify the manufacturing process of a pattern cured product and shorten the complicated manufacturing process (for example, see Patent Document 1).

By the way, in recent years, miniaturization of transistors, which has supported high performance of computers, has reached a limit of a scaling law, and a stacked device structure in which semiconductor elements are three-dimensionally stacked for further higher performance and higher speed. Is attracting attention.

Among the stacked device structures, a multi-die fan-out wafer-level package (Multi-die Fanout Wafer Level Packaging) is a package that collectively seals a plurality of dies in one package, and has been conventionally proposed. It has attracted a great deal of attention because it can be expected to have lower cost and higher performance than conventional fan-out wafer level packages (where one die is encapsulated in one package).

In the production of a multi-die fan-out wafer-level package, low-temperature curability is strongly required from the viewpoint of protecting a high-performance die and protecting a sealing material having low heat resistance and improving yield (for example, see Patents). Reference 2).

Further, as a resin composition, a resin composition containing a polyimide precursor is disclosed (for example, see Patent Document 3).

JP 2009-265520 A International Publication No. WO 2008/111470 JP 2016-199662 A

An object of the present invention is to provide a photosensitive resin composition having excellent storage stability, which can form a cured product having excellent mechanical properties even at a low temperature curing of 230 ° C. or lower, a method for producing a pattern cured product, a cured product, and an interlayer. An object of the present invention is to provide an insulating film, a cover coat layer, a surface protective film, and an electronic component.

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) a polymerizable monomer,
(C) a photopolymerization initiator,
A photosensitive resin composition containing (D) a cyclization catalyst and (E) a solvent.
2. 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).

(In the formula (1), X ₁ is a tetravalent group having one or more aromatic groups, and the —COOR ₁ group and the —CONH— group are located at ortho positions to each other, and the —COOR ₂ group and the —CO And the groups are at ortho positions to each other, Y ₁ is a divalent aromatic group, R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the following formula (2), or a carbon number (1-4) wherein at least one of R ₁ and R ₂ is a group represented by the formula (2).)

(In the formula (2), R ₃ to 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. The component (D) comprises N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N, N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2 ′-(4-methyl 3. The photosensitive resin composition according to 1 or 2, which is at least one selected from the group consisting of (phenylimino) diethanol.
4. The photosensitive resin composition according to 1 or 2, wherein the component (D) contains a compound represented by the following formula (17).

(In the formula (17), R _31A to R _33A each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group. And at least one of R _31A to R _33A is a monovalent aromatic group. R _31A to R _33A may form a ring with adjacent groups.
5. 5. The photosensitive resin composition according to any one of 1 to 4, wherein the component (C) includes (C1) a compound represented by the following formula (15) and (C2) a compound represented by the following formula (16).

(In the formula (15), R _11A is an alkyl group having 1 to 12 carbon atoms, a1 is an integer of 0 to 5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A And R _14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, and when a1 is an integer of 2 or more, R _11A may be the same or different. .)

(In the formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, and R _22A and R _23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms. A cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _21A may be the same or different. May be.)
6. 6. The photosensitive resin composition according to any one of 1 to 5, wherein the component (B) contains a polymerizable monomer having an aliphatic cyclic skeleton.
7. 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (B) has a group containing a polymerizable unsaturated double bond.
8. 8. The photosensitive resin composition according to 7, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds.
9. 8. The photosensitive resin composition according to any one of 1 to 7, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

(In the 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). N1 is 0 or 1 , N2 is an integer of 0 to 2, and n1 + n2 is 1 or more. At least one of n1 R ₆ and n2 R ₇ is a group represented by the following formula (4).)

(In the formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer of 0 to 10.)
10. 10. The photosensitive resin composition according to 9, wherein n1 + n2 is 2 or 3.
11. 11. The photosensitive resin composition according to any one of 1 to 10, wherein the component (B) contains a polymerizable monomer represented by the following formula (5).

12. 12. The photosensitive resin composition according to any one of 1 to 11, further comprising (F) a thermal polymerization initiator.
13. 13. The photosensitive resin composition according to any one of 1 to 12, further comprising an antioxidant.
14. a step of applying the photosensitive resin composition according to any one of 1 to 13 on a substrate and drying to form a photosensitive resin film;
Pattern-exposing the photosensitive resin film to obtain a resin film;
A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film,
Heat treating the pattern resin film.
15. 15. The method for producing a cured pattern according to 14, wherein the temperature of the heat treatment is 230 ° C. or lower.
16. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 13.
17． 17. The cured product according to 16, which is a pattern cured product.
18. An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured product according to 16 or 17.
19. An electronic component comprising the interlayer insulating film, the cover coat layer, or the surface protective film according to 19.18.

According to the present invention, even when cured at a low temperature of 230 ° C. or lower, a photosensitive resin composition having excellent storage stability that can form a cured product having excellent mechanical properties, a method for producing a pattern cured product, a cured product, and an interlayer An insulating film, a cover coat layer, a surface protective film, and an electronic component can be provided.

It is a manufacturing process figure of an electronic component concerning one embodiment of the present invention.

Hereinafter, embodiments of the photosensitive resin composition of the present invention, a method of manufacturing a cured pattern using the same, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component will be described in detail. The present invention is not limited by the following embodiments.

In the present specification, “A or B” may include either one of A and B, and may include both. In this specification, the term “step” is used not only for an independent step but also for the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. included.
The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, in the present specification, the content of each component in the composition, if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total of the plurality of substances present in the composition Means quantity. Further, the exemplified materials may be used alone or in combination of two or more unless otherwise specified.
The “(meth) acryl group” in the present specification means “acryl group” and “methacryl group”.

The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as “component (A)”), (B) a polymerizable monomer (also referred to as “crosslinking agent”). (Hereinafter also referred to as “(B) component”), (C) a photopolymerization initiator (hereinafter also referred to as “(C) component”), and (D) a cyclization catalyst (hereinafter “(D) component). ) Component), and (E) a solvent (hereinafter, also referred to as “component (E)”).

Thus, a cured product having excellent mechanical properties can be formed even at a low temperature of 230 ° C. or lower.
Further, storage stability can be improved.
As an optional effect, a cured product having an excellent cyclization rate can be formed even at a low temperature of 230 ° C. or lower.
As an optional effect, the sensitivity can be improved.

感光 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 components.

The component (A) is not particularly limited, but is preferably a polyimide precursor which has a high transmittance when i-line is used as a light source at the time of patterning and shows high cured product properties even at a low temperature of 230 ° C or lower.

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

The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). Thereby, the transmittance of i-line is high, and a favorable cured product can be formed even at the time of low-temperature curing of 230 ° C. or less.
The content of the structural unit represented by the formula (1) is preferably at least 50 mol%, more preferably at least 80 mol%, and preferably at least 90 mol%, based on all the constituent units of the component (A). More preferred. The upper limit is not particularly limited, and may be 100 mol%.

(In the formula (2), R ₃ to 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 (preferably an integer of 2 to 5) , More preferably 2 or 3).

In the tetravalent group having an aromatic group of one or more (preferably 1 to 3, more preferably 1 or 2) of X _{1 in} the formula (1), the aromatic group may be an aromatic hydrocarbon group, It may be a group heterocyclic group. Aromatic hydrocarbon groups are preferred.

Examples of the aromatic hydrocarbon group represented by X _{1 in} the formula (1) include a divalent to tetravalent (divalent, trivalent, or tetravalent) group formed from a benzene ring, and a divalent to tetravalent group formed from naphthalene. And divalent to tetravalent groups formed from perylene.

Examples of the tetravalent group having one or more aromatic groups represented by X _{1 in} the formula (1) include, but are not limited to, a tetravalent group represented by the following formula (6).

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

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

The divalent aromatic group of Y _{1 in} the formula (1) may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. Divalent aromatic hydrocarbon groups are preferred.

Examples of the divalent aromatic hydrocarbon group represented by Y _{1 in} the formula (1) include, but are not limited to, a group represented by the following formula (7).

(In the formula (7), R ₁₂ to R ₁₉ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent organic group having a halogen atom.)

Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) represented by R ₁₂ to R _{19 in} the formula (7) include a methyl group. For example, R ₁₂ and R ₁₅ to R ₁₉ may be a hydrogen atom, and R ₁₃ and R ₁₄ may be a monovalent aliphatic hydrocarbon group.

The monovalent organic group having a halogen atom (preferably a fluorine atom) represented by R ₁₂ to R _{19 in} the formula (7) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, It preferably has 1 to 6 carbon atoms, and examples thereof include a trifluoromethyl group.

Examples of the aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms for R ₁ and R _{2 in} the formula (1) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n- Butyl group and the like.

At least one of R ₁ and R _{2 in} the formula (1) is a group represented by the formula (2), and both are preferably groups represented by the formula (2).

Examples of the aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms represented by R ₃ to R _{5 in} the formula (2) include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. Can be A methyl group is preferred.

The polyimide precursor having the structural unit represented by the formula (1) is, for example, a tetracarboxylic dianhydride represented by the following formula (8) and a diamino compound represented by the following formula (9): By reacting in an organic solvent such as -methyl-2-pyrrolidone to obtain a polyamic acid, adding a compound represented by the following formula (10), and reacting in an organic solvent to partially introduce an ester group. Obtainable.
The tetracarboxylic dianhydride represented by the formula (8) and the diamino compound represented by the formula (9) may be used alone or in a combination of two or more.

(In the formula (8), _{X 1} is a group corresponding to _{X 1} of the formula (1).)

(In the formula (9), Y ₁ is as defined in the formula (1).)

(In the formula (10), R is a group represented by the above formula (2).)

The component (A) may have a structural unit other than the structural unit represented by the formula (1).
Examples of the structural unit other than the structural unit represented by Formula (1) include a structural unit represented by Formula (11).

(In the formula (11), X ₂ is a tetravalent group having one or more aromatic groups, -COOR ₅₁ group and -CONH- group are at ortho positions to each other, -COOR ₅₂ group and -COOR Y ₂ is a divalent aromatic group, and R ₅₁ and R ₅₂ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. )

Examples of the tetravalent group having one or more aromatic groups of X _{2 in} the formula (11) include the same as the tetravalent group having one or more aromatic groups of X _{1 in} the formula (1).
Examples of the divalent aromatic group of Y _{2 in} the formula (11) include the same as the divalent aromatic group of Y _{1 in} the formula (1).
Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R ₅₁ and R _{52 in} the formula (11) include the same as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms represented by R ₁ and R ₂ .

は The structural unit other than the structural unit represented by the formula (1) may be used alone or in combination of two or more.

含有 The content of the structural unit other than the structural unit represented by the formula (1) is preferably less than 50 mol% with respect to all the constituent units of the component (A).

In the component (A), the ratio of the carboxy group esterified with the group represented by the formula (2) to all carboxy groups and all carboxy esters is preferably 50 mol% or more, and 60 to 100 mol%. Mol% is more preferable, and 70 to 90 mol% is still more preferable.

The molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in number average molecular weight.
The number average molecular weight can be measured, for example, by a gel permeation chromatography method, and can be determined by conversion using a standard polystyrene calibration curve.

The component (B) may have a group (preferably two or more) containing a polymerizable unsaturated double bond (preferably, a (meth) acryl group because it can be polymerized by a photopolymerization initiator). preferable. The component (B) is preferably a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds. In order to improve the crosslink density and photosensitivity and to suppress the swelling of the pattern after development, it is preferable to have a few groups containing a polymerizable unsaturated double bond.

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

The component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton (preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms). As a result, hydrophobicity can be imparted to the cured product that can be formed, and a decrease in adhesion between the cured product and the substrate under high-temperature and high-humidity conditions can be suppressed.

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

(In the 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). 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 (preferably 2 or 3) of n1 R ₆ and n2 R ₇ is It is a group represented by the formula (4).)

When there are two R ₇ , the two R ₇ may be the same or different.

(In the formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer of 0 to 10 (preferably 0, 1 or 2 ).)

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

Further, as the component (B), for example, the following polymerizable monomers may be used.

In the formula (12), R ₂₁ to 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).

When two or more R ₂₁ are present, two or more R ₂₁ may be the same or different.
When two or more R ₂₂ are present, two or more R ₂₂ may be the same or different.

At least one (preferably 2 or 3) of the n3 R ₂₁ is a group represented by the above formula (4).
At least one (preferably 2 or 3) of the n4 R ₂₂ is a group represented by the above formula (4).
n5 or at least one of _{R 23} and n6 amino _{R 24} (preferably 2) is a group represented by the above formula (4).

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R ₆ and R _{7 in} the formula (3) and R ₂₁ to R _{24 in} the formula (12) include a carbon atom having 1 carbon atom represented by R ₁ and R _{2 in} the formula (1). And the same as the aliphatic hydrocarbon groups (1) to (4).

The aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by R ₉ to R _{11 in} the formula (4) is the same as the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by R ₃ to R _{5 in} the formula (2). Things.

(B) component may contain a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton. As a result, a cured product having good mechanical properties can be obtained.

Examples of the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethyl Methylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate Pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid Triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, ethylene oxide (EO) -modified bisphenol A diacrylate (for example, FA324A (manufactured by Hitachi Chemical Co., Ltd.) as a commercial product) and the like. Can be

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

The component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton from the viewpoint of obtaining good mechanical properties and photosensitive properties.
When a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton are contained, the content of the polymerizable monomer having an aliphatic cyclic skeleton is set to 100 parts by mass of the component (A). On the other hand, 1 to 40 parts by mass is preferable. From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 5 to 35 parts by mass. The content of the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton is preferably from 1 to 20 parts by mass based on 100 parts by mass of the component (A). From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 5 to 15 parts by mass.

The content of the component (B) is preferably 1 to 50 parts by mass based on 100 parts by mass of the component (A). From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 3 to 50 parts by mass, and still more preferably 5 to 40 parts by mass.
When the content is within the above range, a practical relief pattern is easily obtained, and residues after development of the unexposed portions are easily suppressed.

Examples of the component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, and fluorenone;
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenyl ketone;
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone;
Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal,
Benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione -2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl]-, 1- (O-acetyloxime) and compounds represented by the following formulas: Preferable examples include, but are not limited to, oxime esters.

オキシ Especially, oxime esters are preferred in terms of photosensitivity.

The component (C) preferably contains (C1) a compound represented by the following formula (15) (hereinafter, also referred to as “(C1) component”).
The component (C1) preferably has a higher sensitivity to actinic rays than the component (C2) described below, and is preferably a highly sensitive photosensitizer.

In the formula (15), R _11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A and R _14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 (preferably 1 to 4) carbon atoms, a phenyl group or a tolyl group. When a1 is an integer of 2 or more, R _11A may be the same or different.

R _11A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1. R _12A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. R _13A and R _14A are preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

The compound represented by the formula (15) includes, for example, a compound represented by the following formula (15A), and is available as “IRGACURE OXE 02” manufactured by BASF Japan Ltd.

The component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter, also referred to as “(C2) component”).
The component (C2) preferably has lower sensitivity to actinic rays than the component (C1), and is preferably a photosensitive agent having a standard sensitivity.

In the formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, and R _22A and R _23A are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms). An alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _21A may be the same or different.

c1 is preferably 0. R _22A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. R _23A is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, even more preferably a methoxy group or an ethoxy group.

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

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

The component (C) preferably contains at least one selected from the group consisting of the component (C1) and the component (C2).
Further, the component (C) preferably contains the component (C1) and the component (C2).

The content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the component (A). 5 parts by mass.
When it is in the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern is easily obtained.

When the component (C1) is contained, the content of the component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.07 to 2.0 parts by mass, per 100 parts by mass of the component (A). The amount is 5 parts by mass, more preferably 0.09 to 1.0 part by mass.

When the component (C2) is contained, the content of the component (C2) is usually from 0.5 to 15.0 parts by mass, preferably from 1.0 to 15.0 parts by mass, per 100 parts by mass of the component (A). 0 parts by mass.

When the component (C1) and the component (C2) are contained, the content of the component (C1) is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the component (A), and the component (C2) Is preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the component (A).

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

The photosensitive resin composition of the present invention contains (D) a cyclization catalyst.
The component (D) includes 2- (methylphenylamino) ethanol, 2- (ethylanilino) ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N, N-dimethylaniline, N-phenylethanolamine, It is preferably at least one selected from the group consisting of 4-phenylmorpholine and 2,2 '-(4-methylphenylimino) diethanol, and N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, , N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2 '-(4-methylphenylimino) diethanol are more preferably at least one selected from the group consisting of:

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

(In the formula (17), R _31A to R _33A each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group. , and _the at least one (preferably one) monovalent aromatic group _.R 31A _{~ R 33A} ring adjacent groups (e.g., substituents (e.g., methyl group R 31A _{~ R 33A} , A phenyl group) may be formed.)

Preferably, at least one of R _31A to R _33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group.

Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) represented by R _31A to R _{33A in} the formula (17) include a methyl group and an ethyl group.
As the monovalent aliphatic hydrocarbon group having a hydroxy group represented by R _31A to R _{33A in} the formula (17), one or more (preferably 1 to 3) is _added to the monovalent aliphatic hydrocarbon group represented by R _31A to R _33A. And the like. Specific examples include a methylol group and a hydroxyethyl group. Hydroxyethyl groups are preferred.

The monovalent aromatic group represented by R _31A to R _{33A in} the formula (17) may be a monovalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms). It may be a valent aromatic heterocyclic group. Monovalent aromatic hydrocarbon groups are preferred.
Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The monovalent aromatic groups of R _31A to R _{33A in} the formula (17) may have a substituent. The substituent, a monovalent aliphatic having hydroxy group _R 31A _{~ R 33A} monovalent aliphatic hydrocarbon group _R 31A _{~ R 33A} of the aforementioned formula (17), and the above equation (17) The same thing as a hydrocarbon group is mentioned.

As the component (D), one type may be used alone, or two or more types may be used in combination.
The content of the component (D) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of improving the imidation ratio and sensitivity. From the viewpoint of storage stability, the amount is more preferably 0.3 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass.

The photosensitive resin composition of the present invention contains (E) a solvent.
The component (E) includes 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, N-dimethyl morpholine and the like. Generally, there is no particular limitation as long as it can sufficiently dissolve other components.
Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N, N-dimethylformamide are preferred from the viewpoint of excellent solubility of each component and coatability in forming a photosensitive resin film. , N, N-Dimethylacetamide is preferably used.

Further, as the component (E), a compound represented by the following formula (21) may be used.

(In the formula, R ₄₁ to R ₄₃ are each independently an alkyl group having 1 to 10 carbon atoms.)

In formula (21), _examples of the alkyl group having 1 to 10 (preferably 1 to 3, more preferably 1 or 3) carbon atoms of R ₄₁ to R ₄₃ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and the like.
The compound represented by the formula (21) is preferably 3-methoxy-N, N-dimethylpropanamide (for example, trade name “KJCMPA-100” (manufactured by KJ Chemicals Corporation)).

As the component (E), one type may be used alone, or two or more types may be used in combination.
The content of the component (E) is not particularly limited, but is generally 50 to 1000 parts by mass based on 100 parts by mass of the component (A).

The photosensitive resin composition of the present invention may further contain (F) a thermal polymerization initiator (hereinafter, also referred to as “component (F)”) from the viewpoint of accelerating the polymerization reaction.
The component (F) is not decomposed by heating (drying) for removing a solvent during film formation, but is decomposed by heating at the time of curing to generate radicals. Compounds that promote the polymerization reaction of component (B) are preferred.
The component (F) is preferably a compound having a decomposition point of 110 ° C to 200 ° C, and more preferably a compound having a decomposition point of 110 ° C to 175 ° C from the viewpoint of accelerating the polymerization reaction at a lower temperature.

Specific examples include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, Peroxy ketals such as 1-di (t-butylperoxy) cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, dicumyl peroxide Dialkyl peroxides such as -t-butyl peroxide and the like, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbon Peroxydicarbonate such as tert-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy Peroxyesters such as -2-ethylhexanoate; and bis (1-phenyl-1-methylethyl) peroxide. Examples of commercially available products include “Park Mill D”, “Park Mill P”, and “Park Mill H” (all manufactured by NOF CORPORATION).

When the component (F) is contained, the content of the component (F) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), and is 0 to ensure good flux resistance. From 2 to 20 parts by mass, more preferably from 0.3 to 10 parts by mass, from the viewpoint of suppressing the decrease in solubility due to decomposition during drying.

感光 The photosensitive resin composition of the present invention may further contain an antioxidant. By containing an antioxidant, oxygen radicals and peroxide radicals generated during high-temperature storage or reflow treatment can be supplemented, and a decrease in adhesion (adhesion) can be further suppressed. Further, oxidation of the electrode during the insulation reliability test can be suppressed, and diffusion from the electrode to the resin film or the pattern resin film can be suppressed.

Examples of antioxidants include N, N'-bis [2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy] ethyl] oxamide, N, N'-bis-3 -(3,5-di-tert-butyl-4'-hydroxyphenyl) propionylhexamethylenediamine, 1,3,5-tris (3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) -1 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione,
2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3- Methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), isooctyl -3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,3 5-triazine-2,4,6- (1H, 3H, 5H) -trione, 2,2′-methylene-bis (4-methyl-6-t-butylphenol), 2,2′-methylene-bis (4 -Ethyl-6-t-butylphenol),
Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione, 1,3,5-tris [4- (1-ethylpro 1) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t -Butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl -3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,
Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate], 1,3,5-tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6- ( 1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4 , 6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5 ) -Trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -Trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,
1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, And 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.

は The antioxidant may be used alone or in combination of two or more.

When an antioxidant is contained, the content of the antioxidant is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the component (A). Preferably it is 0.1 to 5 parts by mass.

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

Normally, the coupling agent reacts with the component (A) in the heat treatment after development to crosslink, or the coupling agent itself is polymerized in the heat treatment step. Thereby, the adhesiveness between the obtained cured product and the substrate can be further improved.

Preferred silane coupling agents include compounds having a urea bond (—NH—CO—NH—). Thereby, even when curing is performed at a low temperature of 230 ° C. or lower, the adhesiveness to the substrate can be further improved.
The compound represented by the following formula (13) is more preferable because it exhibits excellent adhesion when cured at a low temperature.

(In the 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.)

Specific examples of the compound represented by the formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. And 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, with 3-ureidopropyltriethoxysilane being preferred.

As the silane coupling agent, a silane coupling agent having a hydroxy group or a glycidyl group may be used. When a silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having a urea bond in a molecule are used in combination, it is possible to further improve the adhesion of a cured product to a substrate during low-temperature curing.
Examples of the silane coupling agent having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, and tert-silane. Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol, Sobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, 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 (dipropyl hydroxy silyl) benzene, 1,4-bis (dibutyl hydroxy silyl) benzene, and compounds represented by the following formula (14) below. Among them, a compound represented by the formula (14) is particularly preferable in order to further improve the adhesiveness to the substrate.

(In the formula (14), R ₃₃ is a monovalent organic group having a hydroxy group or a glycidyl group, and R ₃₄ and R ₃₅ are each independently an alkyl group having 1 to 5 carbon atoms. An integer of 10 and d is an integer of 1 to 3.)

Examples of the compound represented by the formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyl Triethoxysilane, and the like.

The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a group having a nitrogen atom, and more preferably a silane coupling agent having an amino group or an amide bond.
Examples of the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-glycidyl) (Xymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane and the like.

Further, as a silane coupling agent having an amide bond, R ₃₆ — (CH ₂ ) _e —CO—NH— (CH ₂ ) _f —Si (OR ₃₇ ) ₃ (R ₃₆ is a hydroxy group or a glycidyl group; And f are each independently an integer of 1 to 3, and R ₃₇ is a methyl group, an ethyl group or a propyl group).

The silane coupling agent may be used alone or in combination of two or more.

When a silane coupling agent is used, the content of the silane coupling agent is preferably from 0.1 to 20 parts by mass, more preferably from 0.3 to 10 parts by mass, based on 100 parts by mass of the component (A). -10 parts by mass is more preferred.

塗布 By containing a surfactant or a leveling agent, applicability (for example, suppression of striation (unevenness of film thickness)) and developability can be improved.

Examples of the surfactant or the leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and the like. "," F173 "," R-08 "(manufactured by DIC Corporation), trade names" Florado FC430 "," FC431 "(manufactured by Sumitomo 3M Limited), trade names" organosiloxane polymer KP341 "," KBM303 "," KBM403 "," KBM803 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

は The surfactant and the leveling agent may be used alone or in a combination of two or more.

When a surfactant or a leveling agent is contained, the content of the surfactant or the leveling agent is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, per 100 parts by mass of the component (A). Preferably, the amount is 0.05 to 3 parts by mass.

By including a rust inhibitor, corrosion of copper and copper alloy can be suppressed and discoloration can be prevented.
Examples of the rust inhibitor include a triazole derivative and a tetrazole derivative.
The rust inhibitor may be used alone or in combination of two or more.

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 more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (A). 3 parts by mass is more preferred.

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 inhibitor.

Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2-ene. Examples include naphthylamine, cuperon, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like.

The polymerization inhibitor may be used alone or in combination of two or more.

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is preferably 0 to 100 parts by mass of the component (A) from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the obtained cured product. 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.05 to 5 parts by mass.

The photosensitive resin composition of the present invention essentially comprises the components (A) to (E) and optionally the component (F), a coupling agent, a surfactant, a leveling agent, a rust inhibitor and a polymerization inhibitor. 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,
(A) to (E) components,
(A)-(F) component, or (A)-(E) component, and optionally, (F) component, coupling agent, surfactant, leveling agent, rust inhibitor and polymerization inhibitor. Good.

The cured product of the present invention can be obtained by curing the above-described photosensitive resin composition.
The cured product of the present invention may be used as a pattern cured product or a cured product without a pattern.
The thickness of the cured product of the present invention is preferably 5 to 20 μm.

In the method for producing a cured pattern product of the present invention, a step of applying the above-described photosensitive resin composition on a substrate and drying to form a photosensitive resin film, and pattern-exposing the photosensitive resin film to form a resin film The method includes a step of obtaining, a step of developing the resin film after pattern exposure using an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film.
Thereby, a cured pattern can be obtained.

方法 A method for producing a cured product having no pattern includes, for example, a step of forming the above-described photosensitive resin film and a step of performing heat treatment. Further, a step of exposing may be provided.

Examples of the substrate include a semiconductor substrate such as a glass substrate and a Si substrate (silicon wafer), a metal oxide insulator substrate such as a TiO ₂ substrate and a SiO ₂ substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

The coating method is not particularly limited, but can be performed using a spinner or the like.

Drying can be performed using a hot plate, an oven, or the like.
The drying temperature is preferably from 90 to 150 ° C., and more preferably from 90 to 120 ° C. from the viewpoint of ensuring the dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed two or more times.
Thereby, a photosensitive resin film in which the above-described photosensitive resin composition is formed in a film shape can be obtained.

(4) The thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 6 to 50 μm, and still more preferably 7 to 30 μm.

In the pattern exposure, for example, a predetermined pattern is exposed through a photomask.
The actinic rays to be irradiated include i-rays, ultraviolet rays such as broadband (BB), visible rays, and radiation, but i-rays are preferred.
As the exposure device, a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, or the like can be used.

By performing development, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, unexposed portions are removed with a developer.
As the organic solvent used as the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed.
Examples of the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, Cyclopentanone, cyclohexanone and the like can be mentioned.
Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

界面 A surfactant may be added to the developer. The addition amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the developer.

The development time can be, for example, twice as long as the time until the photosensitive resin film is immersed and completely dissolved.
The development time varies depending on the component (A) used, but is preferably from 10 seconds to 15 minutes, more preferably from 10 seconds to 5 minutes, and further preferably from 20 seconds to 5 minutes from the viewpoint of productivity.

After the development, washing may be performed with a rinsing solution.
As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or the like may be used alone or in a suitable mixture, or may be used in a stepwise combination. Good.

By subjecting the pattern resin film to a heat treatment, a cured pattern can be obtained.
The polyimide precursor of the component (A) undergoes a dehydration and ring closure reaction by the heat treatment step, and usually becomes a corresponding polyimide.

The temperature of the heat treatment is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and still more preferably 230 ° C. or lower or 180 to 230 ° C.
By being within the above range, damage to the substrate and the device can be suppressed small, the device can be produced with high yield, and energy saving in the process can be realized.

The time of the heat treatment is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
When the content is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can sufficiently proceed.
The atmosphere for the heat treatment may be the air or an inert atmosphere such as nitrogen, but is preferably under a nitrogen atmosphere from the viewpoint of preventing oxidation of the pattern resin film.

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

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 at least one selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protective film, and the like, a highly reliable semiconductor device, multilayer wiring board, various electronic devices, laminated Electronic components such as devices (such as a multi-die fan-out wafer level package) can be manufactured.

An example of a manufacturing process of a semiconductor device as an electronic component of the present invention will be described with reference to the drawings.
FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure as an electronic component according to an embodiment of the present invention.
In FIG. 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. It is formed. After that, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film 4, and a window 6A is formed by a known photolithography technique so that a predetermined portion of the interlayer insulating film 4 is exposed. Provided.

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

Further, the second conductor layer 7 is formed by using a known photolithography technique, and is electrically connected to the first conductor layer 3.
When a multilayer wiring structure of three or more layers is formed, each layer can be formed by repeating the above steps.

Next, a window 6C is opened by pattern exposure using the above-mentioned photosensitive resin composition, and a surface protective film 8 is formed. The surface protection film 8 protects the second conductor layer 7 from external stress, α-rays and the like, and the obtained semiconductor device has excellent reliability.
In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples. The present invention is not limited to the following examples.

Synthesis Example 1 (Synthesis of A1)
7.07 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were converted to N-methyl- It was dissolved in 30 g of 2-pyrrolidone (NMP) and stirred at 30 ° C. for 4 hours and then at room temperature overnight to obtain a polyamic acid. Under water cooling, 9.45 g of trifluoroacetic anhydride was added thereto, and the mixture was stirred at 45 ° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. The reaction solution was dropped into distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor A1.
The number average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene. The number average molecular weight of A1 was 40,000.

Measurement was performed using 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of A1.

Measuring device: detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm

Further, the esterification rate of A1 (reaction rate of the carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80 mol% based on the total carboxy groups of the polyamic acid (the remaining 20 mol% was carboxy groups).

Measuring equipment: Bruker BioSpin AV400M
Magnetic field strength: 400 MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

Examples 1 to 3 and Comparative Examples 1 to 5
(Preparation of photosensitive resin composition)
The photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared using the components and amounts shown in Table 1. The compounding amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of A1.

各 Each component used is as follows. As the component (A), A1 obtained in Synthesis Example 1 was used.

Component (B): polymerizable monomer B1: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula B1)

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

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

Component (C): photopolymerization initiator C1: IRUGCURE OXE 02 (manufactured by BASF Japan Co., Ltd., ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 -(O-acetyloxime))
C2: G-1820 (PDO) (1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, manufactured by Lambson Corporation)

Component (D): cyclization catalyst D1: 2HE (N-phenyldiethanolamine manufactured by Morin Chemical Industry Co., Ltd.)

(D ′) Component D2: U-CAT SA810 (manufactured by San Apro Co., Ltd., compound represented by the following formula D2)

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

D4: 4-hydroxypyridine

(E) component: solvent E1: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd., compound represented by the following formula E1)

Component (F): Thermal polymerization initiator F1: Parkmill D (manufactured by NOF CORPORATION, bis (1-phenyl-1-methylethyl) peroxide, a compound represented by the following formula F1)

(Evaluation of sensitivity)
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 105 ° C. for 120 seconds, and then dried at 115 ° C. for 120 seconds to form a dried film. A photosensitive resin film having a thickness of 13 μm was formed.
The development time was set to twice the time required for the obtained photosensitive resin film to be completely dissolved by immersion in cyclopentanone.
Further, a photosensitive resin film is prepared in the same manner as described above, and an i-line of 100 to 1100 mJ / cm ² is applied to the obtained photosensitive resin film using an i-line stepper FPA-3000iW (manufactured by Canon Inc.). Exposure was performed by irradiating a predetermined pattern at an irradiation amount of 100 mJ / cm ² .
The exposed resin film was developed into cyclopentanone using Act8 for the above development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

(4) The sensitivity was defined as the lower limit of the exposure amount at which the thickness of the obtained pattern resin film was 80% or more of the thickness of the photosensitive resin film before exposure. Table 1 shows the results.

(Manufacture of cured pattern 1)
The pattern resin film obtained by the evaluation of the sensitivity was heated at 200 ° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured pattern (film after curing). (Thickness: 10 μm).

(Manufacture of cured pattern 2)
The pattern resin film obtained in the evaluation of the sensitivity was heated at 400 ° C. for 1 hour in a vertical diffusion furnace μ-TF under a nitrogen atmosphere to obtain a cured pattern.

(Evaluation of cyclization rate)
The IR (infrared spectroscopy) spectrum of the pattern resin film obtained by the evaluation of the sensitivity was measured under the following conditions using FT-IR IRAfinity-1S (manufactured by Shimadzu Corporation). This value is referred to as IR1.
The IR spectrum was measured by a transmission method with a measurement range of 400 to 4000 cm ⁻¹ and an accumulation count of 16 times.
The measurement of the IR spectrum used a silicon wafer as a substrate. First, the substrate on which the photosensitive resin composition was not applied was measured and used as a background. Next, measurement was performed on the resin film portion of the pattern resin film using the above background, and an IR spectrum was obtained.

The IR of the cured pattern obtained in Production 1 of the cured pattern was measured in the same manner as described above. This value is set to IR2.
The IR of the cured pattern obtained in Production 2 of the cured pattern was measured in the same manner as described above. This value is referred to as IR3.

環 The cyclization rate was determined by dividing the value obtained by subtracting IR1 from IR2 by the value obtained by subtracting IR1 from IR3 to obtain a percentage. A was 65% or more, and B was less than 65%. Table 1 shows the results.

(Evaluation of storage stability)
The above-mentioned photosensitive resin composition was spin-coated on a Si substrate at a rotation speed at which the film thickness after drying became 13 μm within 24 hours after preparation, and on a hot plate at 105 ° C. for 120 seconds at 115 ° C. For 120 seconds to form a photosensitive resin film. The silicon wafer was exposed by scribing a part of the film, and the height from the exposed silicon wafer surface to the film surface was measured using a needle-type profiler Dektak 150 (manufactured by Bruker). The same applies to the above, and the same applies to the following). This is referred to as film thickness 1.
After the above photosensitive resin composition was adjusted, it was allowed to stand at room temperature (25 ° C.) for 14 days. After standing, spin coating was performed on the Si substrate at the same rotation speed as when the photosensitive resin film for measuring the film thickness 1 was formed, and heated on a hot plate at 105 ° C. for 120 seconds and at 115 ° C. for 120 seconds. After drying, a photosensitive resin film was formed. The film thickness was measured as described above. This is referred to as film thickness 2.
The case where the absolute value obtained by subtracting the film thickness 1 from the film thickness 2 was divided by the film thickness 1 and the percentage value was 5% or less was defined as A. The case of exceeding 5% was designated as B. Table 1 shows the results.

(Production of cured pattern 3)
The above-described photosensitive resin composition is spin-coated on a Si substrate, and heated and dried on a hot plate at 105 ° C. for 120 seconds and at 115 ° C. for 120 seconds to form a photosensitive resin film of 12.0 to 13.0 μm. Formed.
The photosensitive resin film thus obtained is exposed to a broad band (BB) using a mask aligner MA-8 (manufactured by SUSS Microtech), and the exposed resin film is developed with cyclopentanone to obtain a 10 mm width. Was obtained.
The obtained pattern resin film was cured at 200 ° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF to obtain a cured pattern having a thickness of 10 μm.

(Evaluation of growth rate)
The cured pattern obtained in Production 3 of the cured pattern was immersed in a 4.9% by mass aqueous hydrofluoric acid solution, and the cured product having a width of 10 mm was peeled from the wafer.
The peeled cured product having a width of 10 mm was subjected to a tensile test using Autograph AGS-X 100N (manufactured by Shimadzu Corporation). The distance between the chucks was set to 20 mm, the tensile speed was set to 5 mm / min, and the measurement temperature was set to 18 to 25 ° C.
When the average value of the elongation percentage was more than 50%, it was set to A, when it was more than 45% and 50% or less, it was set to B, and when it was 45% or less, it was set to C. Table 1 shows the results before PCT (pressure cooker test).

Further, the cured pattern obtained in the above-mentioned production 3 of the cured pattern was cured at 121 ° C., 100 RH (relative humidity)% and 2 atm using a PCT tester HASTEST (PC-R8D, manufactured by Hirayama Seisakusho) Treated for 100 hours.
The cured pattern was taken out from the PCT test apparatus, the cured pattern was peeled off in the same manner as described above, a tensile test was performed, and the average elongation was determined.
When the average value of the elongation percentage was more than 50%, it was set to A, when it was more than 45% and 50% or less, it was set to B, and when it was 45% or less, it was set to C. Table 1 shows the results after PCT. "-" Indicates that no measurement was performed.

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

While certain embodiments and / or examples of the invention have been described in detail above, those skilled in the art will recognize those exemplary embodiments and / or examples without departing substantially from the novel teachings and advantages of the invention. It is easy to make many changes to the embodiments. Accordingly, many of these changes are within the scope of the invention.
The entire contents of the documents and the application based on the Paris Convention priority of the present application are incorporated herein by reference.

Claims

(A) a polyimide precursor having a polymerizable unsaturated bond,
(B) a polymerizable monomer,
(C) a photopolymerization initiator,
A photosensitive resin composition containing (D) a cyclization catalyst and (E) a solvent.
The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

(In the formula (1), X 1 is a tetravalent group having one or more aromatic groups, and the —COOR 1 group and the —CONH— group are located at ortho positions to each other, and the —COOR 2 group and the —CO And the groups are at ortho positions to each other, Y 1 is a divalent aromatic group, R 1 and R 2 are each independently a hydrogen atom, a group represented by the following formula (2), or a carbon number (1-4) wherein at least one of R 1 and R 2 is a group represented by the formula (2).)

(In the formula (2), R 3 to 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.)
The component (D) comprises N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N, N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2 '-(4-methylaniline. 3. The photosensitive resin composition according to claim 1, which is at least one selected from the group consisting of (phenylimino) diethanol.
The photosensitive resin composition according to claim 1, wherein the component (D) includes a compound represented by the following formula (17).

(In the formula (17), R 31A to R 33A each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group. And at least one of R 31A to R 33A is a monovalent aromatic group. R 31A to R 33A may form a ring with adjacent groups.
The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (C) comprises (C1) a compound represented by the following formula (15) and (C2) a compound represented by the following formula (16). Stuff.

(In the formula (15), R 11A is an alkyl group having 1 to 12 carbon atoms, a1 is an integer of 0 to 5. R 12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R 13A And R 14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, and when a1 is an integer of 2 or more, R 11A may be the same or different. .)

(In the formula (16), R 21A is an alkyl group having 1 to 12 carbon atoms, and R 22A and R 23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms. A cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R 21A may be the same or different. May be.)
(6) The photosensitive resin composition according to any one of (1) to (5), wherein the component (B) contains a polymerizable monomer having an aliphatic cyclic skeleton.
感光 The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (B) has a group containing a polymerizable unsaturated double bond.
The photosensitive resin composition according to claim 7, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds.
8. The photosensitive resin composition according to claim 1, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

(In the 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). N1 is 0 or 1 , N2 is an integer of 0 to 2, and n1 + n2 is 1 or more. At least one of n1 R 6 and n2 R 7 is a group represented by the following formula (4).)

(In the formula (4), R 9 to R 11 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer of 0 to 10.)
The photosensitive resin composition according to claim 9, wherein n1 + n2 is 2 or 3.
11. The photosensitive resin composition according to claim 1, wherein the component (B) contains a polymerizable monomer represented by the following formula (5).
The photosensitive resin composition according to any one of claims 1 to 11, further comprising (F) a thermal polymerization initiator.
The photosensitive resin composition according to any one of claims 1 to 12, further comprising an antioxidant.
A step of applying the photosensitive resin composition according to any one of claims 1 to 13 on a substrate and drying to form a photosensitive resin film;
Pattern-exposing the photosensitive resin film to obtain a resin film;
A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film,
Heat treating the pattern resin film.
The method according to claim 14, wherein the temperature of the heat treatment is 230 ° C or lower.
A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 13.
17. The cured product according to claim 16, which is a patterned cured product.
An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured product according to claim 16 or 17.
An electronic component comprising the interlayer insulating film, the cover coat layer, or the surface protective film according to claim 18.