WO2018155639A1

WO2018155639A1 - Resin composition, cured product, pattern cured product, cured product production method, interlayer insulating film, surface protection film and electronic component

Info

Publication number: WO2018155639A1
Application number: PCT/JP2018/006741
Authority: WO
Inventors: 伸行斉藤; 由香里鯉渕; 生田目　豊
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: 2017-02-23
Filing date: 2018-02-23
Publication date: 2018-08-30
Also published as: CN110300767B; KR20190117503A; KR102511567B1; TW201837084A; TWI762589B; WO2018154688A1; CN110300767A; JP7180588B2; JPWO2018155639A1

Abstract

This resin composition contains: (a) a polyimide or polyimide precursor; (d1) a compound represented by formula (11) or (12); and (d2) one or more compounds selected from the group consisting of a compound represented by formula (13), a compound represented by formula (14), a compound represented by formula (15), and a compound represented by formula (16).

Description

Resin composition, cured product, patterned cured product, method for producing cured product, interlayer insulating film, surface protective film, and electronic component

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

In recent years, organic materials having high heat resistance such as polyimide have been widely applied as protective film materials for semiconductor integrated circuits. A protective film (cured product) using such a polyimide is obtained by heating and curing a resin film formed by applying and drying a polyimide precursor or a resin composition containing a polyimide precursor on a substrate. can get.
With respect to this heat-curing temperature, there is an increasing demand for low-temperature curing. Conventionally, the polyimide precursor is heat-cured at a high temperature of about 370 ° C. However, heat curing at 300 ° C. or lower is required. ing.

It is known that a bifunctional crosslinking agent is effective for application at a curing temperature of about 250 to 300 ° C. (for example, Patent Document 1).

International Publication No. 2015/052885

An object of the present invention is to provide a resin composition, a cured product, a pattern cured product, a method for producing a cured product, an interlayer insulating film, a surface protective film, and an electronic component that can form a cured product having excellent adhesion and chemical resistance. It is.

The present inventors have found that in low-temperature curing, the components remaining in the cured product lower the adhesiveness and chemical resistance.
Furthermore, as a result of intensive studies, the present inventors have found that, when tetraethylene glycol dimethacrylate is used, a crosslinked structure that exhibits good adhesiveness is formed, but adversely affects chemical resistance. Further studies were made from the viewpoint of the number of cross-linking points and the molecular length of the cross-linking agent, and the present invention was achieved.

According to the present invention, the following resin composition and the like are provided.
1. (A) polyimide or polyimide precursor;
(D1) a compound represented by the following formula (11) or (12);
(D2) A group consisting of a compound represented by the following formula (13), a compound represented by the following formula (14), a compound represented by the following formula (15), and a compound represented by the following formula (16) A resin composition containing one or more compounds selected from:

(Wherein R ₁₀₁ is independently a hydrogen atom or a methyl group, R ₁₀₂ is an alkylene group having 1 to 4 carbon atoms, R ₁₀₄ is an alkylene group having 3 to 8 carbon atoms, and n is 2 (It is an integer of ˜5. The plurality of R ₁₀₁ and R ₁₀₂ may be the same or different.)

(Wherein R ₁₁₁ and R ₁₁₃ to R ₁₁₅ are each independently a hydrogen atom, acryloyl group or methacryloyl group, and L ₁ is each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or —R ₁₁₆ - _(oR _{117) n1} - a _{group, R 112} is .A an alkyl group having 1 to 10 carbon atoms, a heterocyclic ring substituted or unsubstituted ring atoms 3 ~ 20 .m is R is an integer of 2 to 6. R ₁₁₆ is a single bond or an alkylene group having 1 to 10 carbon atoms, R ₁₁₇ is an alkylene group having 1 to 10 carbon atoms, n1 is an integer of 1 to 15 . However, at least two _{by R 111} is an acryloyl group or a methacryloyl group, at least two _{R 113} is an acryloyl group or a methacryloyl group, at least two _{R 114} is acryloyl A group or a methacryloyl group, at least two R ₁₁₅ is an acryloyl group or a methacryloyl group.
The plurality of R ₁₁₁ , R ₁₁₃ to R ₁₁₅ and L ₁ may be the same or different. If R ₁₁₆ and _{R 117} have multiple plurality of _{R 116} and _{R 117} may be the same or different. )
2. 2. The resin composition according to 1, wherein the (a) polyimide or polyimide precursor is a polyimide precursor.
3. The resin composition according to 1 or 2, wherein the polyimide precursor has a structural unit represented by the following formula (1).

(In the formula, R ₁ is a tetravalent organic group, R ₂ is a divalent organic group. R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 3 to 20 cycloalkyl groups or monovalent organic groups having a carbon-carbon unsaturated double bond.)
4). 4. The resin composition according to any one of 1 to 3, wherein the polyimide precursor includes structural units represented by the following formulas (1A) to (1C).

(In the formula, X ₁ and X ₂ are each independently a divalent group that is not conjugated to the benzene ring to which they are bonded. R ₃ and R ₄ are each independently a hydrogen atom or an alkyl having 1 to 20 carbon atoms. Group, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond, wherein each R is independently an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. Is a halogenated alkyl group of ˜10, a is each independently an integer of 0 to 3, and b is each independently an integer of 0 to 4. When there are a plurality of R, a plurality of R may be the same Well, it can be different.)
5). 5. The resin composition according to any one of 1 to 4, wherein the component (d1) is a compound represented by the formula (11).
6). 6. The resin composition according to any one of 1 to 5, wherein the component (d2) is a compound represented by the formula (13).
7). 7. The resin composition according to any one of 1 to 6, wherein in the formula (13), R ₁₁₁ is an acryloyl group.
8). The resin composition according to any one of 1 to 7, which further contains (b) a photosensitive agent and is a photosensitive resin composition.
9. The component (b) is (b1) one or more compounds selected from the group consisting of a compound represented by the following formula (21) and a compound represented by the following formula (22), and (b2) the following formula ( The resin composition according to 8, containing one or more compounds selected from the group consisting of one or more compounds selected from the group consisting of a compound represented by 31) and a compound represented by the following formula (32): .

(Wherein R ₁₁ is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R ₁₂ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ₁₃ and R ₁₄ Each 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 ₁₁ may be the same or different.

Wherein R ₁₅ is —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH, R ₁₆ and R ₁₇ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and b1 is an integer of 0 to 5. When b1 is an integer of 2 or more, R ₁₅ may be the same or different.

_{(Wherein, R 21} is an alkyl group having 1 to 12 carbon _{atoms, R 22} and _{R 23} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon A cycloalkyl group, a phenyl group or a tolyl group of 4 to 10, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _{21 s} may be the same or different. )

Wherein R ₂₄ and R ₂₅ are each independently an alkyl group having 1 to 12 carbon atoms, d and e are each independently an integer of 0 to 5, and s and t are each independently 0 And the sum of s and t is 3. When d is an integer of 2 or more, R ₂₄ may be the same or different, and when e is an integer of 2 or more, R ₂₄ ₂₅ may be the same or different, and when s is an integer of 2 or more, the groups in parentheses may be the same or different, and when t is an integer of 2 or more, Each group may be the same or different.)
10. A cured product of the resin composition according to any one of 10.1 to 9.
A pattern cured product of the resin composition according to 11.8 or 9.
A step of applying the resin composition according to any one of 12.1 to 9 on a support substrate and drying to form a resin film;
And the manufacturing method of hardened | cured material including the process of heat-processing the said resin film.
13. The manufacturing method of the hardened | cured material of 12 whose temperature of the said heat processing is 250 degrees C or less.
14 The manufacturing method of the hardened | cured material of 12 whose temperature of the said heat processing is 230 degrees C or less.
15. An interlayer insulating film or a surface protective film produced using the cured product according to 15.10 or the pattern cured product according to 11.
16. An electronic component comprising the interlayer insulating film or surface protective film according to 16.15.

According to the present invention, it is possible to provide a resin composition, a cured product, a patterned cured product, a method for producing a cured product, an interlayer insulating film, a surface protective film, and an electronic component that can form a cured product having excellent adhesion and chemical resistance.

1 is a schematic cross-sectional view of a semiconductor device having an interlayer insulating film and a surface protective film according to an embodiment of the present invention.

Hereinafter, embodiments of the resin composition, the cured product, the pattern cured product, the cured product manufacturing method, the interlayer insulating film, the surface protective film, and the electronic component of the present invention will be described in detail. The present invention is not limited to the following embodiments.

In this specification, “A or B” may include either one of A and B, or may include both. In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. 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. In addition, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. Further, the exemplary materials may be used singly or in combination of two or more unless otherwise specified.

In this specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryloyl group” means “acryloyl group” and “methacryloyl group”.

The resin composition of the present invention comprises (a) a polyimide or a polyimide precursor (hereinafter also referred to as “component (a)”, preferably a polyimide precursor), and (d1) the following formula (11) or (12 ) (Hereinafter also referred to as “component (d1)”), (d2) a compound represented by the following formula (13), a compound represented by the following formula (14), and the following formula (15) ) And one or more compounds selected from the group consisting of compounds represented by the following formula (16) (hereinafter also referred to as “component (d2)”).

Thereby, chemical-resistance and adhesiveness can be made compatible at the time of low temperature hardening.
Furthermore, since the cross-linking agent is present in the cured product while maintaining the cross-linked structure, good adhesion and chemical resistance can be expressed, and the shrinkage of curing is reduced, resulting in a multilayer film Can be ensured.

(Wherein R ₁₁₁ and R ₁₁₃ to R ₁₁₅ are each independently a hydrogen atom, acryloyl group or methacryloyl group, and L ₁ is each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or —R ₁₁₆ - _(oR _{117) n1} - a _{group, R 112} is .A an alkyl group having 1 to 10 carbon atoms, a heterocyclic ring substituted or unsubstituted ring atoms 3 ~ 20 .m is R is an integer of 2 to 6. R ₁₁₆ is a single bond or an alkylene group having 1 to 10 carbon atoms, R ₁₁₇ is an alkylene group having 1 to 10 carbon atoms, n1 is an integer of 1 to 15 . However, at least two _{by R 111} is an acryloyl group or a methacryloyl group, at least two _{R 113} is an acryloyl group or a methacryloyl group, at least two _{R 114} is acryloyl A group or a methacryloyl group, at least two R ₁₁₅ is an acryloyl group or a methacryloyl group.
The plurality of R ₁₁₁ , R ₁₁₃ to R ₁₁₅ and L ₁ may be the same or different. If R ₁₁₆ and _{R 117} have multiple plurality of _{R 116} and _{R 117} may be the same or different. )

The polyimide precursor preferably has a structural unit represented by the following formula (1).

(In the formula, R ₁ is a tetravalent organic group, R ₂ is a divalent organic group. R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 3 to 20 cycloalkyl groups or monovalent organic groups having a carbon-carbon unsaturated double bond.)

In general, the polyimide precursor can be synthesized using a tetracarboxylic acid or a dianhydride thereof and a diamine compound. R ₁ is preferably a residue of tetracarboxylic acid or a dianhydride thereof. R ₂ is preferably a residue of a diamine compound.

The tetravalent organic group of R _{1 in} the formula (1) is preferably a tetravalent organic group represented by the following formulas (2a) to (2e).

(In the formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded. In the formula (2e), Z represents an ether bond (—O—) or (It is a sulfide bond (-S-).)

Examples of the tetracarboxylic acid or dianhydride thereof include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, or 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride. Anhydrides are mentioned.

In addition, with respect to tetracarboxylic acid or dianhydride thereof, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1,2,5 within a range not reducing the stress and i-line transmittance of the cured product. , 6-Naphthalenetetracarboxylic dianhydride is 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic acid Dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3- Hexafluoro-2,2-bis (3,4-dica Boxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis {4 ′-(2,3-dicarboxyphenoxy) phenyl} propane dianhydride, 2,2-bis {4 ′-(3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1 , 3,3,3-hexafluoro-2,2-bis {4 '-(2,3-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-bis {4 '-(3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, etc. It may be used.

Tetracarboxylic acid or its dianhydride may be used alone or in combination of two or more.

The “divalent group that is not conjugated with the benzene ring to be bonded” of X and Y in the formula (2d) is, for example, —O—, —S—, or a divalent group represented by the following formula.

(In the formula, R ₅ represents a carbon atom or a silicon atom. R ₆ each independently represents a hydrogen atom or a halogen atom (for example, a fluorine atom).)

Examples of the diamine compound containing R ₂ include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 2,2 '-Bis (trifluoromethyl) benzidine, 2,2'-dimethylbenzidine, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4 , 4'- (or 3, 4'-, 3, 3'-, 2, 4'-, 2, 2'-) diaminodiphenyl ether, 4, 4'- (or 3, 4'-, 3, 3 ' -, 2,4'-, 2,2 '-) diaminodiphenyl sulfone, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diamino Diphenyl sulfide, o-tolidine, o-tolidine sulfone, 4, 4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4 ' -Benzophenonediamine, bis- {4- (4'-aminophenoxy) phenyl} sulfone, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4 ' -Diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis {4- (3'-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl) ) Propane, diaminopolysiloxane and the like.
These may be used alone or in combination of two or more.

R ₃ and R ₄ in the formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), A cycloalkyl group having 20 (preferably 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms), or a monovalent organic group having a carbon-carbon unsaturated double bond.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
Examples of the monovalent organic group having a carbon-carbon unsaturated double bond include an organic group having a (meth) acryloyl group. Specific examples include (meth) acryloxyalkyl groups having 1 to 10 carbon atoms in the alkyl group.
Examples of the (meth) acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group include (meth) acryloxyethyl group, (meth) acryloxypropyl group, (meth) acryloxybutyl group and the like.

In the case where at least one of R ₃ and R ₄ is a monovalent organic group having a carbon-carbon unsaturated double bond, it is combined with a compound that generates radicals upon irradiation with actinic rays, so This is preferable because crosslinking is possible.

Further, the polyimide precursor may be a polyimide precursor containing structural units represented by the following formulas (1A) to (1C).
Usually, the structural unit represented by Formula (1A) is combined with the structural unit represented by Formula (1B) or the structural unit represented by Formula (1C).

(In the formula, X ₁ and X ₂ are each independently a divalent group that is not conjugated to the benzene ring to which they are bonded. R ₃ and R ₄ are each independently a hydrogen atom or an alkyl having 1 to 20 carbon atoms. Group, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond, wherein each R independently has 1 to 10 carbon atoms (preferably 1 to 3 carbon atoms). An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), or a halogenated alkyl group (for example, a trifluoromethyl group) having 1 to 10 carbon atoms (preferably 1 to 3). Each is an integer of 0 to 3 (preferably 0 or 1), and each b is independently an integer of 0 to 4 (preferably 0 or 1) When R is plural, the plural Rs may be the same , May be different.)

The divalent group that is not conjugated to the benzene ring to which each of X ₁ and X ₂ is bonded is the same as the “divalent group that is not conjugated to the bonded benzene ring” of X and Y in formula (2d). -O- is preferred.

_{R 3} and _{R 4} in the formula (1A) is the same as _{R 3} and _{R 4} in the formula (1).

The tetracarboxylic acid corresponding to the structural unit represented by the formula (1A) or the dianhydride thereof corresponds to the structural unit represented by the formula (1A) among the tetracarboxylic acids or the dianhydrides described above. Examples thereof include tetracarboxylic acid or a dianhydride thereof.
Examples of the diamine compound corresponding to the structural unit represented by Formula (1B) include the diamine compound corresponding to the structural unit represented by Formula (1B) among the diamine compounds described above.
Moreover, as a diamine compound corresponding to the structural unit represented by Formula (1C), the diamine compound etc. corresponding to the structural unit represented by Formula (1C) are mentioned among the diamine compounds mentioned above.
These may be used alone or in combination of two or more.

The molecular weight of the polyimide precursor is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, and more preferably 20,000 to 85,000 in terms of polystyrene. More preferably it is. When the weight average molecular weight is 10,000 or more, the stress after curing tends to be sufficiently reduced. Moreover, when it is 100,000 or less, there exists a tendency for the solubility to a solvent to become favorable, the viscosity of a solution reduces and it becomes easy to improve handleability.
The weight average molecular weight can be measured by a gel permeation chromatography method and can be determined by conversion using a standard polystyrene calibration curve.

Examples of the polyimide include a resin in which the above polyimide precursor is closed.
A polyimide precursor and polyimide may be used in combination.

The component (d1) is a compound represented by the following formula (11) or (12) (preferably a compound represented by formula (11)).

Wherein R ₁₀₁ is independently a hydrogen atom or a methyl group, R ₁₀₂ is an alkylene group having 1 to 4 carbon atoms (preferably an ethylene group), and R ₁₀₄ is an alkylene group having 3 to 8 carbon atoms. group (preferably, n- butylene, cyclohexylene group n-) is, n represents an integer of 2 to 9 (preferably an integer of 2 to 5, more preferably 3 or 4). multiple _{R 101} and R ₁₀₂ may be the same or different.)

As the component (d1), specifically, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol di Examples include acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like.

(D1) A component may be used individually by 1 type and may combine 2 or more types.

Component (d1) is preferably blended in an amount of 5 to 50 parts by weight, more preferably 10 to 35 parts by weight per 100 parts by weight of component (a).
Good adhesiveness can be expressed by being in the said range.

The component (d2) is a compound represented by the following formula (13), a compound represented by the following formula (14), a compound represented by the following formula (15), and a compound represented by the following formula (16). One or more compounds selected from the group consisting of (preferably a compound represented by the formula (13)).

_{(Wherein, R 111} and _R 113 _{~ R 115} are each independently a hydrogen atom, an acryloyl group or a methacryloyl group, _{L 1} are each independently a single bond, an alkylene group (preferably having 1 to 10 carbon atoms, A methylene group, an ethylene group), or a —R ₁₁₆ — (OR ₁₁₇ ) _n1 — group, and R ₁₁₂ is an alkyl group having 1 to 10 carbon atoms (preferably a methyl group or an ethyl group). A substituted or unsubstituted heterocyclic ring having 3 to 20 ring atoms, m is an integer of 2 to 6 (preferably 3 or 4), R ₁₁₆ is a single bond or alkylene having 1 to 10 carbon atoms A group (preferably a methylene group or an ethylene group), R ₁₁₇ is an alkylene group having 1 to 10 carbon atoms (preferably a methylene group or an ethylene group), and n1 is an integer of 1 to 15. Small Kutomo two (preferably, 3 or 4) _{R 111} of an acryloyl group or a methacryloyl group, at least two (preferably 2 or 3) _{R 113} of an acryloyl group or a methacryloyl group, at least two (Preferably 4, 5 or 6) R ₁₁₄ is an acryloyl group or a methacryloyl group, and at least two (preferably 2, 3 or 4) R ₁₁₅ is an acryloyl group or a methacryloyl group.
The plurality of R ₁₁₁ , R ₁₁₃ to R ₁₁₅ and L ₁ may be the same or different. If R ₁₁₆ and _{R 117} have multiple plurality of _{R 116} and _{R 117} may be the same or different. )

In Formula (13), R ₁₁₁ is preferably an acryloyl group.
In the formula (14), R ₁₁₃ is preferably an acryloyl group.
In formula (15), R ₁₁₄ is preferably an acryloyl group.
In the formula (16), R ₁₁₅ is preferably a hydrogen atom or an acryloyl group.

Examples of the heterocyclic ring having 3 to 20 ring atoms of A include an isocyanuric acid ring and a triazine ring. An isocyanuric acid ring and a triazine ring are preferable.
Examples of the substituent for the heterocyclic ring having 3 to 20 ring atoms include the same substituents as described below.

In the formula (13), when there are a plurality of n1, the total of the plurality of n1 is preferably 25 to 40, and more preferably 30 to 40.

As the component (d2), specifically, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetramethacrylate,
Tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate And methacryloyloxyethyl isocyanurate.

(D2) A component may be used individually by 1 type and may combine 2 or more types.

The amount of component (d2) is preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass, relative to 100 parts by mass of component (a).
By being in the said range, the chemical | medical solution tolerance of hardened | cured material can be improved.

The resin composition of the present invention preferably further contains (b) a photosensitizer. Thereby, it can be set as the photosensitive resin composition.
The component (b) is not particularly limited as long as it is a compound that can generate radicals upon irradiation with actinic rays. Examples of actinic rays include ultraviolet rays such as i-rays, visible rays, and radiation.

Examples of the component (b) include oxime compounds, acylphosphine oxide compounds, acyl dialkoxymethane compounds, and the like.

The component (b) is (b1) one or more compounds selected from the group consisting of the compound represented by the following formula (21) and the compound represented by the following formula (22) (hereinafter referred to as “component (b1)”. It is also preferable to contain.
The component (b1) preferably has higher sensitivity to actinic rays than the component (b2) described later, and is preferably a highly sensitive photosensitizer.

In the formula (21), R ₁₁ is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R ₁₂ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a phenyl group or a tolyl group. When a1 is an integer of 2 or more, R ₁₁ may be the same or different.

R ₁₁ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1. R ₁₂ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. R ₁₃ and R ₁₄ are preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

Examples of the compound represented by the formula (21) include a compound represented by the following formula (21-1), and are available as “IRGACURE OXE 02” manufactured by BASF Japan Ltd.

In the formula (22), R ₁₅ is —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH. R ₁₆ and R ₁₇ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group. . b1 is an integer of 0 to 5. When b1 is an integer of 2 or more, R ₁₅ may be the same or different.
R ₁₅ is preferably —O (CH ₂ ) ₂ OH. b1 is preferably 0 or 1. R ₁₆ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or a hexyl group. R ₁₇ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and more preferably a methyl group or a phenyl group.

Examples of the compound represented by the formula (22) include a compound represented by the following formula (22-1), and are available as “IRGACURE OXE 01” manufactured by BASF Japan Ltd. Moreover, the compound represented by the following formula (22-2) is mentioned, and is available as “NCI-930” manufactured by ADEKA Corporation.

The component (b) is composed of (b2) one or more compounds selected from the group consisting of the compound represented by the following formula (31) and the compound represented by the following formula (32) (hereinafter referred to as “(b2) It is also preferable to contain a component ".
The component (b2) preferably has a lower sensitivity to actinic rays than the component (b1), and is preferably a standard photosensitizer.

In the formula (31), R ₂₁ is an alkyl group having 1 to 12 carbon atoms, and R ₂₂ and R ₂₃ 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 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 ₂₁ may be the same or different.

c1 is preferably 0. R ₂₂ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. R ₂₃ is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and further preferably a methoxy group or an ethoxy group.

Examples of the compound represented by the formula (31) include a compound represented by the following formula (31-1), which is available as “G-1820 (PDO)” manufactured by Lambson.

In the formula (32), R ₂₄ and R ₂₅ are each independently an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), and d and e are each independently an integer of 0 to 5 And s and t are each independently an integer of 0 to 3, and the sum of s and t is 3. When d is an integer of 2 or more, R ₂₄ may be the same or different. When e is an integer of 2 or more, R ₂₅ may be the same or different. When s is an integer of 2 or more, the groups in parentheses may be the same or different. When t is an integer of 2 or more, the groups in parentheses may be the same or different.

d is preferably 0. R ₂₅ is preferably each independently an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. e is preferably an integer of 2 to 4, more preferably 3. The combination (s, t) of s and t is preferably (1, 2) or (2, 1).

Examples of the compound represented by the formula (32) include a compound represented by the following formula (32-1), which is available as “IRGACURE TPO” manufactured by BASF Japan Ltd. Moreover, the compound represented by the following formula (32-2) is mentioned, and is available as “IRGACURE 819” manufactured by BASF Japan Ltd.

(B) A component may be used individually by 1 type and may combine 2 or more types.

The component (b) preferably contains one or more selected from the group consisting of the component (b1) and the component (b2).
Moreover, it is preferable that (b) component contains (b1) component and (b2) component.
It is more preferable to use the compound represented by the above formula (21) as the component (b1) and the compound represented by the above formula (32) as the component (b2).

When the component (b) is contained, the amount of the component (b) is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the component (a).
By being within the above range, it is possible to maintain both the remaining film ratio and good resolution in a wide range of exposure.

When the component (b1) and the component (b2) are contained, the content of the component (b1) is usually 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the component (a), preferably 0. 0.05 to 1.0 part by mass, and more preferably 0.15 to 0.6 part by mass.

When the component (b1) and the component (b2) are contained, the content of the component (b2) is usually 0.5 to 10.0 parts by mass, preferably 0 with respect to 100 parts by mass of the component (a). .5 to 5.0 parts by mass.

When the component (b1) and the component (b2) are contained, the content of the component (b1) is 0.05 to 5.00 parts by mass with respect to 100 parts by mass of the component (a), and the component (b2) The content of is preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of component (a).

When the component (b1) and the component (b2) are contained, the mass ratio of the content of the component (b1) and the component (b2) is preferably 1: 3 to 1:30, more preferably 1: 5 to 1:20.

When the component (b1) and the component (b2) are contained, the total amount of the component (b1) and the component (b2) is preferably 0.6 to 11.0 parts by mass with respect to 100 parts by mass of the component (a). More preferably, it is 1.0 to 6.0 parts by mass, and still more preferably 1.15 to 5.6 parts by mass.

The resin composition of the present invention may further contain (c) a solvent (hereinafter also referred to as “component (c)”).

As the solvent for component (c), an organic solvent is preferred.
As the component (c), preferable examples include gamma butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylsulfoxide, hexamethylphosphoryl Examples include polar solvents such as amide, dimethylimidazolidinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N, N-dimethylpropanamide and N-acetyl-ε-caprolactam.

Further, as the component (c), for example, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like may be used.
Specifically, for example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxy Propane, propylene glycol 1-monomethyl ether 2-acetate and the like can be used.

(C) A component may be used individually by 1 type, or may use 2 or more types together.

When the component (c) is included, the amount of the component (c) is preferably 50 to 1000 parts by mass, more preferably 100 to 500 parts by mass with respect to 100 parts by mass of the component (a).

The resin composition of the present invention may further contain (e) a sensitizer (hereinafter also referred to as “(e) component”). This makes it possible to maintain both the remaining film ratio and good resolution in a wide range of exposure amounts.

(E) Sensitizers include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10- Anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis- (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2 -Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, diacetylbenzyl, benzyldimethyl ketal, benzyl diethyl ketal, dipheni Disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis (p-diethylaminobenzylidene) -4-methyl-4-azacyclohexanone, 6-bis (p-dimethylaminobenzylidene) -cyclopentanone, 2,6-bis (p-diethylaminobenzylidene) -4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compound, biscoumarin compound, N-phenylglycine, N-phenyldiethanolamine, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.

(E) A component may be used individually by 1 type, or may use 2 or more types together.

When the component (e) is contained, the amount of the component (e) is preferably 0.1 to 1.0 part by weight, and 0.2 to 0.8 part by weight with respect to 100 parts by weight of the component (a). Is more preferable.

The resin composition of the present invention may further contain (f) a stabilizer (hereinafter also referred to as “component (f)”). Thereby, leaving stability can be made favorable.

Examples of the component (f) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2 -Naphtylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, and compounds represented by the following formula F1.

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

When the component (f) is contained, the amount of the component (f) is preferably 0.05 to 1.0 part by weight, and 0.1 to 0.8 part by weight with respect to 100 parts by weight of the component (a). Is more preferable.

The resin composition of the present invention may further contain (g) an adhesive (hereinafter also referred to as “(g) component”). Thereby, the adhesiveness of hardened | cured material and various support substrates can be improved.

As the component (g), 2-ureidomethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, or 4- Examples thereof include ureidobutyltriethoxysilane, and 3-ureidopropyltriethoxysilane is preferred.

(G) A component may be used individually by 1 type, or may use 2 or more types together.

When the component (g) is contained, the blending amount of the component (g) is preferably 0.5 to 10 parts by mass and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the component (a).

The resin composition of the present invention may further contain (h) a rust inhibitor (hereinafter also referred to as “(h) component”). Thereby, discoloration of a copper substrate at the time of using a copper substrate can be prevented, and adhesiveness can be improved.

The component (h) is preferably a compound having a triazole skeleton or a tetrazole skeleton.

As the component (h), 5-aminotetrazole, benzotriazole, 1-hydroxybenzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole And mercaptobenzoxazole. Among these, 5-aminotetrazole, benzotriazole or 1-hydroxybenzotriazole is preferable.

(H) A component may be used individually by 1 type, or may use 2 or more types together.

When the component (h) is contained, the amount of the component (h) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the component (a).

The resin composition of the present invention may further contain a dissolution accelerator, a surfactant, a leveling agent and the like.

The resin composition of the present invention essentially comprises the components (a), (d1) and (d2), and optionally the components (b), except for the solvent (component (c)), (e) to (h). ) Component, a dissolution accelerator, a surfactant, and a leveling agent, and may contain other inevitable impurities as long as the effects of the present invention are not impaired.
The resin composition of the present invention, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass, excluding the solvent (component (c)),
(A), (d1) and (d2) components,
(A), (b), (d1) and (d2) components or (a), (b), (d1) and (d2) components, and optionally (e) to (h) components, dissolution promoters, You may consist of surfactant and a leveling agent.

The cured product of the present invention can be obtained by curing the above-described resin composition.
When the photosensitive resin composition is used, the cured product of the present invention may be used as a cured product having a pattern (hereinafter referred to as a pattern cured product) or may be used as a cured product having no pattern.
The film thickness of the cured product of the present invention is preferably 1 to 20 μm.

The method for producing a cured product of the present invention includes a step of applying the resin composition described above on a support substrate and drying to form a resin film, and a step of heat-treating the resin film. Furthermore, you may provide the process of exposing.

Moreover, in the manufacturing method of pattern hardened | cured material, the above-mentioned photosensitive resin composition is apply | coated and dried on a support substrate, the process of forming the photosensitive resin film, the process of pattern-exposing the photosensitive resin film, pattern exposure, for example The resin film is developed using an organic solvent to obtain a pattern resin film, and the pattern resin film is heated.

Examples of the support substrate include a metal substrate such as Cu, a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride, and the like.
Examples of the coating method include dipping, spraying, screen printing, and spin coating.

As drying, for example, drying is performed by heating using a hot plate, an oven, or the like (for example, 90 to 150 ° C., 1 to 5 minutes).
The thickness of the resulting photosensitive resin film is preferably 1 to 20 μm.

As the exposure for pattern exposure, it is preferable to use the light described in the component (b). After exposure, post-exposure heating (PEB) may be performed as necessary. The post-exposure heating temperature is preferably 70 ° C. to 140 ° C., and the post-exposure heating time is preferably 1 minute to 5 minutes.

The temperature of the heat treatment is preferably 250 ° C. or lower, and more preferably 230 ° C. or lower. Thereby, a cyclization reaction and a crosslinking reaction proceed and a film can be formed.
The heat treatment time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours.
Multi-stage heating may be performed.

The heat treatment can be performed using, for example, an oven such as an inert gas oven, 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. . In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the process under nitrogen because the oxidation of the pattern can be prevented.

The cured product of the present invention can be used as an interlayer insulating film or a surface protective film.
The interlayer insulating film and the surface protective film of the present invention can be used for electronic parts and the like. Thereby, an electronic component with high reliability can be obtained.
The electronic component of the present invention can be used for semiconductor devices, multilayer wiring boards, and the like. The semiconductor device and the multilayer wiring board can be used for various electronic devices.
The electronic component of the present invention is not particularly limited except that it has the above-described surface protective film, interlayer insulating film, and the like, and can have various structures.

FIG. 1 shows a schematic cross-sectional view of a semiconductor device having an interlayer insulating film and a surface protective film of the present invention. An Al wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the Al wiring layer 2, and a surface protective layer of the device A (surface protective film) 4 is formed. A rewiring layer 6 is formed from the pad portion 5 of the wiring layer 2 and extends to an upper portion of the core 8 which is a connection portion with a conductive ball 7 formed of solder, gold or the like as an external connection terminal. Further, a cover coat layer 9 is formed on the surface protective layer 4. The rewiring layer 6 is connected to the conductive ball 7 through the barrier metal 10, and a collar 11 is provided to hold the conductive ball 7. When a package having such a structure is mounted, an underfill 12 may be interposed in order to further relieve stress.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. In addition, this invention is not limited to the following Example.

Synthesis Example 1 (Synthesis of Polymer I)
In a 1.0 liter flask equipped with a stirrer and a thermometer, 62.0 g (199.9 mmol) of 4,4′-oxydiphthalic dianhydride, 5.2 g (40.0 mmol) of 2-hydroxyethyl methacrylate and catalyst Amount of 1,4-diazabicyclo [2.2.2. Octanetriethylenediamine was dissolved in 250.0 g of N-methyl-2-pyrrolidone, stirred at 45 ° C. for 1 hour and then cooled to 25 ° C., and 5.5 g (50.9 mmol) of m-phenylenediamine, After adding 23.8 g (118.9 mmol) of dianiline (4,4′-diaminodiphenyl ether) and 100 mL of dried N-methyl-2-pyrrolidone, the mixture was stirred at 45 ° C. for 150 minutes and then cooled to room temperature. To this solution, 78.5 g (373.8 mmol) of trifluoroacetic anhydride was added dropwise and stirred for 20 minutes. Then, 53.1 g (408.0 mmol) of 2-hydroxyethyl methacrylate was added and stirred at 45 ° C. for 20 hours. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. This is polymer I.
The weight average molecular weight was calculated | required on condition of the following by standard polystyrene conversion using the gel permeation chromatograph (GPC) method. The weight average molecular weight of the polymer I was 35,000.

It measured using 1 ml of solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of polymer I.
Measuring device: Detector RID-20AD manufactured by Shimadzu Corporation
Pump: LC-20AD manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 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

Synthesis Example 2 (Synthesis of Polymer II)
In a 1.0 liter flask equipped with a stirrer and a thermometer, 62.0 g (199.9 mmol) of 4,4′-oxydiphthalic dianhydride, 5.2 g (40.0 mmol) of 2-hydroxyethyl methacrylate and catalyst Amount of 1,4-diazabicyclo [2.2.2. Octanetriethylenediamine was dissolved in 250.0 g of N-methyl-2-pyrrolidone, stirred at 45 ° C. for 1 hour, cooled to 25 ° C., and 35.95 g (169.8 mmol) of 2,2′-dimethylbenzidine. ) And 100 mL of dried N-methyl-2-pyrrolidone, followed by stirring at 45 ° C. for 150 minutes and then cooling to room temperature. To this solution, 78.5 g (373.8 mmol) of trifluoroacetic anhydride was added dropwise and stirred for 20 minutes. Then, 53.1 g (408.0 mmol) of 2-hydroxyethyl methacrylate was added and stirred at 45 ° C. for 20 hours. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. This is designated as Polymer II.
The weight average molecular weight of Polymer II was determined in the same manner as in Synthesis Example 1. The weight average molecular weight of the polymer II was 35,000.

Examples 1 to 7 and Comparative Example 1
(Preparation of resin composition)
A resin composition was prepared with the components and blending amounts shown in Table 1. The blending amounts in Table 1 are the parts by mass of the components (b) to (h) with respect to 100 parts by mass of the component (a).

Each component used is as follows. As the component (a), the polymer I obtained in Synthesis Example 1 and the polymer II obtained in Synthesis Example 2 were used.

(B) Component B1: G-1820 (PDO) (Lambson, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime)

(C) Component NMP: N-methyl-2-pyrrolidone

(D1) Component D1-1: TEGDMA (Sartomer, tetraethylene glycol dimethacrylate)

(D2) Component D2-1: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., tetramethylolmethane tetraacrylate, compound represented by the following formula D2-1)
D2-2: A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate, compound represented by the following formula D2-2)
D2-3: M-215 (manufactured by Shin-Nakamura Chemical Co., Ltd., acryloyloxyethyl isocyanurate, compound represented by the following formula D2-3)
D2-4: A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd., trimethylolpropane triacrylate, compound represented by the following formula D2-4)
D2-5: DPE-6A (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate, a compound represented by the following formula D2-5)

(E) Component E1: 4,4′-bis (diethylamino) benzophenone

(F) Component F1: Taobn (a compound represented by the following formula F1 manufactured by Hampford Research)

(G) Component G1: UCT-801 (manufactured by United Chemical Technologies, 3-ureidopropyltriethoxysilane)

(H) Component H1: 1,2,3-benzotriazole (Wako Pure Chemical Industries, Ltd.)
H2: 5-aminotetrazole

(Manufacture of cured product)
The obtained resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 110 ° C. for 4 minutes, and the solvent was evaporated to obtain a coating film having a film thickness of 13 μm after curing. . This was heat-cured at 225 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured product.

(Residual film rate after curing)
In the production of the cured product, the film thickness after heating for 4 minutes on a 110 ° C. hot plate and the film thickness after curing were measured using Filmetics (manufactured by Filmetics). ). The cured film thickness of 10 μm was divided by the film thickness after heating for 4 minutes on a 110 ° C. hot plate, and then the percentage was obtained to determine the remaining film ratio after curing. The results are shown in Table 1.

(Measurement of GTN-68P chemical resistance)
GTN-68P (manufactured by Senju Metal Industry Co., Ltd.) was applied to the cured product with a pipette. The cured product after application was placed on a hot plate at 245 ° C. and held for 1 minute. Thereafter, the cured product was moved from the hot plate and cooled to room temperature. The cured product after cooling was washed with isopropyl alcohol and dried, and then the film thickness was measured.
The film thickness change rate (%) was calculated from the film thickness change before and after the application of GTN-68P. A positive value means membrane swelling, and a negative value means membrane dissolution. The results are shown in Table 1.

(Measurement of WS-600 chemical resistance)
GTN-68P was measured in the same manner as the chemical resistance, except that WS-600 (manufactured by Alpha Advanced Materials) was used instead of GTN-68P. The results are shown in Table 1.

(Production of cured product on Cu substrate)
A cured product was obtained in the same manner as in the above (manufacture of cured product) except that a Cu substrate was used instead of the 6-inch silicon wafer.

(Adhesive evaluation)
Using a cross-cut guide (manufactured by Kortec Co., Ltd.), with a razor, cut 10 × 10 grids into the cured product obtained by manufacturing the cured product on the above-described Cu substrate. Divided into 100 pieces.
Adhesive tape (manufactured by 3M Japan Co., Ltd.) was applied thereto, and the adhesive tape was peeled off. When peeling the adhesive tape, the adhesiveness was evaluated as follows according to the number of small pieces of the cured product peeled from the substrate. The results are shown in Table 1.
A: The remaining mass was 100-80.
B: The remaining mass was less than 80

Examples 8 to 9 and Comparative Examples 2 to 3
(Preparation of resin composition)
A resin composition was prepared with the components and blending amounts shown in Table 2. The compounding quantity of Table 2 is a mass part of each component with respect to 100 mass parts of (a) component.

Each component used is as follows. Polymers I, NMP, D1-1, D2-1, F1 and G1 are as described above.

(B) Component B2: IRGACURE OXE-02 (manufactured by BASF Japan Ltd., Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyl) Oxime)
B3: IRGACURE 819 (manufactured by BASF Japan Ltd., bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide)

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

(H) Component H2: 5-aminotetrazole

(Manufacture and evaluation of cured products)
With respect to the obtained resin composition, cured products were produced in the same manner as in Examples 1 to 7 and Comparative Example 1, and GTN-68P chemical resistance, WS-600 chemical resistance and adhesiveness were evaluated. The results are shown in Table 2.

The resin composition of the present invention can be used for electronic parts such as semiconductor devices, multilayer wiring boards, and various electronic devices.

Although several embodiments or examples of the present invention have been described in detail above, those skilled in the art will recognize many examples or examples without departing from the novel teachings and advantages of the present invention. It is easy to make changes. Accordingly, many of these modifications are within the scope of the present invention.
The contents of this application and all the contents of the international application on which the priority of Paris of the present application is based are incorporated herein by reference.

Claims

(A) polyimide or polyimide precursor;
(D1) a compound represented by the following formula (11) or (12);
(D2) A group consisting of a compound represented by the following formula (13), a compound represented by the following formula (14), a compound represented by the following formula (15), and a compound represented by the following formula (16) A resin composition containing one or more compounds selected from:

(Wherein R 101 is independently a hydrogen atom or a methyl group, R 102 is an alkylene group having 1 to 4 carbon atoms, R 104 is an alkylene group having 3 to 8 carbon atoms, and n is 2 (It is an integer of ˜5. The plurality of R 101 and R 102 may be the same or different.)

(Wherein R 111 and R 113 to R 115 are each independently a hydrogen atom, acryloyl group or methacryloyl group, and L 1 is each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or —R 116 - (oR 117) n1 - a group, R 112 is .A an alkyl group having 1 to 10 carbon atoms, a heterocyclic ring substituted or unsubstituted ring atoms 3 ~ 20 .m is R is an integer of 2 to 6. R 116 is a single bond or an alkylene group having 1 to 10 carbon atoms, R 117 is an alkylene group having 1 to 10 carbon atoms, n1 is an integer of 1 to 15 . However, at least two by R 111 is an acryloyl group or a methacryloyl group, at least two R 113 is an acryloyl group or a methacryloyl group, at least two R 114 is acryloyl A group or a methacryloyl group, at least two R 115 is an acryloyl group or a methacryloyl group.
The plurality of R 111 , R 113 to R 115 and L 1 may be the same or different. If R 116 and R 117 have multiple plurality of R 116 and R 117 may be the same or different. )
2. The resin composition according to claim 1, wherein the (a) polyimide or polyimide precursor is a polyimide precursor.
The resin composition according to claim 1 or 2, wherein the polyimide precursor has a structural unit represented by the following formula (1).

(In the formula, R 1 is a tetravalent organic group, R 2 is a divalent organic group. R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 3 to 20 cycloalkyl groups or monovalent organic groups having a carbon-carbon unsaturated double bond.)
The resin composition according to any one of claims 1 to 3, wherein the polyimide precursor includes structural units represented by the following formulas (1A) to (1C).

(In the formula, X 1 and X 2 are each independently a divalent group that is not conjugated to the benzene ring to which they are bonded. R 3 and R 4 are each independently a hydrogen atom or an alkyl having 1 to 20 carbon atoms. Group, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond, wherein each R is independently an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. Is a halogenated alkyl group of ˜10, a is each independently an integer of 0 to 3, and b is each independently an integer of 0 to 4. When there are a plurality of R, a plurality of R may be the same Well, it can be different.)
The resin composition according to any one of claims 1 to 4, wherein the component (d1) is a compound represented by the formula (11).
The resin composition according to any one of claims 1 to 5, wherein the component (d2) is a compound represented by the formula (13).
7. The resin composition according to claim 1, wherein in the formula (13), R 111 is an acryloyl group.
The resin composition according to any one of claims 1 to 7, which further comprises (b) a photosensitive agent and is a photosensitive resin composition.
The component (b) is (b1) one or more compounds selected from the group consisting of a compound represented by the following formula (21) and a compound represented by the following formula (22), and (b2) the following formula ( The resin according to claim 8, comprising one or more compounds selected from the group consisting of one or more compounds selected from the group consisting of a compound represented by 31) and a compound represented by the following formula (32). Composition.

(Wherein R 11 is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R 12 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R 13 and R 14 Each 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 11 may be the same or different.

Wherein R 15 is —OH, —COOH, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH or —COO (CH 2 ) 2 OH, R 16 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and b1 is an integer of 0 to 5. When b1 is an integer of 2 or more, R 15 may be the same or different.

(Wherein, R 21 is an alkyl group having 1 to 12 carbon atoms, R 22 and R 23 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon A cycloalkyl group, a phenyl group or a tolyl group of 4 to 10, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R 21 s may be the same or different. )

Wherein R 24 and R 25 are each independently an alkyl group having 1 to 12 carbon atoms, d and e are each independently an integer of 0 to 5, and s and t are each independently 0 And the sum of s and t is 3. When d is an integer of 2 or more, R 24 may be the same or different, and when e is an integer of 2 or more, R 24 25 may be the same or different, and when s is an integer of 2 or more, the groups in parentheses may be the same or different, and when t is an integer of 2 or more, Each group may be the same or different.)
A cured product of the resin composition according to any one of claims 1 to 9.
A pattern cured product of the resin composition according to claim 8 or 9.
Applying the resin composition according to any one of claims 1 to 9 on a support substrate and drying to form a resin film;
And the manufacturing method of hardened | cured material including the process of heat-processing the said resin film.
The method for producing a cured product according to claim 12, wherein the temperature of the heat treatment is 250 ° C or lower.
The method for producing a cured product according to claim 12, wherein the temperature of the heat treatment is 230 ° C or lower.
An interlayer insulating film or a surface protective film produced using the cured product according to claim 10 or the patterned cured product according to claim 11.
An electronic component comprising the interlayer insulating film or surface protective film according to claim 15.