KR20190117503A - Resin composition, hardened | cured material, pattern hardened | cured material, manufacturing method of hardened | cured material, interlayer insulation film, surface protection film, and electronic components - Google Patents

Abstract

(a) a polyimide or a polyimide precursor, (d1) a compound represented by the following formula (11) or (12), (d2) a compound represented by the following formula (13), represented by the following formula (14) A resin composition containing at least one compound selected from the group consisting of a compound, a compound represented by the following formula (15), and a compound represented by the following formula (16).

Description

Resin composition, hardened | cured material, pattern hardened | cured material, manufacturing method of hardened | cured material, interlayer insulation film, surface protection film, and electronic components

This invention relates to a resin composition, hardened | cured material, a pattern hardened | cured material, the manufacturing method of hardened | cured material, an interlayer insulation film, a surface protective film, and an electronic component.

Recently, an organic material having high heat resistance such as polyimide has been widely applied as a protective film material of a semiconductor integrated circuit. A protective film (cured product) using such a polyimide can be obtained by heating and curing a resin film formed by coating and drying a resin composition containing a polyimide precursor or a polyimide precursor on a substrate.

With respect to this heat-hardening temperature, the request of low temperature hardening is high and conventionally, although the heat hardening of the polyimide precursor was performed at the high temperature of about 370 degreeC, heat hardening of 300 degrees C or less is calculated | required.

And in order to apply at the hardening temperature of about 250-300 degreeC, it is known that using a bifunctional crosslinking agent is effective (for example, patent document 1).

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 capable of forming a cured product excellent in adhesion and chemical resistance.

The present inventors discovered that at low temperature hardening, the component which remained in hardened | cured material reduces adhesiveness and chemical liquid tolerance.

Further, the inventors of the present invention conducted a thorough study and found that when tetraethylene glycol dimethacrylate is used, a crosslinked structure exhibiting good adhesion is formed, but adversely affects chemical resistance. And from a viewpoint of the number of crosslinking points of a crosslinking agent, and a molecular length, further research was carried out and the present invention was reached.

According to this invention, the following resin compositions etc. are provided.

1. (a) a polyimide or polyimide precursor,

(d1) the compound represented by following formula (11) or (12),

(d2) 1 selected from the 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): Resin composition containing the above compound.

(In formula, R <_101> is a hydrogen atom or a methyl group each independently, R <_102> is a C1-C4 alkylene group, R <_104> is a C3-C8 alkylene group and n is an integer of 2-5. A plurality of R ₁₀₁ and R ₁₀₂ may be the same or different.)

(In formula, R <_111> and R <_113> -R <_115> are respectively independently a hydrogen atom, an acryloyl group, or a methacryloyl group, L <_1> is respectively independently a single bond, a C1-C10 alkylene group, or- R <_112> -(OR <_117> ) _{n <} 1> _-group and R <_112> is a C1-C10 alkyl group A is a substituted or unsubstituted heterocyclic ring with 3-20 ring atoms, m is 2-6 R ₁₁₆ is a single bond or an alkylene group having 1 to 10 carbon atoms, and R ₁₁₇ is an alkylene group having 1 to 10 carbon atoms, n1 is an integer of 1 to 15. However, at least two R ₁₁₁ are acryl It is a royl group or a methacryloyl group, At least 2 R ₁₁₃ is acryloyl group or a methacryloyl group, At least 2 R ₁₁₄ is acryloyl group or a methacryloyl group, At least 2 R ₁₁₅ is acryloyl group Or methacryloyl group.

A plurality of R ₁₁₁ , R ₁₁₃ to R _115, and L ₁ may be the same or different, respectively. When there are many R <_116> and R <_117> , some R <_116> and R <_117> may be same or different, respectively.)

2. The resin composition of 1 whose said (a) polyimide or polyimide precursor is a polyimide precursor.

3. The resin composition of 1 or 2 in which the said polyimide precursor has a structural unit represented by following formula (1).

(In formula, R <_1> is a tetravalent organic group, R <_2> is a divalent organic group. R <_3> and R <_4> is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, Or a monovalent organic group having a carbon-carbon unsaturated double bond.)

4. Resin composition in any one of 1-3 whose said polyimide precursor contains the structural unit represented by following formula (1A)-(1C).

(In formula, X <_1> and X <_2> are respectively independently the benzene ring to which each is couple | bonded, and the bivalent group which is not conjugated. R <_3> and R <_4> are respectively independently a hydrogen atom and a C1-C20 alkyl group. , A cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond, each independently of each other, an R 1 alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms. Each independently is an integer of 0 to 3, and b is each independently an integer of 0 to 4. When there are a plurality of R's, a plurality of R's may be the same or different.)

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. Resin composition in any one of 1-5 whose said (d2) component is a compound represented by said Formula (13).

7. The resin composition according to any one of 1 to 6, wherein in the formula (13), R ₁₁₁ is an acryloyl group.

8. (b) The resin composition as described in any one of 1-7 which further contains a photosensitive agent and is a photosensitive resin composition.

9. The said (b) component is (b1) 1 or more compound chosen from the group which consists of a compound represented by following formula (21) and a compound represented by following formula (22), and (b2) following formula (31) The resin composition of 8 containing the at least 1 compound chosen from the group which consists of a compound represented by the compound and the at least 1 compound chosen from the group which consists of a compound represented by following formula (32).

(In formula, R <_11> is a C1-C12 alkyl group and a1 is an integer of 0-5. R <_12> is a hydrogen atom or a C1-C12 alkyl group. R <_13> and R <_14> is a hydrogen atom each independently And an alkyl group, a phenyl group, or a tolyl group having 1 to 12 carbon atoms, in the case of an integer where a1 is 2 or more, each of 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 is 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, b1 is an integer of 0 to 5. In the case of an integer of b1 or more, R <_15> may be the same respectively and may differ.)

(In formula, R <_21> is a C1-C12 alkyl group, R <_22> and R <_23> is a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, and a C4-C10 cycloalkyl group each independently. And a phenyl group or a tolyl group, c1 is an integer of 0 to 5. In the case of an integer of c1 or more, R ₂₁ may be the same or different.)

(In formula, R <_24> and R <_25> is a C1-C12 alkyl group each independently, d and e are the integers of 0-5 each independently, s and t are the integers of 0-3 each independently And the sum of s and t is 3. In the case of an integer of 2 or more, R ₂₄ may be the same or different, and in the case of an integer of e or more, R ₂₅ may be the same or different, respectively. In the case of an integer of s being 2 or more, the groups in parentheses may be the same or different.In the case of an integer of t of 2 or more, the groups in parentheses may be the same or different.)

10. Hardened | cured material of the resin composition in any one of 1-9.

The pattern hardened | cured material of the resin composition of 11. 11.

The manufacturing method of hardened | cured material containing the process of apply | coating and drying the resin composition in any one of 12.1-9 on a support substrate, and forming a resin film, and the process of heat-processing the said resin film.

13. The manufacturing method of 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 surface protective film produced by using the cured product according to 10 or the pattern cured product according to 11.

An electronic component comprising the interlayer insulating film or surface protective film described in 16.15.

According to the present invention, it is possible 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 capable of forming a cured product excellent in adhesion and chemical resistance.

BRIEF DESCRIPTION OF THE DRAWINGS It is schematic sectional drawing of the semiconductor device which has the interlayer insulation film and surface protection film which are embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of the resin composition of this invention, hardened | cured material, pattern hardened | cured material, the manufacturing method of hardened | cured material, an interlayer insulation film, a surface protective film, and an electronic component is explained in full detail. In addition, this invention is not limited to the following embodiment.

In this specification, "A or B" should just contain either A and B, and may include both. In addition, in this specification, the term "process" is included in this term as long as the desired action of the process is achieved, even if the process is not clearly distinguishable from other processes.

The numerical range shown using "-" shows the range which includes the numerical value described before and after "-" as minimum value and the maximum value value, respectively. In addition, in this specification, content of each component in a composition means the total amount of the said some substance which exists in a composition, unless there is particular notice when two or more substances corresponding to each component exist in a composition. In addition, as long as an example material is not specifically determined, you may use individually and may use it in combination of 2 or more type.

"(Meth) acrylate" in this specification means "acrylate" and the corresponding "methacrylate". Similarly, "(meth) acryloyl group" means "acryloyl group" and "methacryloyl group".

The resin composition of this invention is (a) polyimide or a polyimide precursor (henceforth also called "(a) component. Preferably it is a polyimide precursor.), (D1) following formula (11) or (12 A compound represented by the following (hereinafter also referred to as "(d1) component"), (d2) a compound represented by the following formula (13), a compound represented by the following formula (14), represented by the following formula (15) And at least one compound selected from the group consisting of compounds represented by the following formula (16) (hereinafter also referred to as "(d2) component").

Thereby, chemical resistance and adhesiveness can be compatible at the time of low temperature hardening.

Moreover, since the crosslinking agent exists in hardened | cured material, maintaining a crosslinked structure, favorable adhesiveness and chemical-resistance can be expressed, hardening shrinkage becomes small, and flatness at the time of setting it as a multilayer film can be ensured.

(In formula, R <_101> is a hydrogen atom or a methyl group each independently, R <_102> is a C1-C4 alkylene group, R <_104> is a C3-C8 alkylene group and n is an integer of 2-5. A plurality of R ₁₀₁ and R ₁₀₂ may be the same or different.)

(In formula, R <_111> and R <_113> -R <_115> are respectively independently a hydrogen atom, an acryloyl group, or a methacryloyl group, L <_1> is respectively independently a single bond, a C1-C10 alkylene group, or- R <_112> -(OR <_117> ) _{n <} 1> _-group and R <_112> is a C1-C10 alkyl group A is a substituted or unsubstituted heterocyclic ring with 3-20 ring atoms, m is 2-6 R ₁₁₆ is a single bond or an alkylene group having 1 to 10 carbon atoms, and R ₁₁₇ is an alkylene group having 1 to 10 carbon atoms, n1 is an integer of 1 to 15. However, at least two R ₁₁₁ are acryl It is a royl group or a methacryloyl group, At least 2 R ₁₁₃ is acryloyl group or a methacryloyl group, At least 2 R ₁₁₄ is acryloyl group or a methacryloyl group, At least 2 R ₁₁₅ is acryloyl group Or methacryloyl group.

A plurality of R ₁₁₁ , R ₁₁₃ to R _115, and L ₁ may be the same or different, respectively. R ₁₁₆ R ₁₁₇ and if a plurality, the plurality of R ₁₁₆ and R ₁₁₇ can be the same, respectively, or different.)

It is preferable that a polyimide precursor has a structural unit represented by following formula (1).

(In formula, R <_1> is a tetravalent organic group, R <_2> is a divalent organic group. R <_3> and R <_4> is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, Or a monovalent organic group having a carbon-carbon unsaturated double bond.)

Generally, a polyimide precursor can be synthesize | combined using tetracarboxylic acid or its dianhydride, and a diamine compound. It is preferable that R <_1> is a residue of tetracarboxylic acid or its dianhydride. R ₂ is preferably a residue of a diamine compound.

Tetravalent organic groups of R ₁ in the formula (1), is preferably a tetravalent organic group represented by the following formula (2a) ~ (2e).

(In Formula (2d), X and Y each independently represent a divalent group or a single bond which is not conjugated with the benzene ring to which each is independently bonded. In Formula (2e), Z represents an ether bond (-O-) or sulfone. Feed coupling (-S-).)

Examples of the tetracarboxylic acid or its dianhydride include pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride or 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride.

Moreover, about tetracarboxylic acid or its dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 1,2,5,6 in the range which does not reduce the stress of hardened | cured material and i-ray transmittance | permeability. -Naphthalene tetracarboxylic dianhydride is 2,3,5,6-pyridine tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride , m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic 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 -Dicarboxyphenyl) 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-hex Safluoro-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, or the like may be used.

Tetracarboxylic acid or its dianhydride may be used individually by 1 type, and may combine 2 or more types.

"Divalent group which is not conjugated with the benzene ring couple | bonded" of X and Y of Formula (2d) is -O-, -S-, or a divalent group represented by a following formula, for example.

(In formula, R <_5> is a carbon atom or a silicon atom. R <_6> is a hydrogen atom or a halogen atom (for example, a fluorine atom) each independently.)

As a diamine compound containing R <_2> , 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl and 2,2'-bis (fluoro) -4,4'-diamino Biphenyl, 2,2'-bis (trifluoromethyl) benzidine, 2,2'-dimethylbenzidine, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 1 , 5-diaminonaphthalene, benzidine, 4,4 '-(or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenylether, 4,4 ' -(Or 3,4'-, 3,3'-, 2,4'-, 2,2 '-) diaminodiphenylsulfone, 4,4'-(or 3,4'-, 3,3 ' -, 2,4'-, 2,2 '-) diaminodiphenylsulfide, 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'-diami Nodiphenylmethane, bis {4- (3'-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl) propane, diaminopolysiloxane and the like.

These may be used individually by 1 type and may combine 2 or more types.

R <_3> and R <_4> in Formula (1) are respectively independently a hydrogen atom, a C1-C20 (preferably C1-C10, More preferably, a C1-C6) alkyl group, C3-C20 (preferably Is a cycloalkyl group having 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond.

A methyl group, an ethyl group, n-propyl group, 2-propyl group, n-butyl group etc. are mentioned as a C1-C20 alkyl 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.

As a monovalent organic group which has a carbon-carbon unsaturated double bond, the organic group which has a (meth) acryloyl group is mentioned, for example. Specifically, the (meth) acryloxyalkyl group whose carbon number of an alkyl group is 1-10 is mentioned.

Examples of the (meth) acryloxyalkyl group having 1 to 10 carbon atoms of the alkyl group include a (meth) acryloxyethyl group, a (meth) acryloxypropyl group, and a (meth) acryloxybutyl group.

When at least one of R <_3> and R <_4> is a monovalent organic group which has a carbon-carbon unsaturated double bond, it becomes possible to bridge | crosslink between molecular chains by radical polymerization by combining with the compound which generate | occur | produces a radical by actinic light irradiation. Therefore, it is preferable.

In addition, the polyimide precursor may be a polyimide precursor containing the structural unit represented by following formula (1A)-(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 formula, X <_1> and X <_2> are bivalent groups which are not respectively conjugated with the benzene ring to which each independently couple | bonded. R <_3> and R <_4> is respectively independently a hydrogen atom, a C1-C20 alkyl group, and C3-C3. Or a cycloalkyl group having a carbon number of 20 or a monovalent organic group having a carbon-carbon unsaturated double bond, each independently of each other, R is an alkyl group having 1 to 10 carbon atoms (preferably 1 to 3), for example, a methyl group, an ethyl group, Propyl group) or a halogenated alkyl group having 1 to 10 carbon atoms (preferably 1 to 3) (for example, a trifluoromethyl group), each independently represent an integer of 0 to 3 (preferably 0 or 1) and b are each independently an integer of 0 to 4 (preferably 0 or 1.) When R is plural, plural Rs may be the same or different.)

The divalent group which is not conjugated with the benzene ring to which each of X ₁ and X ₂ are bonded is the same as the "bivalent group which is not conjugated with the bonded benzene ring" of X and Y in formula (2d). It is preferable that it is -O-.

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

As tetracarboxylic acid or its dianhydride corresponding to the structural unit represented by Formula (1A), tetracarboxylic acid or its dianhydride corresponding to the structural unit represented by Formula (1A) among tetracarboxylic acid or its dianhydride mentioned above Can be mentioned.

As a diamine compound corresponding to the structural unit represented by Formula (1B), the diamine compound etc. corresponding to the structural unit represented by Formula (1B) among the diamine compounds mentioned above are mentioned.

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) among the diamine compounds mentioned above are mentioned.

These may be used individually by 1 type and may combine 2 or more types.

It is preferable that the weight average molecular weights in polystyrene conversion are 10,000-100,000, as for the molecular weight of a polyimide precursor, it is more preferable that it is 15,000-100,000, and it is still more preferable that it is 20,000-85,000. When the weight average molecular weight is 10,000 or more, the stress after curing is easily lowered sufficiently. Moreover, in the case of 100,000 or less, there exists a tendency for the solubility to a solvent to become favorable, and the viscosity of a solution will reduce and it will become easy to improve handleability.

A weight average molecular weight can be measured by the gel permeation chromatography method, and can be calculated | required by conversion using a standard polystyrene calibration curve.

As polyimide, resin etc. which closed the polyimide precursor mentioned above are mentioned.

You may use together a polyimide precursor and a polyimide.

(d1) A component is a compound (preferably, a compound represented by Formula (11)) represented by following formula (11) or (12).

(In formula, R <_101> is respectively independently a hydrogen atom or a methyl group, R <_102> is a C1-C4 alkylene group (preferably ethylene group), R <_104> is a C3-C8 alkylene group (preferably Is n-butylene group, n-hexylene group, n is an integer of 2-9 (preferably an integer of 2-5, More preferably, 3 or 4.) The several R <_101> and R <_102> is May be the same or different.)

Specific examples of the component (d1) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol. Dimethacrylate, 1, 4- butanediol diacrylate, 1, 6- hexanediol diacrylate, 1, 4- butanediol dimethacrylate, 1, 6- hexanediol dimethacrylate, etc. are mentioned.

A component (d1) may be used individually by 1 type, and may combine 2 or more types.

5-50 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (d1) component, 10-35 mass parts is more preferable.

By being in the said range, favorable adhesiveness can be expressed.

(d2) A component is a group which consists of a compound represented by following formula (13), the compound represented by following formula (14), the compound represented by following formula (15), and the compound represented by following formula (16). At least one compound (preferably, the compound represented by formula (13)) is selected.

(In formula, R <_111> and R <_113> -R <_115> are respectively independently a hydrogen atom, an acryloyl group, or a methacryloyl group, and L <_1> is respectively independently a single bond and a C1-C10 alkylene group (preferably is a methylene group, an ethylene group), or a _{-R 116 - (oR 117) n1} -. a group where, R ₁₁₂ is an alkyl group having a carbon number of 1 to 10 (preferably, a methyl group, an ethyl group) is a, substituted or unsubstituted A heterocyclic ring having 3 to 20 ring atoms, m is an integer of 2 to 6 (preferably 3 or 4), and R ₁₁₆ is a single bond or an alkylene group having 1 to 10 carbon atoms (preferably , Methylene group, ethylene group), and R ₁₁₇ is a C1-C10 alkylene group (preferably methylene group, ethylene group) n1 is an integer of 1-15. However, at least 2 (preferably is 3 or 4) and R ₁₁₁ is a group or a methacrylic group as acrylic, at least two (preferably 2 or 3), R ₁₁₃ is an acryloyl group or a methacryloyl group, at least 2 (Preferably, 4, 5 or 6), R ₁₁₄ is an acryloyl group or a methacryloyl group, at least two (preferably 2, 3 or 4) group or a methacrylate of the R ₁₁₅ as acrylic It is a diary.

A plurality of R ₁₁₁ , R ₁₁₃ to R _115, and L ₁ may be the same or different, respectively. When there are many R <_116> and R <_117> , some R <_116> and R <_117> may be same or different, respectively.)

In Formula (13), R ₁₁₁ is preferably an acryloyl group.

In Formula (14), R ₁₁₃ is preferably an acryloyl group.

In Formula (15), R ₁₁₄ is preferably an acryloyl group.

In 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. Isocyanuric acid ring and triazine ring are preferable.

Examples of the substituent on the heterocyclic ring having 3 to 20 ring atoms include the same substituents as the optional substituents described later.

In formula (13), when there are many n1, it is preferable that the sum total of several n1 is 25-40, and 30-40 are more preferable.

Specific examples of the component (d2) include trimethylolpropanediacrylate, trimethylolpropanetriacrylate, trimethylolpropanedimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol. Tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa Methacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanate Nurulate etc. are mentioned.

(d2) A component may be used individually by 1 type and may combine 2 or more types.

5-25 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (d2) component, 10-20 mass parts is more preferable.

By being in the said range, the chemical liquid tolerance of hardened | cured material can be improved.

It is preferable that the resin composition of this invention contains (b) photosensitive agent further. Thereby, it can be set as the photosensitive resin composition.

(b) A component will not be restrict | limited in particular, if it is a compound which can generate | occur | produce a radical by actinic light irradiation. Examples of the active light include ultraviolet rays such as i-rays, visible light, radiation, and the like.

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

(b) A component is (b1) 1 or more compound chosen from the group which consists of a compound represented by following formula (21) and a compound represented by following formula (22) (henceforth "a component (b1).") It is preferable to contain.

It is preferable that (b1) component has a sensitivity with respect to actinic light higher than (b2) component mentioned later, and it is preferable that it is a high sensitivity photosensitive agent.

In formula (21), R <_11> is a C1-C12 alkyl group and a1 is an integer of 0-5. 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 respectively and may differ.

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 each independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

As a compound represented by Formula (21), the compound represented by following formula (21-1) is mentioned, for example, It can obtain as "IRGACURE @ OXE # 02" by BASF Japan.

In 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 0-5. When b1 is an integer greater than or equal to 2, R <_15> may be the same respectively and may differ.

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.

As a compound represented by Formula (22), the compound represented by following formula (22-1) is mentioned, for example, It can obtain as "IRGACURE @ OXE # 01" by BASF Japan Corporation. Moreover, the compound represented by following formula (22-2) is mentioned, It can obtain as "NCI-930" by ADEKA Corporation.

In addition, (b) component is also called (b2) 1 or more compound chosen from the group which consists of a compound represented by following formula (31) and a compound represented by following formula (32) (henceforth "a component (b2)". It is preferable to contain.).

The component (b2) preferably has a lower sensitivity to actinic rays than the component (b1), and is preferably a photosensitive agent having a standard sensitivity.

In formula (31), R <_21> is a C1-C12 alkyl group, R <_22> and R <_23> respectively independently represent a hydrogen atom, a C1-C12 alkyl group (preferably C1-C4), and C1-C12 Is an alkoxy group (preferably C1-C4), a C4-C10 cycloalkyl group, a phenyl group, or a tolyl group, and c1 is an integer of 0-5. In the case of an integer of 2 or more, c ₁ 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 a C1-C12 alkoxy group, more preferably a C1-C4 alkoxy group, still more preferably a methoxy group or an ethoxy group.

As a compound represented by Formula (31), the compound represented by following formula (31-1) is mentioned, for example, It is available as "G-1820 (PDO)" by Lambson.

In formula (32), R <_24> and R <_25> is respectively independently a C1-C12 (preferably C1-C4) alkyl group, d and e are the integers of 0-5 each independently, s and t is an integer of 0-3 each independently, and the sum of s and t is 3. In the case of an integer of d or more, R ₂₄ may be the same or different. In the case of an integer of e or more, R ₂₅ may be the same or different. In the case of an integer where s is 2 or more, the groups in parentheses may be the same or different. In the case of an integer of t 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 becomes like this. Preferably it is an integer of 2-4, More preferably, it is 3. The combination (s, t) of s and t is preferably (1,2) or (2, 1).

As a compound represented by Formula (32), the compound represented by following formula (32-1) is mentioned, for example, It can obtain as "IRGACURE 'TPO" by BASF Japan Corporation. Moreover, the compound represented by following formula (32-2) is mentioned, It can obtain as "IRGACURE # 819" by BASF Japan.

(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).

In addition, it is preferable that (b) component contains (b1) component and (b2) component.

It is more preferable to use the compound represented by the said Formula (21) as a component (b1), and to use the compound represented by the said Formula (32) as a component (b2).

When it contains (b) component, 0.1-15 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (b) component, 0.2-10 mass parts is more preferable.

By being in the said range, maintenance of a residual film rate and favorable resolution can be compatible in a wide range of exposure amount.

When it contains (b1) component and (b2) component, content of (b1) component is 0.05-5.0 mass parts normally with respect to 100 mass parts of (a) component, Preferably it is 0.05-1.0 mass part, More preferably, it is 0.15-0.6 mass part.

When it contains (b1) component and (b2) component, content of (b2) component is 0.5-10.0 mass parts normally with respect to 100 mass parts of (a) component, Preferably it is 0.5-5.0 mass parts.

When (b1) component and (b2) component are included, content of (b1) component is 0.05-5.00 mass parts with respect to 100 mass parts of (a) component, while content of (b2) component is (a) component It is preferable in it being 0.5-10.0 mass parts with respect to 100 mass parts.

When it contains (b1) component and (b2) component, the mass ratio of content of (b1) component and (b2) component becomes like this. Preferably it is 1: 3-1: 30, More preferably, it is 1: 5 ~ 1:20.

When it contains (b1) component and (b2) component, the total amount of (b1) component and (b2) component becomes like this. Preferably it is 0.6-11.0 mass part with respect to 100 mass parts of (a) component, More preferably, Is 1.0-6.0 mass parts, More preferably, it is 1.15-5.6 mass parts.

The resin composition of this invention may further contain the (c) solvent (henceforth also called "(c) component.").

As a solvent of (c) component, an organic solvent is preferable.

As (c) component, As a preferable thing, gamma-butyrolactone, N-methyl- 2-pyrrolidone, N-acetyl- 2-pyrrolidone, N, N- dimethylacetamide, N, N- Dimethyl sulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N, N-dimethylpropanamide, and N-acetyl-ε-caprolactam Polar solvents may be mentioned.

Moreover, as (c) component, you may use ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc., for example.

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, and 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-acetoxypropane, 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 containing (c) component, 50-1000 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (c) component, 100-500 mass parts is more preferable.

The resin composition of the present invention may further contain (e) a sensitizer (hereinafter also referred to as "(e) component"). Thereby, in a wide range of exposure amount, maintenance of a residual film rate and favorable resolution can be made compatible.

(e) As a sensitizer, Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butyl anthraquinone, 1 , 2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis- (diethyl amino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, diacetylbenzyl , Benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrene quinone, riboflavin tetrabutylate, acridine orange, erythrosin, phenanthrene quinone, 2-isopropyl thioxanthone, 2,6- Bis (p-diethylaminobenzylidene) -4-methyl-4-azacyclohexanone, 6-bis (p-dimethylaminobenzylidene) -cyclopentanone, 2,6-bis (p-diethylaminobenzyl Den) -4-phenylcyclohexanone, aminostyrylketone, 3-ketocoumarin compound, biscoumarin compound, N-phenylglycine, N-phenyldiethanolamine, and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone etc. are mentioned.

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

When it contains (e) component, 0.1-1.0 mass part is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (e) component, 0.2-0.8 mass part is more preferable.

The resin composition of the present invention may further contain a (f) stabilizer (hereinafter also referred to as "(f) component"). As a result, the standing stability can be improved.

As the component (f), for example, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogarol, phenothiazine, resorcinol, ordininitrobenzene, paradinitobenzene , Metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, couperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosoamines, and the compound represented by the following formula F1 Can be mentioned.

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

When it contains (f) component, 0.05-1.0 mass part is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (f) component, 0.1-0.8 mass part is more preferable.

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

As the (g) component, 2-ureidomethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureido Butyl trimethoxysilane, 4-ureido butyl triethoxysilane, etc. are mentioned, 3-ureido propyl triethoxysilane is preferable.

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

When it contains (g) component, 0.5-10 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (g) component, 1-8 mass parts is more preferable.

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

As for (h) component, the compound which has a triazole skeleton or a tetrazole skeleton is preferable.

As (h) component, 5-amino tetrazole, benzotriazole, 1-hydroxy benzotriazole, 1H- benzotriazole-1- acetonitrile, benzotriazole-5-carboxylic acid, 1H- benzotriazole-1 Methanol, carboxy benzotriazole, mercaptobenzoxazole, etc. are mentioned. Among these, 5-amino tetrazole, 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 it contains (h) component, 0.1-10 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the compounding quantity of (h) component, 0.2-5 mass parts is more preferable.

The resin composition of this invention may further contain a dissolution promoter, surfactant, a leveling agent, etc.

The resin composition of this invention is essentially (a), (d1) and (d2) component, and (b) component, (e)-(h) component except a solvent ((c) component), It consists of a dissolution promoter, a surfactant, and a leveling agent, and may contain other unavoidable impurities within a range that does not impair the effects of the present invention.

80 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, or 100 mass% of the resin composition of this invention removes a solvent ((c) component),

(a), (d1) and (d2) components,

(a), (b), (d1) and (d2) components or

(a), (b), (d1) and (d2) components, and (e)-(h) component, a dissolution promoter, surfactant, and a leveling agent may be arbitrarily comprised.

The hardened | cured material of this invention can be obtained by hardening the resin composition mentioned above.

When setting it as the photosensitive resin composition, the hardened | cured material of this invention may be used as hardened | cured material with which a pattern was formed (henceforth a pattern hardened | cured material), and may be used as hardened | cured material without a pattern.

As for the film thickness of the hardened | cured material of this invention, 1-20 micrometers is preferable.

The manufacturing method of the hardened | cured material of this invention includes the process of apply | coating and drying the resin composition mentioned above on a support substrate, and forming a resin film, and the process of heat-processing a resin film. Moreover, you may provide the process of exposing.

In addition, in the manufacturing method of a pattern hardened | cured material, the above-mentioned photosensitive resin composition is apply | coated and dried on a support substrate, the process of forming a photosensitive resin film, the process of pattern-exposing the photosensitive resin film, and the resin film which carried out pattern exposure, the organic solvent, for example. And developing to obtain a patterned resin film, and a step of heat treating the patterned resin film.

As the support substrate, it may be a metal substrate, a glass substrate, semiconductor, metal oxide insulator (for example, TiO _2, SiO ₂ and the like), silicon nitride, etc., such as Cu.

As a method of application | coating, an immersion method, a spray method, the screen printing method, the rotation coating method, etc. are mentioned.

As drying, it is made to dry by heating (for example, 90-150 degreeC, 1 to 5 minutes) using a hotplate, oven, etc., for example.

As for the film thickness of the photosensitive resin film obtained, 1-20 micrometers is preferable.

As exposure of pattern exposure, it is preferable to use the light demonstrated by (b) component. After exposure, you may perform post-exposure heating (PEB) as needed. 70 degreeC-140 degreeC is preferable, and, as for the temperature of post-exposure heating, the time of post-exposure heating is 1 minute-5 minutes are preferable.

250 degrees C or less is preferable, and, as for the temperature of heat processing, 230 degrees C or less is more preferable. Thereby, a cyclization reaction and a crosslinking reaction advance and can form a film | membrane.

20 minutes-6 hours are preferable, and, as for the time of heat processing, 30 minutes-3 hours are more preferable.

You may perform multistage heating.

The heat treatment is, for example, an inert gas oven, a quartz tube furnace, a hot plate, a rapid thermal anneal, a vertical diffusion furnace, an infrared curing furnace, It can carry out using ovens, such as an electron beam hardening furnace and a microwave hardening furnace. In addition, although either air or inert atmosphere, such as nitrogen, can be selected, it is preferable to carry out under nitrogen, since the oxidation of a 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 surface protective film of the present invention can be used for electronic parts and the like. Thereby, highly reliable electronic components can be obtained. The electronic component of this invention can be used for a semiconductor device, a multilayer wiring board, etc. The semiconductor device and the multilayer wiring board can be used for various electronic devices and the like.

The electronic component of the present invention is not particularly limited except having the surface protective film, the interlayer insulating film, and the like described above, and can have various structures.

1 is 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, and an insulating layer (insulating film) 3 (for example, a P-SiN layer) is formed on the upper part, and the surface protection of the device A layer (surface protective film) 4 is formed. In the pad part 5 of the wiring layer 2, the redistribution layer 6 is formed, and it extends to the upper part of the core 8 which is a connection part with the electroconductive ball 7 formed with the solder, gold, etc. which are external connection terminals. . Furthermore, the cover coat layer 9 is formed on the surface protection layer 4. The redistribution layer 6 is connected to the conductive balls 7 via a barrier metal 10, but a collar 11 is provided to hold the conductive balls 7. . When mounting the package of such a structure, in order to further relieve stress, the underfill 12 may be interposed.

Example

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated further more concretely based on an Example and a comparative example. 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 a catalytic 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 m-phenylenediamine 5.5 g (50.9 mmol), 23.8 g (118.9 mmol) of oxydianiline (4,4'-diaminodiphenyl ether) and 100 mL of dried N-methyl-2-pyrrolidone were added, followed by stirring at 45 ° C. for 150 minutes. After cooling to room temperature. Trifluoroacetic anhydride 78.5g (373.8mmol) was dripped at this solution, and after stirring for 20 minutes, 53.1g (408.0mmol) of 2-hydroxyethyl methacrylate was added, and it stirred at 45 degreeC for 20 hours. This reaction liquid was dripped at distilled water, the precipitate was collected by filtration, and it dried under reduced pressure, and the polyamic acid ester was obtained. Let this be polymer I.

The weight average molecular weight was calculated | required by standard polystyrene conversion using the gel permeation chromatography (GPC) method on condition of the following. The weight average molecular weight of polymer I was 35,000.

0.5 mg of polymer I was measured using a solution of 1 ml of solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)]].

Measuring device: Detector Shimazu Seisakusho RID-20AD

Pump #: Shimazu Seisakusho LC-20AD

Measurement condition: 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: UV270 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 a catalytic 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 then 2,2′-dimethyl After adding 35.95 g (169.8 mmol) of benzidine and 100 mL of dry N-methyl-2-pyrrolidone, the mixture was stirred at 45 ° C. for 150 minutes and then cooled to room temperature. Trifluoroacetic anhydride 78.5g (373.8mmol) was dripped at this solution, and after stirring for 20 minutes, 53.1g (408.0mmol) of 2-hydroxyethyl methacrylate was added, and it stirred at 45 degreeC for 20 hours. The reaction solution was added dropwise to distilled water, and the precipitates were collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. Let this be polymer II.

The weight average molecular weight of the polymer II was calculated | required similarly to the synthesis example 1. The weight average molecular weight of polymer II was 35,000.

Examples 1-7 and Comparative Example 1

(Preparation of resin composition)

The resin composition was prepared with the component and compounding quantity shown in Table 1. The compounding quantity of Table 1 is a mass part of (b)-(h) component with respect to 100 mass parts of (a) component.

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

(b) ingredients

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

(c) component

NMP: N-methyl-2-pyrrolidone

(d1) component

D1-1: TEGDMA (made by Tautomer, tetraethylene glycol dimethacrylate)

(d2) component

D2-1: A-TMMT (Shin-Nakamura Chemical Co., Ltd. make, tetramethylol methane tetraacrylate, the compound represented by following formula D2-1)

D2-2: A-9300 (made by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate, the compound represented by following formula D2-2)

D2-3: M-215 (Shin-Nakamura Chemical Co., Ltd. make, acryloyloxyethyl isocyanurate, the compound represented by following formula D2-3)

D2-4: A-TMPT (Shin-Nakamura Chemical Co., Ltd. make, trimethylolpropane triacrylate, the compound represented by following formula D2-4)

D2-5: DPE-6A (made by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate, the compound represented by following formula D2-5)

(e) Ingredient

E1: 4,4'-bis (diethylamino) benzophenone

(f) ingredients

F1: Taobn (compound represented by Hampford® Research Company, represented by the following formula F1)

(g) Ingredients

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

(h) Ingredient

H1: 1,2,3-benzotriazole (made by Wakojun Yaku Co., Ltd.)

H2: 5-aminotetrazole

(Production of Hardened Materials)

The obtained resin composition was apply | coated on the 6-inch silicon wafer by the spin coat method, it heated for 4 minutes on the 110 degreeC hotplate, the solvent was volatilized, and the coating film which hardens the film thickness after 13 micrometers was obtained. This was heat-hardened at 225 degreeC for 1 hour in nitrogen atmosphere using the vertical type | mold diffusion furnace (made by Mitshiro Samosa Systems Co., Ltd.), and the hardened | cured material was obtained.

(Residual ratio after curing)

In manufacture of the said hardened | cured material, the film thickness after heating for 4 minutes and the film thickness after hardening were measured using Filmetrics (made by Filmetrics) on the 110 degreeC hotplate (measurement of film thickness is the same below). After dividing 10 micrometers of film thicknesses after hardening by the film thickness after heating for 4 minutes on a 110 degreeC hotplate, it was set as a percentage and the residual film rate after hardening was calculated | required. The results are shown in Table 1.

(Measurement of GTN-68P Drug Resistance)

GTN-68P (made by Senju-Ginjoku Kogyo Co., Ltd.) was apply | coated to the said hardened | cured material with a pipette. The hardened | cured material after application was put on the hot plate at 245 degreeC, and it hold | maintained for 1 minute. Then, hardened | cured material was moved from the hotplate, and it cooled to room temperature. After the hardened | cured material after cooling was wash | cleaned with isopropyl alcohol, and it dried, the film thickness was measured.

The film thickness change rate (%) was computed from the film thickness change before and after GTN-68P application. Positive values indicate swelling of the membrane and negative values indicate dissolution of the membrane. The results are shown in Table 1.

(Measurement of WS-600 drug resistance)

It measured similarly to GTN-68P chemical-resistance except using WS-600 (made by Alpha® Advanced® Materials) 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 (manufacturing a cured product) except that a Cu substrate was used instead of the 6-inch silicon wafer.

(Evaluation of adhesiveness)

Using a crosscut guide (manufactured by Gotech Co., Ltd.) on a cured product obtained by the production of a cured product on the Cu substrate described above, a 10 × 10 checkerboard sheath was cut out with a razor, and the cured product was cut into 100 pieces. Divided into).

The adhesive tape (made by 3M Japan Corporation) was affixed there, and the said adhesive tape was peeled off. When peeling an adhesive tape, adhesiveness was evaluated as follows by the number of the small pieces of hardened | cured material peeled from the board | substrate. The results are shown in Table 1.

A: The remaining mass was 100-80

B: The remaining mass was less than 80

Examples 8-9 and Comparative Examples 2-3

(Preparation of resin composition)

The resin composition was prepared with the component and compounding quantity shown in Table 2. The compounding quantity of Table 2 is the mass part of each component with respect to 100 mass parts of (a) component.

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

(b) ingredients

B2: IRGACURE 'OXE-02 (made by BASF Japan Co., Ltd., ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyl oxime)

B3: IRGACURE # 819 (BASF Japan Corporation make, bis (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide)

(d2) component

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

(h) Ingredient

H2: 5-aminotetrazole

Preparation and Evaluation of Hardened Materials

About the obtained resin composition, hardened | cured material was produced like Example 1-7 and Comparative Example 1, and GTN-68P chemical liquid tolerance, WS-600 chemical liquid resistance, and adhesiveness were evaluated. The results are shown in Table 2.

Industrial availability

The resin composition of this invention can be used for electronic components, such as a semiconductor device, a multilayer wiring board, and various electronic devices.

While the embodiments or examples of the present invention have been described in detail above, those skilled in the art can easily make many changes to these exemplary embodiments or examples without departing substantially from the novel teachings and effects of the present invention. Therefore, many of these modifications are included within the scope of the present invention.

The content of the documents described in this specification and the international application that serves as the basis for the Paris priority of the present application are incorporated herein.

Claims (16)

(a) a polyimide or polyimide precursor,
(d1) the compound represented by following formula (11) or (12),
(d2) 1 selected from the 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): Resin composition containing the above compound.

(In formula, R <_101> is a hydrogen atom or a methyl group each independently, R <_102> is a C1-C4 alkylene group, R <_104> is a C3-C8 alkylene group and n is an integer of 2-5. A plurality of R ₁₀₁ and R ₁₀₂ may be the same or different.)

(In formula, R <_111> and R <_113> -R <_115> are respectively independently a hydrogen atom, an acryloyl group, or a methacryloyl group, L <_1> is respectively independently a single bond, a C1-C10 alkylene group, or- R <_112> -(OR <_117> ) _{n <} 1> _-group and R <_112> is a C1-C10 alkyl group A is a substituted or unsubstituted heterocyclic ring with 3-20 ring atoms, m is 2-6 R ₁₁₆ is a single bond or an alkylene group having 1 to 10 carbon atoms, and R ₁₁₇ is an alkylene group having 1 to 10 carbon atoms, n1 is an integer of 1 to 15. However, at least two R ₁₁₁ are acryl It is a royl group or a methacryloyl group, At least 2 R ₁₁₃ is acryloyl group or a methacryloyl group, At least 2 R ₁₁₄ is acryloyl group or a methacryloyl group, At least 2 R ₁₁₅ is acryloyl group Or methacryloyl group.
A plurality of R ₁₁₁ , R ₁₁₃ to R _115, and L ₁ may be the same or different, respectively. When there are many R <_116> and R <_117> , some R <_116> and R <_117> may be same or different, respectively.) The method according to claim 1,
The resin composition whose said (a) polyimide or polyimide precursor is a polyimide precursor. The method according to claim 1 or 2,
The resin composition in which the said polyimide precursor has a structural unit represented by following formula (1).

(In formula, R <_1> is a tetravalent organic group, R <_2> is a divalent organic group. R <_3> and R <_4> is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, Or a monovalent organic group having a carbon-carbon unsaturated double bond.) The method according to any one of claims 1 to 3,
The resin composition in which the said polyimide precursor contains the structural unit represented by following formula (1A)-(1C).

(In formula, X <_1> and X <_2> are bivalent groups which are not respectively conjugated with the benzene ring to which each independently couple | bonded. R <_3> and R <_4> is respectively independently a hydrogen atom, a C1-C20 alkyl group, and C3-C3. It is a cycloalkyl group of -20, or a monovalent organic group which has a carbon-carbon unsaturated double bond, R is respectively independently a C1-C10 alkyl group, or a C1-C10 halogenated alkyl group. B is an integer of 0 to 3, each independently, an integer of 0 to 4. When R is plural, a plurality of R may be the same or different.) The method according to any one of claims 1 to 4,
Resin composition whose said (d1) component is a compound represented by said Formula (11). The method according to any one of claims 1 to 5,
Resin composition whose said (d2) component is a compound represented by said Formula (13). The method according to any one of claims 1 to 6,
In the formula (13), R ₁₁₁ is acryloyl group. The method according to any one of claims 1 to 7,
(b) The resin composition which further contains a photosensitive agent and is a photosensitive resin composition. The method according to claim 8,
The said (b) component is represented by (b1) at least 1 compound chosen from the group which consists of a compound represented by following formula (21) and a compound represented by following formula (22), and (b2) following formula (31) A resin composition containing at least one compound selected from the group consisting of at least one compound selected from the group consisting of a compound represented by the compound represented by the following formula (32).

(In formula, R <_11> is a C1-C12 alkyl group and a1 is an integer of 0-5. R <_12> is a hydrogen atom or a C1-C12 alkyl group. R <_13> and R <_14> is a hydrogen atom each independently And an alkyl group, a phenyl group, or a tolyl group having 1 to 12 carbon atoms, in the case of an integer where a1 is 2 or more, each of 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 is 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, b1 is an integer of 0 to 5. In the case of an integer of b1 or more, R <_15> may be the same respectively and may differ.)

(In formula, R <_21> is a C1-C12 alkyl group, R <_22> and R <_23> is a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, and a C4-C10 cycloalkyl group each independently. And a phenyl group or a tolyl group, c1 is an integer of 0 to 5. In the case of an integer of c1 or more, R ₂₁ may be the same or different.)

(In formula, R <_24> and R <_25> is a C1-C12 alkyl group each independently, d and e are the integers of 0-5 each independently, s and t are the integers of 0-3 each independently And the sum of s and t is 3. In the case of an integer of 2 or more, R ₂₄ may be the same or different, and in the case of an integer of e or more, R ₂₅ may be the same or different, respectively. In the case of an integer of s being 2 or more, the groups in parentheses may be the same or different.In the case of an integer of t of 2 or more, the groups in parentheses may be the same or different.) Hardened | cured material of the resin composition of any one of Claims 1-9. The pattern hardened | cured material of the resin composition of Claim 8 or 9. The process of apply | coating and drying the resin composition of any one of Claims 1-9 on a support substrate, and forming a resin film,
And the process of heat-processing the said resin film. The method according to claim 12,
The manufacturing method of the hardened | cured material whose temperature of the said heat processing is 250 degrees C or less. The method according to claim 12,
The manufacturing method of the hardened | cured material whose temperature of the said heat processing is 230 degrees C or less. The interlayer insulation film or surface protective film produced using the hardened | cured material of Claim 10 or the pattern hardened | cured material of Claim 11. An electronic component comprising the interlayer insulating film or surface protective film of claim 15.

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