CN113168092A

CN113168092A - Photosensitive resin composition, method for producing patterned cured product, interlayer insulating film, covercoat, surface protective film, and electronic component

Info

Publication number: CN113168092A
Application number: CN201980065227.5A
Authority: CN
Inventors: 米田聪; 朝田皓; 副岛和也; 松家则孝; 榎本哲也
Original assignee: Actri Microsystems Co ltd
Current assignee: Actri Microsystems Co ltd; HD MicroSystems Ltd
Priority date: 2018-10-03
Filing date: 2019-10-02
Publication date: 2021-07-23
Also published as: TWI816900B; JP7405088B2; KR20210068418A; WO2020071437A1; TW202028863A; JPWO2020071437A1

Abstract

A photosensitive resin composition comprising: (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 patterned cured product, interlayer insulating film, covercoat, surface protective film, and electronic component

Technical Field

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

Background

Conventionally, polyimide or polybenzene having excellent heat resistance, electrical properties, mechanical properties and the like has been used as a surface protective film and an interlayer insulating film of a semiconductor device

And (3) azole. In recent years, photosensitive resin compositions that impart photosensitive characteristics to these resins themselves have been used, and if such photosensitive resin compositions are used, the production process of patterned cured products can be simplified, and complicated production processes can be shortened (see, for example, patent document 1).

In recent years, miniaturization of transistors supporting high performance of computers has approached the limit of the rule of proportionality, and a stacked device structure in which semiconductor elements are three-dimensionally stacked has attracted attention for further improvement in performance and high speed.

Among the stacked device structures, a Multi-die Fanout Wafer Level package (Multi-die Fanout Wafer Level Packaging) is a package manufactured by collectively sealing a plurality of chips in one package, and is drawing attention because it can be expected to reduce the cost and improve the performance as compared with a fan-out Wafer Level package (manufactured by sealing one chip in one package) proposed in the related art.

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

Further, as the resin composition, a resin composition containing a polyimide precursor is disclosed (for example, see patent document 3).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-265520

Patent document 2: international publication No. 2008/111470

Patent document 3: japanese patent laid-open publication No. 2016-199662

Disclosure of Invention

The purpose of the present invention is to provide a photosensitive resin composition which can form a cured product having excellent mechanical properties even when cured at a low temperature of 230 ℃ or less and has excellent storage stability, a method for producing a pattern cured product, a cured product, an interlayer insulating film, a coverlay, a surface protective film, and an electronic component.

According to the present invention, the following photosensitive resin composition and the like can be provided.

1. A photosensitive resin composition comprising:

(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.

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

[ solution 1]

(in the formula (1), X₁Is a 4-valent radical having more than 1 aromatic group, -COOR₁The radicals and the-CONH-radicals being in ortho-position to one another, -COOR₂The radicals and the-CO-radicals are in the ortho position relative to one another. Y is₁Is a 2-valent aromatic group. R₁And R₂Each independently represents a hydrogen atom, a group represented by the following formula (2) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R₁And R₂At least one of them is a group represented by the above formula (2). )

[ solution 2]

(in the formula (2), R₃～R₅Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10. )

3. The photosensitive resin composition according to

claim

1 or 2, wherein the component (D) is at least one selected from the group consisting of N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2, 2' - (4-methylphenylimino) diethanol.

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

[ solution 3]

(in the formula (17), R_31A～R_33AEach independently is a hydrogen atom, a 1-valent aliphatic hydrocarbon group having a hydroxyl group, or a 1-valent aromatic group, R_31A～R_33AAt least one of (a) is a 1-valent aromatic group. R_31A～R_33AThe rings may be formed by adjacent groups. )

5. 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).

[ solution 4]

(in the formula (15), R_11AIs an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R_12AIs a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R_13AAnd R_14AEach independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group. In the case where a1 is an integer of 2 or more, R_11AEach may be the same or different. )

[ solution 5]

(in the formula (16), R_21AIs an alkyl group having 1 to 12 carbon atoms, R_22AAnd R_23AEach independently represents 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. In the case where c1 is an integer of 2 or more, R_21AEach may be the same or different. )

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. 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. The photosensitive resin composition according to claim 7, wherein the component (B) is a polymerizable monomer having a group containing 2 or more polymerizable unsaturated double bonds.

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

[ solution 6]

(in the formula (3), R₆And R₇Each independently is 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 greater than or equal to 1. n 1R₆And n 2R₇At least one of them is a group represented by the following formula (4). )

[ solution 7]

(in the formula (4), R₉～R₁₁Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10. )

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

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

[ solution 8]

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

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

14. A method for producing a pattern cured product, comprising the steps of:

a step of forming a photosensitive resin film by coating the photosensitive resin composition of any one of 1 to 13 on a substrate and drying the coating;

pattern-exposing the photosensitive resin film to obtain a resin film;

a step of obtaining a pattern resin film by developing the pattern-exposed resin film with an organic solvent; and

and a step of heat-treating the patterned resin film.

15. The method for producing a pattern cured product according to claim 14, wherein the temperature of the heat treatment is 230 ℃ or lower.

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

17. The cured product according to claim 16, which is a pattern cured product.

18. An interlayer insulating film, a cover coat layer or a surface protective film, which is produced using the cured product of 16 or 17.

19. An electronic part comprising the interlayer insulating film, covercoat or surface protective film of 18.

According to the present invention, it is possible to provide a photosensitive resin composition, a method for producing a pattern cured product, a cured product, an interlayer insulating film, a coverlay, a surface protective film, and an electronic component, which can form a cured product having excellent mechanical properties even when cured at a low temperature of 230 ℃ or lower and have excellent storage stability.

Drawings

Fig. 1 is a process diagram for manufacturing an electronic component according to an embodiment of the present invention.

Detailed Description

The photosensitive resin composition of the present invention, a method for producing a pattern cured product using the same, a cured product, an interlayer insulating film, a covercoat, a surface protective film, and an electronic component will be described in detail below. The present invention is not limited to the following embodiments.

In the present specification, "a or" B "may include either one of a and B, or both of them. The term "step" in the present specification includes not only an independent step but also a step that can achieve a desired action of the step even when the step is not clearly distinguished from other steps.

The numerical range represented by the term "to" represents a range including the numerical values recited before and after the term "to" as the minimum value and the maximum value, respectively. In the present specification, the content of each component in the composition refers to the total amount of a plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Further, the exemplified materials may be used alone or in combination of two or more unless otherwise specified.

The "(meth) acryloyl group" in the present specification means "acryloyl group" and "methacryloyl group".

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

(E) a solvent (hereinafter, also referred to as "component (E)").

Thus, even when cured at a low temperature of 230 ℃ or lower, a cured product having excellent mechanical properties can be formed.

In addition, the storage stability can be improved.

Further, as an optional effect, a cured product having an excellent cyclization ratio can be formed even by curing at a low temperature of 230 ℃ or lower.

As an arbitrary effect, the sensitivity can be improved.

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 high transmittance when i-line is used as a light source in patterning and exhibits high cured product characteristics even when cured at a low temperature of 230 ℃.

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

(A) The component (b) is preferably a polyimide precursor having a structural unit represented by the following formula (1). Thus, i-line has high transmittance, and a good cured product can be formed even when cured at a low temperature of 230 ℃ or lower.

The content of the structural unit represented by formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, based on the total structural units of component (a). The upper limit is not particularly limited, and may be 100 mol%.

[ solution 9]

[ solution 10]

(in the formula (2), R₃～R₅Each independently represents 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). )

X of formula (1)₁In the 4-valent group having 1 or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups in the (a) aromatic group, the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Preferably aromaticA hydrocarbyl group.

X as formula (1)₁The aromatic hydrocarbon group of (2) to (4) is a 2 to (2, 3 or 4) valent group formed from a benzene ring, a 2 to 4 valent group formed from naphthalene, a 2 to 4 valent group formed from perylene, or the like.

X as formula (1)₁Examples of the 4-valent group having 1 or more aromatic groups in (b) include, but are not limited to, the 4-valent group of the following formula (6).

[ solution 11]

(in the formula (6), X and Y each independently represent a 2-valent group which is not conjugated to the benzene ring to which each is bonded or a single bond; Z is an ether group (-O-) or a thioether group (-S-) (preferably-O-)

In the formula (6), the 2-valent group of X and Y which is not conjugated to the benzene ring to which each is bonded is preferably-O-, -S-, methylene, bis (trifluoromethyl) methylene or difluoromethylene, more preferably-O-.

Y of formula (1)₁The 2-valent aromatic group in (b) may be a 2-valent aromatic hydrocarbon group or a 2-valent aromatic heterocyclic group. Preferably a 2-valent aromatic hydrocarbon group.

Y as formula (1)₁Examples of the 2-valent aromatic hydrocarbon group(s) include, but are not limited to, the group of the following formula (7).

[ solution 12]

(in the formula (7), R₁₂～R₁₉Each independently a hydrogen atom, a 1-valent aliphatic hydrocarbon group, or a 1-valent organic group having a halogen atom. )

R as formula (7)₁₂～R₁₉The 1-valent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) may include a methyl group and the like. For example, may be R₁₂And R₁₅～R₁₉Is a hydrogen atom, R₁₃And R₁₄Is a 1-valent aliphatic hydrocarbon group.

R of formula (7)₁₂～R₁₉The 1-valent organic group having a halogen atom (preferably a fluorine atom) of (a) is preferably a 1-valent aliphatic hydrocarbon group having a halogen atom (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), and examples thereof include a trifluoromethyl group and the like.

R as formula (1)₁And R₂Examples of the aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms include methyl, ethyl, n-propyl, 2-propyl, n-butyl and the like.

R of formula (1)₁And R₂At least one of the groups represented by the formula (2) is preferably a group represented by the formula (2).

R as formula (2)₃～R₅Examples of the aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. Preferably methyl.

The polyimide precursor having the structural unit represented by formula (1) can be obtained, for example, as follows: a tetracarboxylic dianhydride represented by the following formula (8) is reacted with a diamino compound represented by the following formula (9) in an organic solvent such as N-methyl-2-pyrrolidone to obtain a polyamic acid, and a compound represented by the following formula (10) is added and reacted in the organic solvent to partially introduce an ester group.

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

[ solution 13]

(in the formula (8), X₁Is X of formula (1)₁The corresponding groups. )

[ solution 14]

H₂N-Y₁-NH₂···(9)

(in the formula (9), Y₁As defined in formula (1). )

[ solution 15]

R-OH···(10)

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

(A) The component (b) 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 the structural unit represented by formula (11).

[ solution 16]

(in the formula (11), X₂Is a 4-valent radical having more than 1 aromatic group, -COOR₅₁The radicals and the-CONH-radicals being in ortho-position to one another, -COOR₅₂The radicals and the-CO-radicals are in the ortho position relative to one another. Y is₂Is a 2-valent aromatic group. R₅₁And R₅₂Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. )

X of formula (11)₂The 4-valent group having 1 or more aromatic groups in (A) may be represented by X of the formula (1)₁The same group as the 4-valent group having 1 or more aromatic groups in (a).

Y of formula (11)₂The 2-valent aromatic group in (2) may be represented by Y in the formula (1)₁The 2-valent aromatic group of (1) is the same group.

R of formula (11)₅₁And R₅₂The aliphatic hydrocarbon group having 1 to 4 carbon atoms includes₁And R₂The same as the aliphatic hydrocarbon group having 1 to 4 carbon atoms.

One kind of structural unit other than the structural unit represented by formula (1) may be used alone, or two or more kinds may be combined.

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

In the component (a), the ratio of the esterified carboxyl groups in the group represented by the formula (2) to all the carboxyl groups and all the carboxylic acid esters is preferably 50 mol% or more, more preferably 60 to 100 mol%, and still more preferably 70 to 90 mol%.

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

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

(B) The component (b) preferably has (preferably 2 or more) groups containing a polymerizable unsaturated double bond (preferably a (meth) acryloyl group, from the viewpoint of being polymerizable by a photopolymerization initiator). (B) The component (C) is preferably a polymerizable monomer having 2 or more groups containing a polymerizable unsaturated double bond. In order to increase the crosslinking density and sensitivity and suppress swelling of a pattern after development, the photosensitive composition preferably has 2 to 3 groups containing a polymerizable unsaturated double bond.

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.

(B) The component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton (preferably 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms). This can impart hydrophobicity to the curable material that can be formed, and can suppress a decrease in adhesion between the curable material and the substrate under high-temperature and high-humidity conditions.

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

[ solution 17]

(in the formula (3), R₆And R₇Each independently is 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 greater than or equal to 1 (preferably 2 or 3). n 1R₆And n 2R₇At least one (preferably 2 or 3) of the above groups is a group represented by the following formula (4). )

At R₇In the case of 2, 2R₇May be the same or different.

[ solution 18]

(in the formula (4), R₉～R₁₁Each independently represents 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). )

(B) The component (C) more preferably contains a polymerizable monomer represented by the following formula (5).

[ solution 19]

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

[ solution 20]

In the formula (12), R₂₁～R₂₄Each independently is an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the formula (4). n3 is an integer of 1 to 3 (preferably 2 or 3). n4 is an integer of 1 to 3 (preferably 2 or 3). n5 is 0 or 1, and n6 is 0 or 1. n5+ n6 is greater than or equal to 1 (preferably 2).

At R₂₁When there are 2 or more, 2 or more R₂₁May be the same or different.

At R₂₂When there are 2 or more, 2 or more R₂₂May be the same or different.

n 3R₂₁At least one (preferably 2 or 3) of (a) and (b) is a group represented by the above formula (4).

n 4R₂₂At least one (preferably 2 or 3) of (a) and (b) is a group represented by the above formula (4).

n 5R₂₃And n 6R₂₄At least one (preferably 2) of them is a group represented by the above formula (4).

R as formula (3)₆And R₇And R of formula (12)₂₁～R₂₄The aliphatic hydrocarbon group having 1 to 4 carbon atoms of (A) includes R of the formula (1)₁And R₂The same as the aliphatic hydrocarbon group having 1 to 4 carbon atoms.

R as formula (4)₉～R₁₁The aliphatic hydrocarbon group having 1 to 3 carbon atoms of (A) includes a group represented by formula (2) R₃～R₅The same as the aliphatic hydrocarbon group having 1 to 3 carbon atoms.

(B) The component (b) may contain a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton. This enables to obtain a cured product having good mechanical properties.

Examples of the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and mixtures thereof, Tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloxyethyl isocyanurate, methacryloxyethyl isocyanurate, Ethylene Oxide (EO) -modified bisphenol a diacrylate (for example, FA324A (manufactured by hitachi chemical co., ltd.)) and the like are commercially available.

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

From the viewpoint of obtaining good mechanical properties and photosensitive properties, 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.

When the polymerizable monomer having an aliphatic cyclic skeleton and the 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 preferably 1 to 40 parts by mass with respect to 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 35 parts by mass. The content of the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton is preferably 1 to 20 parts by mass with respect to 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 relative to 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.

In the case of the above range, a practical concave-convex pattern can be easily obtained, and the residue after development of the unexposed portion can be easily suppressed.

Preferred 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-hydroxycyclohexyl phenyl ketone;

thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone;

benzil derivatives such as benzil, benzil dimethyl ketal, and benzil- 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-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-acetyl oxime), and oxime esters such as compounds represented by the following formula, but not limited thereto.

[ solution 21]

In particular, oxime esters are preferable from the viewpoint of sensitivity.

(C) Component (C1) preferably contains a compound represented by the following formula (15) (hereinafter, also referred to as "component (C1)").

(C1) The component (C) is preferably a photosensitizer having higher sensitivity to active light than the component (C2) described later, and is preferably high sensitivity.

[ solution 22]

In the formula (15), R_11AIs an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R_12AIs a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R_13AAnd R_14AEach independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a phenyl group or a tolyl group. In the case where a1 is an integer of 2 or more, R_11AEach may be the same or different.

R_11APreferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1. R_12APreferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. R_13AAnd R_14AEach of the alkyl groups is preferably 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), which is available as "IRGACURE OXE 02" manufactured by BASF japan ltd.

[ solution 23]

The component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter, also referred to as a component (C2)).

(C2) The component (C) is preferably a photosensitizer having a sensitivity to active light lower than that of the (C1) component, preferably a standard sensitivity.

[ solution 24]

In the formula (16), R_21AIs an alkyl group having 1 to 12 carbon atoms, R_22AAnd R_23AEach independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (preferably 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. In the case where c1 is an integer of 2 or more, R_21AEach may be the same or different.

c1 is preferably 0. R_22APreferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. R_23APreferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still 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.

[ solution 25]

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

(C) The component (C) preferably contains one or more 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 still more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the component (A).

In the case where the amount is within the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical uneven pattern is likely to be 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 2.5 parts by mass, and more preferably 0.09 to 1.0 part by mass, based on 100 parts by mass of the component (A).

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

When the component (C1) and the component (C2) are contained, the content of the component (C1) is preferably 0.05 to 5.0 parts by mass per 100 parts by mass of the component (a), and the content of the component (C2) is preferably 0.5 to 15.0 parts by mass per 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 1:2 to 1:15, and more preferably 1:3 to 1: 10.

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

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

(D) Component (c) preferably contains a compound represented by the following formula (17).

[ solution 26]

(in the formula (17), R_31A～R_33AEach independently is a hydrogen atom, a 1-valent aliphatic hydrocarbon group having a hydroxyl group, or a 1-valent aromatic group, R_31A～R_33AAt least one (preferably one) of (a) is a 1-valent aromatic group. R_31A～R_33ARings (for example, a 5-membered ring or a 6-membered ring which may have a substituent (for example, methyl group, phenyl group)) may be formed from adjacent groups to each other. )

Preferably further R_31A～R_33AAt least one of the groups is a 1-valent aliphatic hydrocarbon group, a 1-valent aliphatic hydrocarbon group having a hydroxyl group, or a 1-valent aromatic group.

R as formula (17)_31A～R_33AThe 1-valent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) includes a methyl group, an ethyl group and the like.

R as formula (17)_31A～R_33AThe 1-valent aliphatic hydrocarbon group having a hydroxyl group in (1) is exemplified by the group represented by R_31A～R_33AAnd a group having 1 or more (preferably 1 to 3) hydroxyl groups bonded to the 1-valent aliphatic hydrocarbon group(s) of (a). Specifically, the hydroxyl group includes a hydroxymethyl group and a hydroxyethyl group. Preferably hydroxyethyl.

R as formula (17)_31A～R_33AThe 1-valent aromatic group of (a) may be a 1-valent aromatic hydrocarbon group (preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms), and may be a 1-valent aromatic heterocyclic group. Preferably a 1-valent aromatic hydrocarbon group.

Examples of the 1-valent aromatic hydrocarbon group include a phenyl group and a naphthyl group.

R of formula (17)_31A～R_33AThe 1-valent aromatic group in (1) may have a substituent.Examples of the substituent include R of the above formula (17)_31A～R_33AAnd R of the above formula (17)_31A～R_33AThe same applies to the 1-valent aliphatic hydrocarbon group having a hydroxyl group.

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

The content of the component (D) is preferably 0.1 to 20 parts by mass per 100 parts by mass of the component (A) from the viewpoint of improving the imidization rate 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.

Examples of the component (E) include N-methyl-2-pyrrolidone, γ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, N-butyl acetate, ethyl ethoxypropionate, methyl 3-methoxypropionate, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, and N-dimethylmorpholine, and the component (E) is not particularly limited as long as the other components can be dissolved sufficiently.

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

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

[ solution 27]

(in the formula, R₄₁～R₄₃Each independently is an alkyl group having 1 to 10 carbon atoms. )

As R in formula (21)₄₁～R₄₃Has 1 to 10 (preferably 1 to c)3, more preferably 1 or 3), and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like.

The compound represented by the formula (21) is preferably 3-methoxy-N, N-dimethylpropionamide (for example, trade name "KJCMPA-100" (manufactured by KJ chemical Co., Ltd.)).

(E) The component (b) may be used alone or in combination of two or more.

(E) The content of the component (A) is not particularly limited, but is generally 50 to 1000 parts by mass per 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.

As the component (F), the following compounds are preferable: the components (B) are not decomposed by heating (drying) for removing the solvent during film formation, but are decomposed by heating during curing to generate radicals, thereby promoting polymerization of the components (B) or the components (a) and (B).

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

Specific examples thereof include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, and 1, 1-bis (t-butylperoxy) cyclohexane; hydrogen peroxide such as 1,1,3, 3-tetramethylbutylhydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, etc.; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate and bis (2-ethylhexyl) peroxydicarbonate; peroxy esters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy benzoate, and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate; bis (1-phenyl-1-methylethyl) peroxide, and the like. Commercially available products include trade names "Percumyl D", "Percumyl P" and "Percumyl H" (manufactured by Nikkiso Co., Ltd.).

When the component (F) is contained, the content of the component (F) is preferably 0.1 to 20 parts by mass per 100 parts by mass of the component (a), more preferably 0.2 to 20 parts by mass in order to ensure good flux resistance, and still more preferably 0.3 to 10 parts by mass in view of suppressing a decrease in solubility due to decomposition during drying.

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

Examples of the antioxidant include N, N ' -bis [2- [2- (3, 5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy ] ethyl ] oxamide, N ' -bis-3- (3, 5-di-tert-butyl-4 ' -hydroxyphenyl) propionyl hexamethylenediamine, 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-tert-butyl-4-methylphenol, 2, 5-di-tert-butylhydroquinone, octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4 ' -methylenebis (2, 6-di-tert-butylphenol), 4 ' -thio-bis (3-methyl-6-tert-butylphenol), 4 ' -butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 2-thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], (meth) acrylic acid, methacrylic acid, acrylic acid, methacrylic acid, acrylic, N, N ' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamamide), isooctyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-tris [ 4-triethylmethyl-3-hydroxy-2, 6-dimethylbenzyl ] -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, 2 ' -methylene-bis (4-methyl-6-tert-butylphenol), 2 ' -methylene-bis (4-ethyl-6-tert-butylphenol),

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

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

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

1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid, and the like.

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

When the antioxidant is contained, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (a).

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

In general, the coupling agent reacts with the component (a) to crosslink in the heat treatment after development, or the coupling agent itself polymerizes in the step of the heat treatment. This can further improve the adhesion between the obtained cured product and the substrate.

As a preferable silane coupling agent, a compound having a urea bond (-NH-CO-NH-) can be mentioned. Thereby, even when curing is performed at a low temperature of 230 ℃ 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 adhesiveness when cured at low temperature.

[ solution 28]

(in the formula (13), R₃₁And R₃₂Each 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 formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, and 4-ureidobutyltriethoxysilane, and 3-ureidopropyltriethoxysilane is preferable.

As the silane coupling agent, a silane coupling agent having a hydroxyl group or a glycidyl group may also be used. When a silane coupling agent having a hydroxyl group or a glycidyl group and a silane coupling agent having a urea bond in the molecule are used in combination, the adhesion of a cured product to a substrate during low-temperature curing can be further improved.

Examples of the silane coupling agent having a hydroxyl group or a glycidyl group include methylphenylsilane diol, ethylphenylsilane diol, n-propylphenylsilane diol, isopropylphenylsilane diol, n-butylphenyl silane diol, isobutylphenylsilane diol, tert-butylphenyl silane diol, diphenylsilane diol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butyleethylphenylsilanol, isobutylethylphenylsilanol, tert-butyleethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyl diphenylsilanol, tert-butyl diphenylsilanol, phenylsilane triol, 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 a compound represented by the following formula (14). Among them, the compound represented by the formula (14) is particularly preferable in order to further improve the adhesion to the substrate.

[ solution 29]

(in the formula (14), R₃₃Is a 1-valent organic radical having a hydroxyl group or a glycidyl group, R₃₄And R₃₅Each independently an alkyl group having 1 to 5 carbon atoms. c is an integer of 1 to 10, and d is an integer of 1 to 3. )

Examples of the compound represented by formula (14) include: hydroxymethyl trimethoxysilane, hydroxymethyl triethoxysilane, 2-hydroxyethyl trimethoxysilane, 2-hydroxyethyl triethoxysilane, 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 4-hydroxybutyl trimethoxysilane, 4-hydroxybutyl triethoxysilane, glycidoxymethyl trimethoxysilane, glycidoxymethyl triethoxysilane, 2-glycidoxyethyl trimethoxysilane, 2-glycidoxyethyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 4-glycidoxybutyl trimethoxysilane, 4-glycidoxybutyl triethoxysilane, etc.

The silane coupling agent having a hydroxyl group or a glycidyl group preferably further contains a group having a nitrogen atom, and preferably a silane coupling agent further having an amino group or an amide bond.

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

Examples of the silane coupling agent further having an amide bond include: r₃₆-(CH₂)_e-CO-NH-(CH₂)_f-Si(OR₃₇)₃(R₃₆Is a hydroxyl group or a glycidyl group, e and f are each independently an integer of 1 to 3, R₃₇Methyl, ethyl or propyl) and the like.

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 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 1 to 10 parts by mass, per 100 parts by mass of the component (a).

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

Examples of the surfactant and the leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether, and examples of commercially available products include trade names "MEGAFAX F171", "F173", and "R-08" (manufactured by DIC corporation); trade names "FLUORAD FC 430" and "FC 431" (manufactured by Sumitomo 3M Co., Ltd.); the trade names "Organosiloxane Polymer (Organosiloxane Polymer) KP 341", "KBM 303", "KBM 403" and "KBM 803" (manufactured by shin-Etsu chemical Co., Ltd.).

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

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

By containing the rust inhibitor, corrosion of copper and copper alloy can be suppressed and discoloration can be prevented.

Examples of the rust inhibitor include triazole derivatives and tetrazole derivatives.

One kind of rust inhibitor may be used alone, or two or more kinds may be used in combination.

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 still more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the component (a).

By containing 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, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, Cupferron (Cupfron), 2, 5-toluenequinone, tannic acid, p-benzylaminophenol, and nitrosamines.

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

When the 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 still more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the component (a), from the viewpoints of storage stability of the photosensitive resin composition and heat resistance of the resulting cured product.

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

The photosensitive resin composition of the present invention may contain, for example, not less than 80 mass%, not less than 90 mass%, not less than 95 mass%, not less than 98 mass%, or 100 mass% of the total amount of the photosensitive resin composition

(A) Components (A) to (E),

(A) Component (1) to (F), or

(A) Components (A) to (E), and optionally component (F), a coupling agent, a surfactant, a leveling agent, an anticorrosive agent and a polymerization inhibitor.

The cured product of the present invention can be obtained by curing the photosensitive resin composition.

The cured product of the present invention can be used as a patterned cured product or an unpatterned cured product.

The thickness of the cured product of the present invention is preferably 5 to 20 μm.

The method for producing a patterned cured product of the present invention comprises the steps of: a step of forming a photosensitive resin film by coating the photosensitive resin composition on a substrate and drying the composition; a step of obtaining a resin film by pattern-exposing a photosensitive resin film; a step of developing the resin film after pattern exposure with an organic solvent to obtain a pattern resin film; and a step of performing heat treatment on the pattern resin film.

This enables to obtain a patterned cured product.

The method for producing a non-patterned cured product includes, for example, a step of forming the photosensitive resin film and a step of performing a heat treatment. The method may further comprise an exposure step.

Examples of the substrate include a glass substrate and an Si substrateA semiconductor substrate (silicon wafer) or the like; TiO 2₂Substrate and SiO₂Metal oxide insulator substrates such as substrates; silicon nitride substrates, copper alloy substrates, and the like.

The coating method is not particularly limited, and may be performed using a spin coater or the like.

Drying may be performed using a hot plate, an oven, or the like.

The drying temperature is preferably 90 to 150 ℃, and more preferably 90 to 120 ℃ from the viewpoint of ensuring the solubility contrast.

The drying time is preferably 30 seconds to 5 minutes.

The drying may be carried out 2 or more times.

Thus, a photosensitive resin film formed by forming the photosensitive resin composition into a film shape can be obtained.

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.

The pattern exposure is, for example, exposure to a predetermined pattern through a photomask.

Examples of the active light rays to be irradiated include ultraviolet rays such as i-ray and broadband (BB); visible rays, radiation, and the like, i-rays are preferred.

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

By performing development, a patterned resin film (pattern resin film) can be obtained. In general, when a negative photosensitive resin composition is used, a developer is used to remove unexposed portions.

The organic solvent used as the developer may be a good solvent for the photosensitive resin film alone or a good solvent and a poor solvent which are suitably mixed and used as the developer.

Examples of the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, 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.

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

The developing time may be 2 times the time required for completely dissolving the photosensitive resin film after immersion.

The developing time varies depending on the component (a) used, and is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 20 seconds to 5 minutes from the viewpoint of productivity.

After development, washing may be performed using a washing solution.

The rinse solution may be used alone or in a suitable mixture of distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and the like, or may be used in combination in stages.

The pattern resin film is heat-treated to obtain a pattern cured product.

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

The temperature of the heat treatment is preferably not more than 250 ℃, more preferably 120 to 250 ℃, and further preferably not more than 230 ℃ or 180 to 230 ℃.

By setting the range as described above, damage to the substrate and the device can be suppressed to a small extent, the device can be produced with a high yield, and energy saving of the process can be achieved.

The time of the heat treatment is preferably 5 hours or less, and more preferably 30 minutes to 3 hours.

When the amount is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can be sufficiently performed.

The atmosphere for the heat treatment may be in the air or an inert atmosphere such as nitrogen, and is preferably a nitrogen atmosphere from the viewpoint of preventing the oxidation of the pattern resin film.

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

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

By using one or more selected from the group consisting of the above-described passivation film, buffer coating film, interlayer insulating film, coverlay film, surface protective film, and the like, it is possible to manufacture highly reliable electronic components such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (multi-chip fan-out type wafer level packages and the like).

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 process diagram for manufacturing 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 an Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film except for predetermined portions 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.

Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolac type, or the like is formed on the interlayer insulating film 4, and a window 6A is provided by a known photolithography technique so as to expose a predetermined portion of the interlayer insulating film 4.

The interlayer insulating film 4 exposed by the window 6A is selectively etched to provide a window 6B.

Next, the photosensitive resin layer 5 is completely removed by using an etching solution that does not etch the first conductor layer 3 exposed through the window 6B but etches only the photosensitive resin layer 5.

A second conductor layer 7 is further formed using a known photolithography technique to be electrically connected to the first conductor layer 3.

In the case of forming a multilayer wiring structure having 3 or more layers, the above-described steps may be repeated to form each layer.

Next, the window 6C is opened by pattern exposure using the photosensitive resin composition, and the surface protective film 8 is formed. The surface protective film 8 protects the second conductor layer 7 from external stress, α -rays, and the like, and the obtained semiconductor device is excellent in reliability.

In the above examples, the photosensitive resin composition of the present invention can be used to form an interlayer insulating film.

Examples

The present invention will be described in further detail below based on examples and comparative examples. The present invention is not limited to the following examples.

Synthesis example 1 (Synthesis of A1)

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 N-methyl-2-pyrrolidone (NMP), stirred at 30 ℃ for 4 hours, and then stirred at room temperature for one hour to obtain polyamic acid. 9.45g of trifluoroacetic anhydride was added thereto under water cooling, and stirred at 45 ℃ for 3 hours, 7.08g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was dropwise added to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor a 1.

The number average molecular weight was determined by Gel Permeation Chromatography (GPC) method in terms of standard polystyrene under the following conditions. The number average molecular weight of A1 was 40,000.

The measurement was performed using 1mL of a solution of the solvent [ Tetrahydrofuran (THF)/Dimethylformamide (DMF) ═ 1/1 (volume ratio) ] relative to 0.5mg of a 1.

A measuring device: l4000UV manufactured by Hitachi, Inc. of Detector

A pump: l6000 manufactured by Hitachi Kabushiki Kaisha

C-R4A Chromatopac, manufactured by Shimadzu corporation

The measurement conditions were as follows: column Gelpack GL-S300 MDT-5X 2

Eluent: THF/DMF 1/1 (volumetric ratio)

LiBr(0.03mol/L)、H₃PO₄(0.06mol/L)

Flow rate: 1.0mL/min, detector: UV270nm

Further, the esterification ratio of a1 (the reaction ratio between carboxyl groups of ODPA and HEMA) was calculated by NMR measurement under the following conditions. The esterification rate was 80 mol% relative to all carboxyl groups of the polyamic acid (the remaining 20 mol% were carboxyl groups).

Measurement equipment: AV400M manufactured by Bruker BioSpin

Magnetic field strength: 400MHz

Reference substance: tetramethylsilane (TMS)

Solvent: dimethyl sulfoxide (DMSO)

Examples 1 to 3 and comparative examples 1 to 5

(preparation of photosensitive resin composition)

Photosensitive resin compositions of examples 1 to 3 and comparative examples 1 to 5 were prepared according to the components and blending amounts shown in Table 1. The blending amount in table 1 is part by mass relative to 100 parts by mass of each component of a 1.

The components used are as follows. As component (A), A1 obtained in Synthesis example 1 was used.

(B) The components: polymerizable monomer

B1: A-DCP (Dicidodecane dimethanol diacrylate, produced by Mitsumura chemical Co., Ltd., described below as a compound represented by formula B1)

[ solution 30]

B2: ATM-4E (ethoxylated pentaerythritol tetraacrylate, a compound represented by the following formula (n11+ n12+ n13+ n 14: 4, manufactured by Mitsumura chemical industries, Ltd.)

[ solution 31]

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

[ solution 32]

(C) The components: photopolymerization initiator

C1: IRUGCURE OXE 02 (ethanone, manufactured by BASF Japan K.K., 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 K.K.)

(D) The components: cyclization catalyst

D1: 2HE (N-phenyldiethanolamine, manufactured by Morin chemical industry Co., Ltd.)

(D') component

D2: U-CAT SA810 (a compound represented by the following formula D2, available from San-Apro Co., Ltd.)

[ solution 33]

D3: U-CAT SA 1(a compound represented by the following formula D3, available from San-Apro Co., Ltd.)

[ chemical 34]

D4: 4-hydroxypyridines

(E) The components: solvent(s)

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

[ solution 35]

(F) The components: thermal polymerization initiator

F1: percumyl D (bis (1-phenyl-1-methylethyl) peroxide, manufactured by Nichikoku corporation, Compound represented by the following formula F1)

[ solution 36]

(evaluation of sensitivity)

The obtained photosensitive resin composition was spin-coated on a silicon wafer using a coater Act8 (manufactured by Tokyo electronics Co., Ltd.), and dried at 105 ℃ for 120 seconds and then at 115 ℃ for 120 seconds to form a photosensitive resin film having a dry film thickness of 13 μm.

The developing time was set to 2 times the time taken for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.

A photosensitive resin film was produced in the same manner as described above, and the obtained photosensitive resin film was subjected to exposure using an i-line stepper FPA-3000iW (available from Canon corporation) at a dose of 100mJ/cm²The irradiation amount of the scales is 100-1100 mJ/cm according to a predetermined pattern²And (4) performing exposure on the i line.

The exposed resin film was developed in cyclopentanone for the above-described development time using Act8, and then washed with Propylene Glycol Monomethyl Ether Acetate (PGMEA) to obtain a patterned resin film.

Sensitivity was defined as the lower limit of the exposure amount at which the film thickness of the obtained pattern resin film became 80% or more of the film thickness of the photosensitive resin film before exposure. The results are shown in table 1.

(preparation of patterned cured Material 1)

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

(preparation of patterned cured Material 2)

The pattern resin film obtained in the sensitivity evaluation was heated at 400 ℃ for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ -TF to obtain a pattern cured product.

(evaluation of cyclization ratio)

The pattern resin film obtained by the sensitivity evaluation was measured for IR (infrared spectroscopy) spectrum under the following conditions using FT-IR IRaffinity-1S (manufactured by Shimadzu corporation). This value is set to IR 1.

The IR spectrum is measured in a range of 400 to 4000cm by a transmission method^-1And 16 times of accumulation.

The measurement of the IR spectrum used a silicon wafer as a substrate. First, a substrate on which a photosensitive resin composition was not applied was measured and set as a background. Next, the resin film portion of the pattern resin film was measured 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 IR 2.

The IR of the cured pattern obtained in the production of cured pattern 2 was measured in the same manner as described above. This value is set to IR 3.

The cyclization ratio was determined by dividing the value obtained by subtracting IR1 from IR2 by the value obtained by subtracting IR1 from IR3 and calculating the percentage. 65% or more is defined as A, and less than 65% is defined as B. The results are shown in table 1.

(evaluation of storage stability)

The photosensitive resin composition was spin-coated on a Si substrate at a spin rate at which the film thickness after drying became 13 μm within 24 hours after the adjustment, and was heat-dried at 105 ℃ for 120 seconds and 115 ℃ for 120 seconds on a hot plate to form a photosensitive resin film. The silicon wafer was exposed by scraping a part of the film, and the height from the exposed silicon wafer surface to the film surface was measured using a probe profiler Dektak150 (manufactured by Bruker Co., Ltd.) (the film thickness was measured in the same manner as above, and also in the following). This was set to film thickness 1.

The photosensitive resin composition was allowed to stand at room temperature (25 ℃) for 14 days after the adjustment. After standing still, the film was spin-coated on a Si substrate at the same number of revolutions as in the case of forming a photosensitive resin film for measuring film thickness 1, and the film was heat-dried on a hot plate at 105 ℃ for 120 seconds and at 115 ℃ for 120 seconds to form a photosensitive resin film. The film thickness was measured in the same manner as described above. This was set to film thickness 2.

A is defined as a value obtained by dividing the absolute value obtained by subtracting the film thickness 1 from the film thickness 2 by the film thickness 1 and calculating a percentage of the value to be less than or equal to 5%. The case where the content exceeds 5% is defined as B. The results are shown in table 1.

(production of patterned cured Material 3)

The photosensitive resin composition is spin-coated on a Si substrate, and is dried by heating at 105 ℃ for 120 seconds and 115 ℃ for 120 seconds on a hot plate to form a photosensitive resin film of 12.0 to 13.0 μm.

The obtained photosensitive resin film was subjected to a broadband (BB) exposure using a mask aligner MA-8 (Suss MicroTec), and the exposed resin film was developed using cyclopentanone to obtain a 10 mm-wide pattern resin film.

The obtained pattern resin film was cured at 200 ℃ for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ -TF to obtain a pattern cured product having a film thickness of 10 μm.

(evaluation of elongation)

The pattern cured product obtained in production 3 of the pattern cured product was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and a 10mm wide cured product was peeled off from the wafer.

A tensile test was conducted on the peeled 10 mm-wide cured product using Autograph AGS-X100N (Shimadzu corporation). The distance between the clamps was 20mm, the stretching speed was 5 mm/min, and the measurement temperature was 18 to 25 ℃, and the average value of the elongation was determined by measuring 3 times for each cured product of each example and comparative example.

The average value of the elongation is a when it exceeds 50%, B when it exceeds 45% and is equal to or less than 50%, and C when it is equal to or less than 45%. The results before PCT (pressure cooker test) are shown in Table 1.

The cured pattern obtained in the above-mentioned production 3 of a cured pattern was treated at 121 ℃ and 100RH (Relative Humidity)%, 2atm for 100 hours using HASTEST (PC-R8D, manufactured by Hill, Ltd.) using a PCT testing apparatus.

The pattern cured product was taken out from the PCT test apparatus, peeled off in the same manner as described above, and subjected to a tensile test to determine an average value of the elongation.

The average value of the elongation is a when it exceeds 50%, B when it exceeds 45% and is equal to or less than 50%, and C when it is equal to or less than 45%. The results after PCT are shown in table 1. "-" indicates no measurement.

[ Table 1]

Industrial applicability

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

While several embodiments and/or examples of the present invention have been described in detail, those skilled in the art will readily appreciate that many modifications are possible in the embodiments and/or examples without materially departing from the novel teachings and advantages of this invention. Accordingly, these many variations are also included in the scope of the present invention.

The documents described in the present specification and the applications based on the paris convention priority base of the present application are incorporated herein in their entirety.

Claims

1. A photosensitive resin composition comprising:

(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.

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

[ solution 37]

In the formula (1), X₁Is a 4-valent radical having more than 1 aromatic group, -COOR₁The radicals and the-CONH-radicals being in ortho-position to one another, -COOR₂The radical and the-CO-radical being in the ortho position relative to one another, Y₁Is a 2-valent aromatic radical, R₁And R₂Each independently represents a hydrogen atom, a group represented by the following formula (2) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R₁And R₂At least one of which is a group represented by the formula (2),

[ solution 38]

In the formula (2), R₃～R₅Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.

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

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

[ solution 39]

In the formula (17), R_31A～R_33AEach independently is a hydrogen atom, a 1-valent aliphatic hydrocarbon group having a hydroxyl group, or a 1-valent aromatic group, R_31A～R_33AAt least one of (a) is a 1-valent aromatic group, R_31A～R_33AThe rings may be formed by adjacent groups.

5. 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),

[ solution 40]

In the formula (15), R_11AIs an alkyl group having 1 to 12 carbon atoms, a1 is an integer of 0 to 5, R_12AIs a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R_13AAnd R_14AEach independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, and when a1 is an integer of 2 or more, R_11AEach of which may be the same or different,

[ solution 41]

In the formula (16), R_21AIs an alkyl group having 1 to 12 carbon atoms, R_22AAnd R_23AEach independently represents 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, c1 is an integer of 0 to 5, and when c1 is an integer of 2 or more, R is_21AEach canThe same or different.

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

7. 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.

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

[ solution 42]

In the formula (3), R₆And R₇Each 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, n1+ n2 is 1 or more, and n 1R' s₆And n 2R₇At least one of which is a group represented by the following formula (4),

[ solution 43]

In the formula (4), R₉～R₁₁Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10.

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

[ solution 44]

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

14. A method for producing a pattern cured product, comprising the steps of:

a step of forming a photosensitive resin film by applying the photosensitive resin composition according to any one of claims 1 to 13 to a substrate and drying the composition;

a step of obtaining a resin film by pattern-exposing the photosensitive resin film;

and a step of heat-treating the pattern resin film.

15. The method for producing a patterned cured product according to claim 14, wherein the temperature of the heat treatment is 230 ℃ or lower.

16. 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 pattern cured product.

18. An interlayer insulating film, a cap coat or a surface protective film produced by using the cured product according to claim 16 or 17.

19. An electronic component comprising the interlayer insulating film, the covercoat, or the surface protective film of claim 18.