CN112876845A

CN112876845A - Resin composition

Info

Publication number: CN112876845A
Application number: CN202011292920.7A
Authority: CN
Inventors: 鹤井一彦
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2019-11-29
Filing date: 2020-11-18
Publication date: 2021-06-01
Also published as: JP7351201B2; JP2021085030A; KR20210067903A; TW202130736A

Abstract

The present invention addresses the problem of providing a resin composition for obtaining a cured product that has excellent flexibility, halo suppression properties, and heat resistance. The resin composition comprises (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler, wherein the content of the component (C) is less than 40% by mass, based on 100% by mass of nonvolatile components in the resin composition.

Description

Resin composition

Technical Field

The present invention relates to a resin composition containing a polyimide resin. And a cured product, a resin sheet, a multilayer flexible substrate and a semiconductor device obtained using the resin composition.

Background

In recent years, there has been an increasing demand for thinner and lighter semiconductor components with high mounting density. In order to meet this demand, attention is being paid to the use of flexible substrates as substrate substrates for use in semiconductor components. The flexible substrate can be thinner and lighter than the rigid substrate. Further, since the flexible substrate is flexible and deformable, it can be mounted by bending it.

Heretofore, a composition containing a carbodiimide resin has been known (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-027097.

Disclosure of Invention

Problems to be solved by the invention

In order to improve flexibility, a polyimide resin may be added to an insulating material of a flexible substrate, and in this case, if the amount of an inorganic filler contained in the insulating material is small, the halo (halo) phenomenon is conspicuous, and heat resistance tends to be lowered.

The present invention addresses the problem of providing a resin composition for obtaining a cured product that has excellent flexibility, halo suppression properties, and heat resistance.

Means for solving the problems

As a result of intensive studies to solve the problems (technical problems) of the present invention, the present inventors have found that a cured product excellent in flexibility, a halo phenomenon suppression property and heat resistance can be obtained by using a resin composition containing (a) a polyimide resin, (B) a carbodiimide resin and less than 40 mass% of (C) an inorganic filler, and have completed the present invention.

That is, the present invention includes the following:

[1] a resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler,

wherein the content of the component (C) is less than 40% by mass, assuming that the nonvolatile component in the resin composition is 100% by mass;

[2] the resin composition according to the above [1], wherein the weight average molecular weight of the component (A) is 1,000 or more and 100,000 or less;

[3] the resin composition according to the above [1] or [2], wherein the content of the component (A) is 15% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass;

[4] the resin composition according to any one of the above [1] to [3], wherein the content of the component (A) is 35% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass;

[5] the resin composition according to any one of the above [1] to [4], wherein the component (B) is a polycarbodiimide;

[6] the resin composition according to any one of the above [1] to [5], wherein a content of an isocyanato group (isocyanato group) in a molecule of the component (B) is 0.2% by mass or less;

[7] the resin composition according to any one of the above [1] to [6], wherein the content of the component (B) is 3% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass;

[8] the resin composition according to any one of the above [1] to [7], wherein the content of the component (B) is 15% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass;

[9] the resin composition according to any one of the above [1] to [8], wherein the mass ratio of the component (B) to the component (A), (component (B)/component (A)), is 0.1 or more;

[10] the resin composition according to any one of the above [1] to [9], wherein the mass ratio of the component (B) to the component (A), (component (B)/component (A)), is 0.5 or less;

[11] the resin composition according to any one of the above [1] to [10], wherein the component (C) is silica;

[12] the resin composition according to any one of the above [1] to [11], wherein the average particle diameter of the component (C) is 1 μm or less;

[13] the resin composition according to any one of the above [1] to [12], further comprising (D) an epoxy resin;

[14] the resin composition according to any one of the above [1] to [13], further comprising (E) a curing agent;

[15] the resin composition according to the above [14], wherein the component (E) comprises an active ester-based curing agent;

[16] the resin composition according to any one of the above [1] to [15], which is used for forming an insulating layer of a multilayer flexible substrate;

[17] a cured product of the resin composition according to any one of the above [1] to [16 ];

[18] a resin sheet comprising a support and, provided thereon, a resin composition layer formed of the resin composition according to any one of the above [1] to [16 ];

[19] a multilayer flexible substrate comprising an insulating layer formed by curing the resin composition according to any one of the above [1] to [16 ];

[20] a semiconductor device comprising the multilayer flexible substrate according to [19 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the resin composition of the present invention, a cured product excellent in flexibility, halo suppression characteristics and heat resistance can be obtained.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the embodiments and examples described below, and can be implemented by arbitrarily changing the embodiments without departing from the scope of the claims and the equivalent scope thereof.

< resin composition >

The resin composition of the present invention is a resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler, wherein the content of the component (C) is less than 40% by mass. By using such a resin composition, a cured product excellent in flexibility, halo suppression properties, and heat resistance can be obtained.

The resin composition of the present invention may contain any component in addition to the polyimide resin (a), the carbodiimide resin (B), and the inorganic filler (C). Examples of the optional component include (D) an epoxy resin, (E) a curing agent, (F) a curing accelerator, (G) other additives, and (H) an organic solvent. The components contained in the resin composition will be described in detail below.

(A) polyimide resin

The resin composition of the present invention comprises (a) a polyimide resin. (A) The polyimide resin is a resin having an imide bond in a repeating unit. (A) The polyimide resin is not particularly limited, and may include, for example: (1) a resin obtained by imidization of a diamine compound and a tetracarboxylic anhydride, or (2) a resin obtained by imidization of a diisocyanate compound and a tetracarboxylic anhydride. (A) The polyimide resin may further contain a modified polyimide resin such as a siloxane-modified polyimide resin.

(A) The polyimide resin is not particularly limited, and may include a structure represented by formula (a1), for example.

[ chemical formula 1]

。

[ in the formula, X¹The group having a valence of 4 obtained by removing 2-CO-O-CO-atoms from a tetracarboxylic dianhydride may be an organic group formed of 2 or more (for example, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom. X²Denotes the removal of 2-NH groups from a diamine compound₂The 2-valent group obtained or the 2-valent group obtained by removing 2-NCO atoms from the diisocyanate compound may be, for example, a group having a skeleton of 2 or more (for example, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) atoms selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atomTo form an organic group. n represents an integer of 2 or more. Angle (c)

X in the formula (A1)¹And X²The organic group (b) is not particularly limited as long as it is within a chemically stable structure, and may be a structure appropriately selected by those skilled in the art, and may be, for example, a structure of a known polyimide resin. (A) When the polyimide resin contains the structure represented by the formula (a1), the polyimide resin preferably contains the structure represented by the formula (a1) in an amount of 60 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and particularly preferably 95 mass% or more.

The diamine compound used for producing the polyimide resin (a) is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

Examples of the aliphatic diamine compound include: linear aliphatic diamine compounds such as 1, 2-ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-hexamethylenediamine, 1, 5-diaminopentane and 1, 10-diaminodecane; branched aliphatic diamine compounds such as 1, 2-diamino-2-methylpropane, 2, 3-diamino-2, 3-butane and 2-methyl-1, 5-diaminopentane; alicyclic diamine compounds such as 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, and 4,4' -methylenebis (cyclohexylamine); dimer acid type diamines (hereinafter also referred to as "dimer diamines"), and the like.

The dimer acid type diamine refers to dimer acid having two terminal carboxyl groups (-COOH) substituted with aminomethyl (-CH)₂-NH₂) Or amino (-NH)₂) And a diamine compound obtained thereby. Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably, an unsaturated fatty acid having 11 to 22 carbon atoms, and particularly preferably, an unsaturated fatty acid having 18 carbon atoms), and its industrial production process is generally standardized in the industry. The dimer acid, particularly, a dimer acid containing 36 carbon atoms as a main component obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid, which are inexpensive and easily available, can be easily usedIs obtained. Further, the dimer acid may contain a monomer acid, a trimer acid, other polymerized fatty acid, and the like in an arbitrary amount depending on the production method, the degree of purification, and the like. In addition, although a double bond remains after the polymerization reaction of the unsaturated fatty acid, in the present specification, a hydride which is further hydrogenated to reduce the degree of unsaturation is also included in the dimer acid. Commercially available dimer acid type diamines are available, and examples thereof include "PRIAMINE 1073", "PRIAMINE 1074" and "PRIAMINE 1075" manufactured by Croda Japan; "VERSAME 551" and "VERSAME 552" manufactured by Cognis Japan.

Examples of the aromatic diamine compound include: phenylenediamine compounds such as 1, 4-phenylenediamine, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 3, 5-diaminobiphenyl, and 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine; naphthalene diamine compounds such as 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 6-diaminonaphthalene and 2, 3-diaminonaphthalene; 4,4 '-diamino-2, 2' -bis (trifluoromethyl) -1,1 '-biphenyl, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis (4-aminophenyl) propane, 4' - (hexafluoroisopropylidene) diphenylamine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenoxy) phenyl ] propane, 4-aminobenzoic acid, 4-, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, α -bis [4- (4-aminophenoxy) phenyl ] -1, 3-diisopropylbenzene, α -bis [4- (4-aminophenoxy) phenyl ] -1, 4-diisopropylbenzene, 4'- (9-fluorenylidene)) diphenylamine, 2-bis (3-methyl-4-aminophenyl) propane, 2-bis (3-methyl-4-aminophenyl) benzene, 4' -diamino-3, 3 '-dimethyl-1, 1' -biphenyl, 4 '-diamino-2, 2' -dimethyl-1, diphenylamine compounds such as 1' -biphenyl, 9' -bis (3-methyl-4-aminophenyl) fluorene, 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl ] -1,1, 3-trimethylindane, and 5-amino-1, 1' -biphenyl-2-yl 4-aminobenzoate.

The diamine compound may be a commercially available product or a product synthesized by a known method. The diamine compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The diisocyanate compound used for producing the polyimide resin (a) is not particularly limited, and examples thereof include aliphatic diisocyanate compounds, aromatic diisocyanate compounds, and both-terminal isocyanato polyurethanes.

Examples of the aliphatic diisocyanate compound include: linear aliphatic diisocyanate compounds such as 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 8-octamethylene diisocyanate and 1, 12-dodecane diisocyanate; branched aliphatic diisocyanate compounds such as 2,2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2,4, 4-trimethyl-1, 6-hexamethylene diisocyanate and 2, 2-dimethyl-1, 5-pentamethylene diisocyanate; isophorone diisocyanate (IPDI), cyclohexane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate (CHDI), 4-methylcyclohexane-1, 3-diisocyanate, 2-methylcyclohexane-1, 4-diisocyanate, dicyclohexylmethane-4, 4 '-diisocyanate, dicyclohexylether-4, 4' -diisocyanate, 1, 4-bis (isocyanotomethyl) cyclohexane (1, 4-bis (isocyanotomethyl) cyclohexane), 1, 3-bis (isocyanotomethyl) cyclohexane, 3a,4,5,6,7,7 a-hexahydro-4, 7-methanoindan-1, alicyclic diisocyanate compounds such as 8-ylidene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane and the like; dimer acid type diisocyanates and the like.

The dimer acid type diisocyanate means an amino group (-NH) of a dimer acid type diamine as described above₂) A diisocyanate compound obtained by substitution with an isocyanto (-NCO).

Examples of the aromatic diisocyanate compound include: 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, toluene-2, 6-diisocyanate, toluene-2, 4-diisocyanate, toluene-3, 5-diisocyanate, 2-methyl-4, 6-diisopropylphenylene-1, 3-diisocyanate, 2,4, 6-triethylphenylene-1, 3-diisocyanate, 4, 6-diethylphenylene-1, 3-diisocyanate, 2, 5-diethylphenylene-1, 4-diisocyanate, 2,4, 6-triisopropylphenylene-1, 3-diisocyanate, 4, 6-diisopropylphenylene-1, benzene diisocyanate compounds such as 3-diisocyanate, 2, 5-diisopropylphenylene-1, 4-diisocyanate, m-Xylylene diisocyanate, p-Xylylene diisocyanate, tetramethyl-m-Xylylene diisocyanate and tetramethyl-p-Xylylene diisocyanate; naphthalene diisocyanate compounds such as 1, 3-naphthalene diisocyanate (naphthalene diisocyanate), 1, 6-naphthalene diisocyanate, 1, 7-naphthalene diisocyanate, 1, 8-naphthalene diisocyanate, 2, 6-naphthalene diisocyanate and 2, 7-naphthalene diisocyanate; bis (isocyanatobenzene) compounds such as diphenylmethane-4, 4' -diisocyanate, diphenylether-2, 4' -diisocyanate, biphenyl-4, 4' -diisocyanate, 3' -dimethylbiphenyl-4, 4' -diisocyanate, 3' -dimethoxybiphenyl-4, 4' -diisocyanate, 3' -dimethoxydiphenylmethane-4, 4' -diisocyanate and 4,4' -dimethoxydiphenylmethane-3, 3' -diisocyanate.

The both-terminal isocyanato polyurethane may be a product obtained by urethanizing an aliphatic diisocyanate compound and/or an aromatic diisocyanate compound as exemplified above with a both-terminal hydroxyl polymer. Examples of the both-terminal hydroxyl polymer include both-terminal hydroxyl polyolefins such as both-terminal hydroxyl polybutadiene, both-terminal hydroxyl hydrogenated polybutadiene, both-terminal hydroxyl polyisoprene, and both-terminal hydroxyl hydrogenated polyisoprene; and double-terminal hydroxyl polyethers such as double-terminal hydroxypolyethylene glycol, double-terminal hydroxypolypropylene glycol, and double-terminal hydroxypoly1, 4-butanediol.

The number average molecular weight of the polymer having hydroxyl groups at both ends is not particularly limited, but is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more. The upper limit of the number average molecular weight of the both-terminal hydroxyl polymer is not particularly limited, but is preferably 10,000 or less, and more preferably 8,000 or less. The number average molecular weight herein may be a value measured by Gel Permeation Chromatography (GPC) (in terms of polystyrene).

The both-terminal isocyanato polyurethane is, for example, a both-terminal isocyanato polyurethane represented by the formula (A2).

[ chemical formula 2]

。

[ in the formula, X^2aEach independently represents a 2-valent group obtained by removing 2-NCO atoms from an aliphatic diisocyanate compound or an aromatic diisocyanate compound, and may be, for example, an organic group formed of 2 to 50 skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom. X^2bEach independently represents a 2-valent group obtained by removing 2-OH groups from the polymer having hydroxyl groups at both ends, and may be an organic group formed of at least 2 (e.g., 2 to 1,000, 2 to 500) skeleton atoms selected from carbon atoms and oxygen atoms. m represents an integer of 1 to 10. And (c) a temperature sensor.

The diisocyanate compound may be a commercially available product, or a product synthesized by a known method or a method based on the known method. The diisocyanate compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The tetracarboxylic anhydride used for producing the polyimide resin (a) is not particularly limited, and examples thereof include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides.

Specific examples of the aliphatic tetracarboxylic dianhydride include: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1, 2,3, 4-tetracarboxylic dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic dianhydride, 3',4,4' -dicyclohexyltetracarboxylic dianhydride, carbonyl-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, methylene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1, 2-ethylene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, oxy-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, thio-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, cyclopentanetetracarboxylic dianhydride, sulfonyl-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, and the like.

Examples of the aromatic tetracarboxylic dianhydride include: pyromellitic dianhydride such as pyromellitic dianhydride and 1,2,3, 4-pyromellitic dianhydride; naphthalene tetracarboxylic acid dianhydrides such as 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride and 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride; anthracene tetracarboxylic acid dianhydrides such as 2,3,6, 7-anthracene tetracarboxylic acid dianhydride; 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 3,3',4,4' -diphenylether tetracarboxylic dianhydride, 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -benzophenone tetracarboxylic dianhydride, 2,3,3',4' -diphenylether tetracarboxylic dianhydride, 2,3,3',4' -diphenylsulfone tetracarboxylic dianhydride, 2' -bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, methylene-4, 4' -diphthalic dianhydride, 1-ethylidene-4, 4' -diphthalic dianhydride, 2, 2-propylidene-4, 4' -diphthalic dianhydride, 1, 2-ethylene-4, 4' -diphthalic dianhydride, 1, 3-trimethylene-4, 4' -diphthalic dianhydride, 1, 4-tetramethylene-4, 4' -diphthalic dianhydride, 1, 5-pentamethylene-4, 4' -diphthalic dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, And diphthalic dianhydrides such as 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride and 4,4'- (4,4' -isopropylidenediphenoxy) diphthalic dianhydride.

The tetracarboxylic dianhydride may be a commercially available product, or a product synthesized by a known method or a method based on the known method. The tetracarboxylic dianhydride may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the structure derived from the aromatic tetracarboxylic dianhydride constituting the polyimide resin (a) is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, further preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 100 mol% based on the total structure derived from the tetracarboxylic dianhydride.

(A) The weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more. (A) The upper limit of the weight average molecular weight of the polyimide resin is not particularly limited, and is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less. (A) The number average molecular weight of the polyimide resin is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more. (A) The upper limit of the number average molecular weight of the polyimide resin is not particularly limited, and is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less. The weight average molecular weight and the number average molecular weight herein may be values measured by Gel Permeation Chromatography (GPC) (in terms of polystyrene).

The content of the polyimide resin (a) in the resin composition is not particularly limited, and is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 35% by mass or less, and particularly preferably 30% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass. The lower limit of the content of the polyimide resin (a) in the resin composition is not particularly limited, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, further more preferably 15% by mass or more, and particularly preferably 20% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

(B) carbodiimide resin

The resin composition of the present invention comprises (B) a carbodiimide resin. (B) A carbodiimide resin is a compound having 1 or more carbodiimide structures (-N = C = N-) in 1 molecule. As the carbodiimide resin (B), a compound having 2 or more carbodiimide structures in 1 molecule is preferable, and among them, a polycarbodiimide having a carbodiimide structure in a repeating unit is preferable. The polycarbodiimide may be cyclic or linear.

The polycarbodiimide is not particularly limited, and may include, for example, one obtained by intermolecular decarboxylation condensation reaction (decarburizing acid condensation) of a diisocyanate compound. The polycarbodiimide obtained as described above has an isocyanato group (-N = C = O) in the molecule, and a part or all of it may be further treated with a known blocking agent such as a monoisocyanate compound, an alcohol compound, an amine compound, a carboxylic acid compound, or an epoxy compound. Examples of the diisocyanate compound used for producing the polycarbodiimide include the same compounds as "diisocyanate compound used for producing the polyimide resin (a)". (B) The carbodiimide resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(B) The carbodiimide resin is not particularly limited, and for example, a polycarbodiimide containing the structure represented by formula (B1) is preferable.

[ chemical formula 3]

。

[ in the formula, X³The group having a valence of 2 obtained by removing 2-NCO groups from a diisocyanate compound is, for example, an organic group formed by 2 or more (for example, 2 to 50, 2 to 40, 2 to 30, 2 to 20) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, and may be, in one embodiment, an alkylene group, an arylene group, an alkyl-substituted arylene group and a combination thereof. p represents an integer of 2 or more. And (c) a temperature sensor.

The "alkylene group" refers to a linear, branched and/or cyclic aliphatic saturated hydrocarbon group having a valence of 2. The number of carbon atoms of the "alkylene group" may be, for example, 2 to 30, 2 to 20, or the like. Examples of the "alkylene group" include straight-chain alkylene groups such as ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene, and 1, 8-octylene; ethylidene (ethylidene), propylidene, isopropylidene, 1-methylethylidene, 1-ethylidene, 1, 3-propylene, 2-methyl-1, 4-butylene, 2, 3-dimethyl-1, 4-butylene, 1, 3-dimethyl-1, 4-butylene, 2-methyl-1, 5-pentylene, 2-dimethyl-1, 5-pentylene, 2, 4-dimethyl-1, 5-pentylene, 1,3, 5-methyl-1, 5-pentylene, 2-methyl-1, 6-hexylene, 2-dimethyl-1, 6-hexylene, 2, 4-dimethyl-1, branched alkylene groups such as 6-hexylene, 1,3, 5-trimethyl-1, 6-hexylene, 2, 4-trimethyl-1, 6-hexylene, and 2,4, 4-trimethyl-1, 6-hexylene; cyclic alkylene groups such as 1, 3-cyclopentylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, 4-methyl-1, 3-cyclohexylene, 2-methyl-1, 3-cyclohexylene and 2-methyl-1, 4-cyclohexylene; cyclic-linear-cyclic alkylene groups such as methylenebis (4, 1-cyclohexylene); cyclic-branched-cyclic alkylene groups such as isopropylidenebis (4, 1-cyclohexylene); a linear-cyclic-linear alkylene group such as 1, 4-cyclohexylenedimethylene group; branched-cyclic-branched alkylene groups such as 1, 4-cyclohexylenediisopropylidene.

By "arylene" is meant a 2-valent aromatic hydrocarbon radical. The "arylene group" may have 6 to 14, 6 to 10, or the like carbon atoms, for example. Examples of the "arylene group" include 1, 3-phenylene, 1, 4-phenylene, 1, 5-naphthylene, 1, 8-naphthylene, and 2, 6-naphthylene. The "alkyl-substituted arylene group" refers to an arylene group substituted with an alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. The number of carbon atoms of the "alkyl-substituted arylene group" may be, for example, 7 to 30, 7 to 20, or the like. Examples of the "alkyl-substituted arylene group" include, for example, a2, 6-tolyl group, a2, 4-tolyl group, a3, 5-tolyl group, a 2-methyl-4, 6-diisopropyl-1, 3-phenylene group, a2, 4, 6-triethyl-1, 3-phenylene group, a 4, 6-diethyl-1, 3-phenylene group, 2, 5-diethyl-1, 3-phenylene, 2, 5-diethyl-1, 4-phenylene, 2,4, 6-triisopropyl-1, 3-phenylene, 4, 6-diisopropyl-1, 3-phenylene, 2, 5-diisopropyl-1, 4-phenylene, and the like. Examples of the combination of alkylene, arylene, and alkyl-substituted arylene include alkylene-arylene-alkylene, alkylene-alkyl-substituted arylene-alkylene, arylene-alkylene-arylene, and alkyl-substituted arylene-alkylene-alkyl-substituted arylene. The alkylene group, arylene group, and alkyl-substituted arylene group may further have an arbitrary substituent.

X in the formula (B1)³The organic group (b) is not particularly limited as long as it is within a chemically stable structure, and may be a structure appropriately selected by those skilled in the art, and may be, for example, a structure of a known polycarbodiimide.

In one embodiment, specific examples of the carbodiimide resin (B) include aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexylcarbodiimide), and poly (isophorone carbodiimide); or aromatic polycarbodiimides such as poly (phenylene carbodiimide), poly (naphthylene carbodiimide), poly (toluene carbodiimide), poly (methyldiisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylenecarbodiimide), poly (tetramethylxylylenecarbodiimide), poly (methylenediphenylcarbodiimide), and poly [ methylenebis (methylphenylene) carbodiimide ].

(B) The content of an isocyanato group (-N = C = O) in a molecule of the carbodiimide resin is preferably 10% by mass or less, more preferably 5% by mass or less and 3% by mass or less, further preferably 2% by mass or less and 1% by mass or less, further more preferably 0.5% by mass or less and 0.2% by mass or less, and particularly preferably 0% by mass, that is, (B) the carbodiimide resin particularly preferably does not contain an isocyanato group.

Examples of commercially available products of the carbodiimide resin (B) include "CARBODILITE (registered trademark) V-02B", "CARBODILITE (registered trademark) V-03", "CARBODILITE (registered trademark) V-04K", "CARBODILITE (registered trademark) V-07", and "CARBODILITE (registered trademark) V-09", manufactured by Nisshinbo Chemicals K.K.; "Stabaxol (registered trademark) P", "Stabaxol (registered trademark) P400", "Hycasyl (registered trademark) 510", manufactured by Rhein Chemie, Inc., and the like.

The content of the carbodiimide resin (B) in the resin composition is not particularly limited, and is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, further more preferably 15% by mass or less, and particularly preferably 10% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass. The lower limit of the content of the carbodiimide resin (B) in the resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further more preferably 3% by mass or more, and particularly preferably 5% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass.

The mass ratio of the carbodiimide resin (B) to the polyimide resin (a) in the resin composition ((B) carbodiimide resin/(a) polyimide resin) is not particularly limited, but is preferably 5 or less, more preferably 1 or less, further preferably 0.5 or less, and further preferably 0.3 or less. The lower limit of the mass ratio ((B) carbodiimide resin/(a) polyimide resin) is not particularly limited, but is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and further preferably 0.2 or more.

(C) inorganic filler

The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in a particulate state.

As the material of the inorganic filler (C), an inorganic compound is used. Examples of the material of the inorganic filler (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, calcium zirconate titanate, zirconium phosphate, zirconium phosphotungstate and the like. Of these, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. In addition, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone in 1 kind, and may be used in combination in 2 or more kinds at an arbitrary ratio.

Examples of commercially available products of the inorganic filler (C) include "SP 60-05" and "SP 507-05" manufactured by Nippon iron-based alloy materials, Inc.; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C", "SC 2500 SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatech (Admatech); "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N" and "Silfil NSS-5N" manufactured by Deshan, Kuyama, K.K.; UFP-30, DAW-03, FB-105FD, available from Denka corporation; "IMSIL A-8", "IMSIL A-10", "IMSIL A-15" and "IMSIL A-25" manufactured by Unimin.

(C) The average particle size of the inorganic filler is not particularly limited, but is preferably 40 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, further more preferably 3 μm or less, and particularly preferably 1 μm or less. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.005 μm or more, more preferably 0.01 μm or more, further preferably 0.03 μm or more, further more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, it can be determined by: the particle size distribution of the inorganic filler was prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was defined as an average particle size. The measurement sample may be a sample obtained by: 100mg of the inorganic filler and 10g of methyl ethyl ketone were weighed into a vial, and dispersed for 10 minutes by ultrasonic waves. For the measurement sample, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus with the use light source wavelengths being blue and red, and the average particle size as the median particle size was calculated from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1m²A value of at least one per gram, more preferably 0.5m²A total of 1m or more, preferably 1m²A total of 5m or more, particularly 5m²More than g. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 50m²A ratio of 30m or less per gram²A total of 20m or less, preferably²A specific ratio of 15m or less per gram²The ratio of the carbon atoms to the carbon atoms is less than g. Inorganic fillingThe specific surface area of the material can be obtained by: according to the BET method, a specific surface area measuring apparatus (Macsorb HM-1210, Mountech corporation) was used to adsorb nitrogen gas to the sample surface, and the specific surface area was calculated by the BET multipoint method.

(C) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. The moisture resistance and dispersibility of the inorganic filler (C) can be improved by surface treatment. Examples of the surface treatment agent include: vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silane coupling agents such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as p-styryltrimethoxysilane; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; amino silane coupling agents such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene)) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris (trimethoxysilylpropyl) isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride; and the like silane coupling agents; and non-silane-coupled alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1, 6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. Among them, amino silane coupling agents are preferable. The surface treatment agent can be used alone in 1 kind, and can be used in combination in any ratio of 2 or more.

Examples of commercially available surface treatment agents include "KBM-1003" and "KBE-1003" (vinyl silane coupling agent) manufactured by shin-Etsu chemical industries, Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502" and "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-9103P", "KBM-573" and "KBM-575" (amino silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido silane coupling agent); "KBM-802" and "KBM-803" (mercapto silane coupling agents); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (acid anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compound), and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably limited to a predetermined range. Specifically, the inorganic filler is surface-treated with a surface treatment agent in an amount of preferably 0.2 to 5% by mass, more preferably 0.2 to 3% by mass, and still more preferably 0.3 to 2% by mass, based on 100% by mass of the inorganic filler.

The degree of surface treatment based on the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler material. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving the dispersibility of the inorganic filler²Above, more preferably 0.1mg/m²Above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition and the increase in melt viscosity in the form of a sheet, 1.0mg/m is preferable²The concentration is more preferably 0.8mg/m or less²The concentration is more preferably 0.5mg/m or less²The following.

(C) The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is subjected to a washing treatment with a solvent (for example, Methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent may be added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, the solid component was dried, and then the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, there may be used "EMIA-320V" manufactured by horiba, Ltd.

The content of the inorganic filler (C) in the resin composition is less than 40% by mass when the nonvolatile content in the resin composition is 100% by mass, and is preferably 39% by mass or less and 38% by mass or less, more preferably 37% by mass or less, further preferably 35% by mass or less, and particularly preferably 33% by mass or less, from the viewpoint of improving flexibility. The lower limit of the content of the inorganic filler (C) in the resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or more, further more preferably 20% by mass or more, and particularly preferably 30% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

(D) epoxy resin

The resin composition of the present invention may contain (D) an epoxy resin as an optional component. The epoxy resin (D) is a curable resin having an epoxy group.

Examples of the epoxy resin (D) include: a biscresol (bixylenol) type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac type epoxy resin, a phenol novolac type epoxy resin, a tert-butyl-o-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic type epoxy resin, an epoxy resin containing a spiro ring, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a phenol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a phenol novolac type epoxy resin, a phenol type epoxy resin, a heterocyclic type epoxy resin, a phenol novolac type epoxy resin, Trimethylol epoxy resin, tetraphenylethane epoxy resin, isocyanurate epoxy resin, phenophthalimidine epoxy resin, phenolphthalein epoxy resin, and the like. (D) The epoxy resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

As the (D) epoxy resin, the resin composition preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the epoxy resin (D).

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resin"), and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resin"). For the resin composition of the present invention, as the epoxy resin, only a liquid epoxy resin may be contained, or only a solid epoxy resin may be contained, or a liquid epoxy resin and a solid epoxy resin may be contained in combination. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin, and more preferably a solid epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.

As the liquid epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include: "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene epoxy resins) manufactured by DIC; "828 US", "828 EL", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630", "630 LSD" and "604" (glycidyl amine type epoxy resins) manufactured by Mitsubishi chemical corporation; "ED-523T" (glycidyl epoxy resin) manufactured by ADEKA corporation; "EP-3950L" and "EP-3980S" (glycidyl amine type epoxy resins) manufactured by ADEKA corporation; EP-4088S (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nissian Ciki Kaisha; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" manufactured by Daxylonite, and "JP-100" and "JP-200" manufactured by Nippon Caoda (epoxy resin having a butadiene structure); "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron and Japan chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

As the solid epoxy resin, a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenylethane-type epoxy resin, a phenol phthalimidine-type epoxy resin, a phenolphthalein-type epoxy resin are preferable.

Specific examples of the solid epoxy resin include: HP4032H (naphthalene epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH", "HP-7200H" and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resins) manufactured by DIC corporation; EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L", "NC 3000 FH" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; "ESN 475V" (naphthalene type epoxy resin) manufactured by NIPPON STEEL Chemical & Material co., Ltd.) (japanese iron Chemical); ESN485 (naphthol type epoxy resin) manufactured by Nippon iron chemical Co., Ltd; ESN375 (dihydroxynaphthalene type epoxy resin) manufactured by Nippon chemical Co., Ltd; "YX 4000H", "YX 4000 HK" and "YL 7890" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical company; "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; "YX 7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation; "WHR 991S" (phenol-phthalimidine type epoxy resin) manufactured by Nippon chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

When the liquid epoxy resin and the solid epoxy resin are used together as the component (D), the mass ratio of the solid epoxy resin to the liquid epoxy resin (solid epoxy resin/liquid epoxy resin) is not particularly limited, but is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1 or more, and particularly preferably 5 or more. The upper limit of the mass ratio of the solid epoxy resin to the liquid epoxy resin is not particularly limited, and is preferably 100 or less, more preferably 50 or less, further preferably 30 or less, and particularly preferably 20 or less.

(D) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 60g/eq to 2,000g/eq, even more preferably 70g/eq to 1,000g/eq, and even more preferably 80g/eq to 500g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

(D) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).

The content of the epoxy resin (D) in the resin composition is not particularly limited, and is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 35% by mass or less, and particularly preferably 30% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass. The lower limit of the content of the epoxy resin (D) in the resin composition is not particularly limited, and is, for example, 0 mass% or more and 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 10 mass% or more, further more preferably 20 mass% or more, and particularly preferably 25 mass% or more, when the nonvolatile content in the resin composition is 100 mass%.

(E) curing agent

The resin composition of the present invention may further comprise (E) a curing agent. (E) The curing agent has a function of curing the epoxy resin (D). The curing agent (E) is not a component belonging to the components (A) to (D).

The curing agent (E) is not particularly limited, and examples thereof include phenol curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, benzoxazine curing agents, and cyanate curing agents. The curing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. (E) The curing agent preferably contains a curing agent selected from phenol-based curing agents, naphthol-based curing agents, and active ester-based curing agents, and particularly preferably contains an active ester-based curing agent.

As the phenol curing agent and the naphthol curing agent, a phenol curing agent having a novolac resin structure (novolak structure) or a naphthol curing agent having a novolac resin structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to an adherend, a nitrogen-containing phenol curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenol curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a phenol novolac resin containing a triazine skeleton is preferable from the viewpoint of satisfying heat resistance, water resistance, and adhesion at a high level. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include: "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Minghe Kaisha, "NHN", "CBN", "GPH" manufactured by Japan Kasei K.K. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD 2090", "TD-2090-60M" manufactured by Nippon iron chemical Co., Ltd.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-C furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and other polymer type acid anhydrides. As commercially available products of the acid anhydride-based curing agent, "HNA-100" and "MH-700" manufactured by Nissan chemical and chemical Co., Ltd.

The active ester-based curing agent is not particularly limited, and in general, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, can be preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac resin. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol on 1 molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a phenol novolac resin (phenol novolac), and an active ester compound containing a benzoyl compound of a phenol novolac resin are preferable, and among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" refers to a 2-valent structural unit formed from phenylene-dicyclopentylene (ジシクロペンタレン) -phenylene.

Commercially available products of the active ester-based curing agent include: "EXB 9451", "EXB 9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65L", "EXB-8000L-65 TM" (manufactured by DIC) as an active ester compound having a dicyclopentadiene type diphenol structure; "EXB-9416-70 BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC) as an active ester compound having a naphthalene structure; "DC 808" (manufactured by mitsubishi chemical corporation) as an active ester-based curing agent which is an acetylated product of a phenol novolac resin; "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation) as active ester-based curing agents (the active ester-based curing agents are benzoyl compounds of phenol novolac resins); and so on.

Specific examples of the benzoxazine-based curing agent include: "JBZ-OP 100D" and "ODA-BOZ" manufactured by JFE chemical company; "HFB 2006M" available from Showa Polymer Co; "P-d" and "F-a" manufactured by four national chemical industries, Inc.

Examples of the cyanate ester-based curing agent include: bisphenol A dicyanate, polyphenol cyanate ester (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2-bis (4-cyanate-group) phenylpropane, 1-bis (4-cyanate-group phenylmethane), bis (4-cyanate-group-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-group-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate-group-phenyl) sulfide, bis (4-cyanate-group-phenyl) ether and other difunctional cyanate ester resins, polyfunctional cyanate ester resins derived from phenol novolac resin, cresol novolac resin and the like, polyfunctional cyanate ester resins, and the like, Prepolymers obtained by partially triazinating these cyanate ester resins, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (both of which are phenol novolac type polyfunctional cyanate ester resins), "BA 230" and "BA 230S 75" (prepolymers obtained by triazinating a part or all of bisphenol a dicyanate ester to form a trimer), which are manufactured by Lonza japan corporation.

When the resin composition contains (D) an epoxy resin and (E) a curing agent, the amount ratio of (D) the epoxy resin to (E) the curing agent is represented by [ (D) the number of epoxy groups of the epoxy resin ]: the ratio of [ (number of reaction of E) curing agent ] is preferably 1: 0.2-1: 2, more preferably 1: 0.3-1: 1.5, more preferably 1: 0.4-1: 1.4. here, the reactive group of the (E) curing agent differs depending on the type of the curing agent, and for example, if the curing agent is a phenol-based curing agent or a naphthol-based curing agent, the reactive group is an aromatic hydroxyl group, and if the curing agent is an active ester-based curing agent, the reactive group is an active ester group.

(E) The reaction group equivalent of the curing agent is preferably 50g/eq to 3,000g/eq, more preferably 100g/eq to 1,000g/eq, even more preferably 100g/eq to 500g/eq, and particularly preferably 100g/eq to 300g/eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of the reactive group.

(E) When the active ester-based curing agent is contained in the curing agent, the content thereof is not particularly limited, and when the total amount of the (E) curing agent is 100 mass%, the content is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more, and particularly preferably 40 mass% or more.

The content of the (E) curing agent in the resin composition is not particularly limited, and is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, further more preferably 15% by mass or less, and particularly preferably 10% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass. The lower limit of the content of the (E) curing agent in the resin composition is not particularly limited, and is, for example, 0 mass% or more and 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 2 mass% or more, further more preferably 4 mass% or more, and particularly preferably 5 mass% or more, when the nonvolatile content in the resin composition is 100 mass%.

(F) curing Accelerator

The resin composition of the present invention may contain (F) a curing accelerator as an optional component. (F) The curing accelerator has a function of accelerating curing of the epoxy resin (D).

The curing accelerator (F) is not particularly limited, and examples thereof include phosphorus-based curing accelerators, urea-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, preferred are phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators, and particularly preferred are amine-based curing accelerators and imidazole-based curing accelerators. The curing accelerator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Examples of the phosphorus-based curing accelerator include: aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium cresol novolak trimer salt, di-t-butylmethylphosphonium tetraphenylborate and the like; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; an aromatic phosphine-quinone addition reaction product such as a triphenylphosphine-p-benzoquinone addition reaction product; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-t-butylphenyl phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-t-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2,4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, triphenylphosphine, tri (4-t-butylphenyl) phosphine, tri (4-methylphenyl), And aromatic phosphines such as tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 2-bis (diphenylphosphino) acetylene, and 2,2' -bis (diphenylphosphino) diphenyl ether.

Examples of the urea-based curing accelerator include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1,1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 3- (3, 4-dimethylphenyl) -1, 1-dimethylurea, 3- (4-isopropylphenyl) -1, 1-dimethylurea, 3- (4-methoxyphenyl) -1, 1-dimethylurea, methyl-3-hydroxyurea, methyl-3-methyl-1-dimethylurea, methyl-3-methyl-4-methylphenyl-1-dimethyl, Aromatic dimethylureas such as 3- (4-nitrophenyl) -1, 1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl ] -1, 1-dimethylurea, 3- [4- (4-chlorophenoxy) phenyl ] -1, 1-dimethylurea, 3- [3- (trifluoromethyl) phenyl ] -1, 1-dimethylurea, N- (1, 4-phenylene) bis (N ', N' -dimethylurea), and N, N- (4-methyl-1, 3-phenylene) bis (N ', N' -dimethylurea) [ tolylbisdimethylurea ].

Examples of the amine-based curing accelerator include: trialkylamines such as triethylamine and tributylamine, 4-Dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5,4,0) -undecene, and the like, and 4-dimethylaminopyridine is preferred.

Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, tris (meth) acrylate ester, or a mixture thereof, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, imidazole compounds such as 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.

Examples of the guanidine-based curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecyl biguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The content of the curing accelerator (F) in the resin composition is not particularly limited, and is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, further more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass. The lower limit of the content of the (F) curing accelerator in the resin composition is not particularly limited, and is, for example, 0 mass% or more and 0.0001 mass% or more, preferably 0.001 mass% or more, more preferably 0.005 mass% or more, further preferably 0.01 mass% or more, further more preferably 0.05 mass% or more, and particularly preferably 0.1 mass% or more, when the nonvolatile content in the resin composition is 100 mass%.

< (G) other additives

The resin composition of the present invention may further contain any additive as a nonvolatile component. Examples of such additives include: organic fillers such as rubber particles, polyamide fine particles, and silicone particles; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine and the like; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentonite (Benton) and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improving agents such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus flame retardants (e.g., phosphoric acid esters, phosphinic acid esters, phosphazene compounds, and red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, and inorganic flame retardants (e.g., antimony trioxide). The additive may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio. (G) The content of other additives can be appropriately set by those skilled in the art.

(H) organic solvent

The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the nonvolatile component. As the organic solvent (H), known organic solvents can be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (H) include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbitol acetate, gamma-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. (H) The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

< method for producing resin composition >

The resin composition of the present invention can be produced, for example, by: to an arbitrary reaction vessel, (a) a polyimide resin (a preliminarily imidized substance), (B) a carbodiimide resin, (C) an inorganic filler, (D) an epoxy resin used as needed, (E) a curing agent used as needed, (F) a curing accelerator used as needed, (G) other additives used as needed, and (H) an organic solvent used as needed are added and mixed in an arbitrary order and/or partially or entirely at the same time. In addition, the temperature may be appropriately set during the addition and mixing of the components, and heating and/or cooling may be performed temporarily or throughout. In addition, stirring or shaking may be performed during the addition and mixing of the components. In addition, when the resin composition is added and mixed or subsequently, the resin composition can be uniformly dispersed by stirring using a stirring device such as a mixer, for example.

< Property of resin composition >

The resin composition of the present invention comprises (a) a polyimide resin, (B) a carbodiimide resin, and (C) an inorganic filler, and the content of the component (C) is less than 40% by mass, so that the halo phenomenon can be suppressed, and a cured product having excellent heat resistance and flexibility can be obtained.

Since the cured product of the resin composition of the present invention can suppress the halo phenomenon, the halo ratio (halo ratio) calculated as in test example 1 described below may be preferably 40% or less, more preferably 35% or less, still more preferably 30% or less, and particularly preferably 25% or less.

Since the cured product of the resin composition of the present invention has excellent heat resistance, the rate of change in elongation at break of the cured product before and after the high-temperature treatment at 200 ℃ for 5 hours (a numerical value determined by formula (1) in test example 2) may be preferably 50% or more, more preferably 60% or more, further preferably 70% or more, and particularly preferably 80% or more, as in test example 2 described below.

Since the cured product of the resin composition of the present invention has excellent flexibility, the number of folding endurance tests performed on the resin composition according to the mode of test example 3 described below may be preferably 3,000 or more, more preferably 5,000 or more, further preferably 8,000 or more, and particularly preferably 10,000 or more.

< use of resin composition >

The resin composition of the present invention can be used in a wide range of applications such as insulating materials for printed wiring boards and multilayer flexible boards, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, filling resins, and component embedding resins. Printed wiring boards, multilayer flexible substrates, and the like can be produced using sheet-like layered materials such as resin sheets and prepregs.

< resin sheet >

The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and particularly preferably 70 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and preferably a film made of a plastic material and a metal foil.

When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, sometimes simply referred to as "PET"), polyethylene naphthalate (hereinafter, sometimes simply referred to as "PEN"), polycarbonates (hereinafter, sometimes simply referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.

When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

The surface of the support to be bonded to the resin composition layer may be subjected to a matting treatment, a corona treatment, or an antistatic treatment.

In addition, as the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available products can be used, and examples thereof include "SK-1", "AL-5" and "AL-7" manufactured by Lindedaceae, as a PET film having a release layer containing an alkyd resin-based release agent as a main component, "Lumiror T60" manufactured by Toray, as a "Purex" manufactured by Ditika, and "Unipel" manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further include other layers as needed. Examples of the other layer include a protective film for the support provided on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust or the like to the surface of the resin composition layer or generation of damage on the surface of the resin composition layer.

The resin sheet can be produced by: the resin composition layer is formed by directly applying the resin composition onto the support using a die coater or the like, or by applying a resin varnish prepared by dissolving the resin composition in an organic solvent onto the support and drying the resin varnish.

Examples of the organic solvent that can be used when applying the coating composition to the support include the same organic solvents as those mentioned in the description of the organic solvent as a component of the resin composition. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. The drying conditions also vary depending on the boiling point of the organic solvent in the resin composition or the resin varnish, and for example, in the case of using a resin composition or a resin varnish containing 30 to 60 mass% of an organic solvent, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, the protective film can be peeled off and used.

< laminated sheet >

The laminated sheet may be a sheet produced by laminating and curing a plurality of resin composition layers. The laminated sheet includes a plurality of insulating layers as a cured product of the resin composition layer. In general, the number of resin composition layers laminated for manufacturing the laminated sheet corresponds to the number of insulating layers included in the laminated sheet. The specific number of insulating layers per 1-layer laminated sheet is usually 2 or more, preferably 3 or more, particularly preferably 5 or more, preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.

The laminated sheet may be a sheet that is used by being bent so that one surface thereof faces each other. The minimum bend radius of the laminated sheet in bending is not particularly limited, but is preferably 0.1mm or more, more preferably 0.2mm or more, further preferably 0.3mm or more, preferably 5mm or less, more preferably 4mm or less, and particularly preferably 3mm or less.

In each insulating layer included in the laminated sheet, a hole may be formed. The holes may function as through holes (vias) or through holes (vias) in the multilayer flexible substrate.

The laminated sheet may further include any element in addition to the insulating layer. For example, the laminated sheet may include a conductor layer as an arbitrary element. The conductor layer is usually formed partially on the surface of the insulating layer or between the insulating layers. The conductor layer generally functions as a wiring in a multilayer flexible substrate.

The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor material may be a single metal or an alloy. Examples of the alloy include alloys of two or more metals selected from the above-described group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal is preferable from the viewpoints of versatility of forming a conductor layer, cost, ease of patterning, and the like; and alloys such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy. Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is more preferable; and nickel-chromium alloys, more preferably copper.

The conductor layer may have a single-layer structure, or may have a multilayer structure including 2 or more single metal layers or alloy layers made of different metals or alloys. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

The conductor layer may be patterned so as to function as a wiring.

The thickness of the conductor layer depends on the design of the multilayer flexible substrate, and is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

The thickness of the laminated sheet is preferably 100 μm or more, more preferably 150 μm or more, particularly preferably 200 μm or more, preferably 2,000 μm or less, more preferably 1,000 μm or less, and particularly preferably 500 μm or less.

< method for producing laminated sheet >

The laminated sheet can be produced by a production method including the steps of: (a) a step of preparing a resin sheet; and (b) laminating and curing a plurality of resin composition layers using the resin sheet. The order of lamination and curing of the resin composition layer is arbitrary as long as a desired laminated sheet can be obtained. Depending on the components contained in the resin composition, for example, after the multilayer resin composition layers are all stacked, the stacked multilayer resin composition layers may be collectively cured. In addition, for example, after each lamination of another resin composition layer on a certain resin composition layer, the already laminated resin composition layer may be cured.

Hereinafter, a preferred embodiment of the step (b) will be described. In the embodiments described below, for the sake of distinction, the resin composition layers are indicated by symbols as "first resin composition layer" and "second resin composition layer", and the insulating layers obtained by curing these resin composition layers are also indicated by symbols as "first insulating layer" and "second insulating layer", similarly to the resin composition layers.

In a preferred embodiment, the step (b) comprises the steps of:

(II) a step of curing the first resin composition layer to form a first insulating layer;

(VI) a step of laminating a second resin composition layer on the first insulating layer; and

(VII) a step of curing the second resin composition layer to form a second insulating layer. The step (b) may further include any of the following steps, if necessary:

(I) a step of laminating a first resin composition layer on a sheet-like support base material;

(III) forming a hole in the first insulating layer;

(IV) a step of roughening the first insulating layer; and

(V) forming a conductor layer on the first insulating layer. Hereinafter, each step will be explained.

The step (I) is a step of laminating a first resin composition layer on a sheet-like support base material before the step (II). The sheet-like support substrate is a peelable member, and for example, a plate-like, sheet-like or film-like member can be used.

The lamination of the sheet-like support substrate with the first resin composition layer may be performed using a vacuum lamination method. In the vacuum lamination method, the heating and pressure bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and pressure bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and pressure bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7hPa or less.

The lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko Co., Ltd, a vacuum applicator (vacuum applicator) manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

In the case of using a resin sheet, the lamination of the sheet-like support base material and the first resin composition layer can be performed, for example, by pressing the resin sheet from the support side and heat-pressure bonding the first resin composition layer of the resin sheet to the sheet-like support base material. Examples of the member for heat-pressure bonding the resin sheet to the sheet-like support base material (hereinafter, also referred to as "heat-pressure bonding member" as appropriate) include a heated metal plate (SUS end plate or the like) and a metal roll (SUS roll). Preferably, the heating and pressure-bonding member is not directly pressed against the resin sheet, but is pressed through an elastic material such as a heat-resistant rubber so that the first resin composition layer sufficiently follows the surface irregularities of the sheet-like support base material.

After the lamination, the smoothing treatment of the first resin composition layer may be performed by pressing under normal pressure (atmospheric pressure), for example, with a heat crimping member. For example, in the case of using a resin sheet, the first resin composition layer of the resin sheet can be smoothed by pressing the resin sheet with the heat and pressure bonding member from the support side. The pressing conditions for the smoothing treatment may be set to the same conditions as the above-described conditions for the heat and pressure bonding of the laminate. The smoothing treatment can be performed using a commercially available laminator. The lamination and smoothing processes can be performed continuously using a commercially available vacuum laminator as described above.

The step (II) is a step of curing the first resin composition layer to form a first insulating layer. The curing conditions of the first resin composition layer are not particularly limited, and the conditions employed in forming the insulating layer of the printed wiring board can be arbitrarily applied. For the first resin composition layer, for example, in the case of containing a thermosetting resin, it can be cured by heat curing it.

In general, specific heat curing conditions differ depending on the kind of the thermosetting resin. For example, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and still more preferably 170 to 210 ℃. The curing time is preferably 5 to 120 minutes, more preferably 10 to 110 minutes, and still more preferably 20 to 100 minutes.

The first resin composition layer may be preheated at a temperature lower than the curing temperature before the first resin composition layer is thermally cured. For example, the first resin composition layer may be preheated at a temperature of 50 ℃ or higher and lower than 120 ℃ (preferably 60 ℃ or higher and 115 ℃ or lower, more preferably 70 ℃ or higher and 110 ℃ or lower) for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes) before the first resin composition layer is thermally cured.

The step (III) is a step of forming a hole in the first insulating layer. In the step (III), a via hole, a through hole, or the like can be formed in the first insulating layer. For the opening, for example, a drill, a laser, plasma, or the like may be used depending on the composition of the resin composition. The size and shape of the hole may be appropriately set according to the design of the multilayer flexible substrate.

The step (IV) is a step of performing roughening treatment on the first insulating layer. In general, in this step (IV), stain (scum) is also removed. Therefore, the roughening treatment is sometimes referred to as desmear treatment. Examples of the roughening treatment include a method in which swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid are sequentially performed.

The swelling liquid is not particularly limited, and examples thereof include alkaline aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available Swelling liquids include "spinning Dip securigant P" and "spinning Dip securigant SBU" manufactured by amatt JAPAN (ato ech JAPAN). The swelling treatment with the swelling solution can be performed, for example, by immersing the cured product in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, the insulating layer is preferably immersed in a swelling solution at 40 to 80 ℃ for 5 to 15 minutes.

The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving permanganate in an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact P", "Concentrate Compact CP" and "Dosing Solution securigant P" manufactured by amett japan. The roughening treatment with an oxidizing agent may be performed by immersing the cured body in an oxidizing agent solution heated to 60 to 80 ℃ for 10 to 30 minutes.

In addition, as the neutralizing solution, an acidic aqueous solution can be used. Examples of commercially available products include "Reduction Solution securigant P" manufactured by anmant japan. The treatment with the neutralizing solution can be performed by immersing the cured product in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of handling and the like, the cured product is preferably immersed in a neutralization solution at 40 to 70 ℃ for 5 to 20 minutes.

The arithmetic average roughness (Ra) of the surface of the first insulating layer after the roughening treatment is preferably 400nm or less, more preferably 300nm or less, and further preferably 200nm or less. The lower limit is not particularly limited, and may be 30nm or more, 40nm or more, or 50nm or more.

The step (V) is a step of forming a conductor layer on the first insulating layer as necessary. Examples of the method for forming the conductor layer include plating, sputtering, and vapor deposition, and among them, plating is preferred. A preferable example is a method of forming a conductor layer having a desired wiring pattern by plating on the surface of the first insulating layer by an appropriate method such as a semi-additive method or a full-additive method. Among them, the semi-addition method is preferable from the viewpoint of ease of production.

An example of forming a conductor layer by a semi-additive method is shown below. First, a plating seed layer is formed on the surface of the first insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

The first insulating layer is obtained in step (II), and step (III), step (IV), and step (V) are performed as necessary, followed by step (VI). Step (VI) is a step of laminating a second resin composition layer on the first insulating layer. The lamination of the first insulating layer and the second resin composition layer can be performed by the same method as the lamination of the sheet-like support base material and the first resin composition layer in the step (I).

However, in the case where the first resin composition layer is formed using a resin sheet, the support of the resin sheet is removed before the step (VI). The removal of the support may be performed between the steps (I) and (II), between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and (V).

After the step (VI), the step (VII) is performed. Step (VII) is a step of curing the second resin composition layer to form a second insulating layer. The curing of the second resin composition layer can be performed by the same method as the curing of the first resin composition layer in the step (II). This makes it possible to obtain a multilayer sheet including a plurality of insulating layers, such as a first insulating layer and a second insulating layer.

In the method according to the above embodiment, (VIII) the step of forming a hole in the second insulating layer, (IX) the step of roughening the second insulating layer, and (X) the step of forming a conductor layer on the second insulating layer may be performed as necessary. The opening of the second insulating layer in the step (VIII) can be performed by the same method as the opening of the first insulating layer in the step (III). In addition, the roughening treatment of the second insulating layer in the step (IX) can be performed by the same method as the roughening treatment of the first insulating layer in the step (IV). Further, the formation of the conductor layer on the second insulating layer in the step (X) can be performed by the same method as the formation of the conductor layer on the first insulating layer in the step (V).

In the above-described embodiment, the embodiment in which the laminated sheet is produced by laminating and curing 2 resin composition layers such as the first resin composition layer and the second resin composition layer was described, but the laminated sheet may be produced by laminating and curing 3 or more resin composition layers. For example, in the method according to the embodiment described above, the lamination and curing of the resin composition layer by the steps (VI) to (VII), and if necessary, the drilling of the insulating layer, the roughening treatment of the insulating layer, and the formation of the conductor layer on the insulating layer by the steps (VIII) to (X) may be repeatedly performed to manufacture the laminated sheet. This can provide a laminated sheet including 3 or more insulating layers.

The method according to the above embodiment may further include any step other than the above steps. For example, when the step (I) is performed, a step of removing the sheet-like support base material may be performed.

< multilayer Flexible substrate >

The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may include only the laminated sheet, or may include not only the laminated sheet but also any member. Examples of the optional member include an electronic component and a cover film.

The multilayer flexible substrate can be manufactured by a manufacturing method including a method of manufacturing the laminated sheet described above. Accordingly, the multilayer flexible substrate can be manufactured by a manufacturing method including the steps of: (a) a step of preparing a resin sheet, and (b) a step of laminating and curing a plurality of resin composition layers using the resin sheet.

The method for manufacturing a multilayer flexible substrate may include any process other than the above-described process. For example, a method for manufacturing a multilayer flexible substrate including an electronic component may include a step of bonding the electronic component to the laminated sheet. As for the bonding condition between the laminated sheet and the electronic component, any condition can be adopted in which the terminal electrode of the electronic component and the conductor layer provided on the laminated sheet as a wiring can be conductor-connected. For example, the method for manufacturing a multilayer flexible substrate provided with a cover film may include a step of laminating a laminated sheet and the cover film.

The multilayer flexible substrate described above can be generally used by being bent so that one surface of a laminated sheet included in the multilayer flexible substrate faces each other. For example, the multilayer flexible substrate may be folded to be housed in a case of a semiconductor device in a reduced-size state. In addition, for example, a multilayer flexible substrate may be provided to a flexible portion in a semiconductor device having the flexible portion.

< semiconductor device >

The semiconductor device includes the multilayer flexible substrate. The semiconductor device includes, for example, a multilayer flexible substrate and a semiconductor chip mounted on the multilayer flexible substrate. In many semiconductor devices, a multilayer flexible substrate is folded so that one surface of a laminated sheet included in the multilayer flexible substrate faces each other, and is accommodated in a case of the semiconductor device.

Examples of the semiconductor device include various semiconductor devices which can be used in, for example, electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, airplanes, and the like).

The semiconductor device can be manufactured by a manufacturing method including, for example, the steps of: the method includes a step of preparing a multilayer flexible substrate, a step of bending the multilayer flexible substrate so that one surface of the laminated sheet faces each other, and a step of housing the bent multilayer flexible substrate in a case.

Examples

The present invention will be specifically described below with reference to examples. The present invention is not limited by these examples. In the following description, "part" and "%" representing amounts mean "part by mass" and "% by mass", respectively, unless otherwise explicitly stated. Unless otherwise stated, the operations described below are performed under an atmosphere of normal temperature and pressure (25 ℃,1 atm).

< Synthesis example 1: synthesis of polyimide resin 1

G-3000 (bifunctional hydroxyl-terminated polybutadiene, number average molecular weight =5047(GPC method), hydroxyl equivalent =1798G/eq., 100 mass% solid content: manufactured by Nippon Caoka Co., Ltd.) 50G, Izod (イプゾール) 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Takekushi Co., Ltd.) 23.5G, and dibutyltin laurate 0.005G were mixed and dissolved uniformly in a reaction vessel. After the mixture became homogeneous, the temperature was raised to 50 ℃, 4.8g of toluene-2, 4-diisocyanate (isocyanate group equivalent =87.08g/eq.) was added with further stirring, and the reaction was carried out for about 3 hours. Next, the reaction mixture was cooled to room temperature, and 8.96g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent =161.1g/eq.) and 0.07g of triethylenediamine and 40.4g of ethylene glycol monoethyl ether acetate (made by cellosolve) were added thereto, and the temperature was raised to 130 ℃ with stirring, and the reaction was carried out for about 4 hours. By FTIR pair 2250cm^-1The disappearance of the NCO peak of (2) was confirmed. When disappearance of NCO peak was confirmed, the reaction was regarded as the end point of the reaction, and after the temperature of the reaction product was lowered to room temperature, the reaction product was filtered through 100 mesh filter cloth to obtain polyimide resin 1 having an imide skeleton, a urethane skeleton, and a butadiene skeleton;

viscosity: seeds (25 deg.C, E type viscometer) 7.5Pa

Acid value: 16.9mgKOH/g

Solid content: 50% by mass

Number average molecular weight: 13723

Glass transition temperature: -10 deg.C

Content ratio of polybutadiene structural portion: 50/(50+4.8+8.96) × 100=78.4 mass%.

< Synthesis example 2: synthesis of polyimide resin 2

Into a 500ml separable flask equipped with a nitrogen introduction tube and a stirring device, 9.13g (30 mmol) of 5-amino-1, 1' -biphenyl-2-yl 4-aminobenzoate, 15.61g (30 mmol) of 4,4' - (4,4' -isopropylidenediphenoxy) bisphthalic dianhydride, 94.64g of N-methyl-2-pyrrolidone, 0.47g (6 mmol) of pyridine, and 10g of toluene were charged, and imidization was performed for 4 hours while toluene was discharged out of the system halfway at 180 ℃ under a nitrogen atmosphere, whereby a polyimide solution containing polyimide resin 2 was obtained (nonvolatile content: 20 mass%). In the polyimide solution, no precipitation of the synthesized polyimide resin 2 was observed. The weight average molecular weight of the polyimide resin 2 was 45,000.

< Synthesis example 3: synthesis of polyimide resin 3

65.0g of aromatic tetracarboxylic dianhydride (BisDA-1000 manufactured by SABIC Japan; 4,4'- (4,4' -isopropylidenediphenoxy) diphthalic dianhydride), 266.5g of cyclohexanone, and 44.4g of methylcyclohexane were charged into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, and the solution was heated to 60 ℃. Then, 43.7g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan K.K.) and 5.4g of 1, 3-bis (aminomethyl) cyclohexane were added dropwise thereto, followed by imidization at 140 ℃ for 1 hour. Thus, a polyimide solution (nonvolatile content: 30% by mass) containing the polyimide resin 3 was obtained. In addition, the weight average molecular weight of the polyimide resin 3 was 25,000.

< Synthesis example 4: synthesis of polyimide resin 4

A500 mL separable flask equipped with a quantitative moisture receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. To the flask were added 20.3g of 4,4' -oxydiphthalic anhydride (ODPA), 200g of gamma-butyrolactone, 20g of toluene, and 29.6g of 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl ] -1,1, 3-trimethylindane, and the mixture was stirred at 45 ℃ for 2 hours under a nitrogen stream to effect a reaction. Then, the reaction solution was heated to about 160 ℃ and, while maintaining the temperature, the condensation water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water was accumulated in the quantitative water receiver and that the outflow of water was no longer observed. After confirmation, the reaction solution was further heated and stirred at 200 ℃ for 1 hour. Then, it was cooled to obtain a polyimide solution (nonvolatile component: 20 mass%) containing a polyimide resin 4 having a1, 1, 3-trimethylindan skeleton. The obtained polyimide resin 4 has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the foregoing polyimide resin 4 was 12,000.

[ chemical formula 4]

。

[ chemical formula 5]

。

< example 1: preparation of resin composition 1

A mixed solvent of 5 parts of a bicresol-type epoxy resin ("YX 4000 HK" manufactured by mitsubishi chemical corporation, having an epoxy equivalent of about 185), 5 parts of a naphthalene-type epoxy resin ("ESN 475V" manufactured by new yokuwa chemical corporation, having an epoxy equivalent of about 332), 10 parts of a bisphenol AF-type epoxy resin ("YL 7760" manufactured by mitsubishi chemical corporation, having an epoxy equivalent of about 238), 2 parts of a cyclohexane-type epoxy resin ("ZX 1658 GS" manufactured by mitsubishi chemical corporation, having an epoxy equivalent of about 135), 40 parts of the polyimide resin 1 (having a nonvolatile component of 50 mass%) obtained in synthetic example 1, and 10 parts of cyclohexanone was heated and dissolved while stirring. After cooling to room temperature, 4 parts of a cresol novolak-type curing agent having a triazine skeleton (a 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a nonvolatile content of 50%) 6 parts of an active ester-type curing agent (an MEK solution having an active group equivalent of about 220 and a nonvolatile content of 65% by mass of EXB-8000L-65M, manufactured by DIC) and 6 parts of spherical silica (an MEK solution having an average particle diameter of 0.5 μ M and a specific surface area of 11.2M, manufactured by Yadu Ma corporation, SC2500SQ were mixed²(g) silica 100 parts, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM 573" manufactured by shin-Etsu chemical Co., Ltd.) 25 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Co., Ltd., polycarbodiimide, 50% nonvolatile toluene solution) 10 parts, and amine-based curing accelerator (4-Dimethylaminopyridine (DMAP))0.2 partAfter the components were uniformly dispersed in a high-speed rotary mixer, they were filtered through a drum filter ("SHP 020" manufactured by ROKITECHNO corporation) to prepare a resin composition 1.

< example 2: preparation of resin composition 2

A resin composition 2 was prepared in the same manner as in example 1, except that 100 parts of the polyimide resin 2 (nonvolatile component: 20 mass%) obtained in synthesis example 2 was used instead of 40 parts of the polyimide resin 1 (nonvolatile component: 50 mass%) obtained in synthesis example 1.

< example 3: preparation of resin composition 3

A resin composition 3 was prepared in the same manner as in example 1, except that 66.7 parts of the polyimide resin 3 (nonvolatile component: 30 mass%) obtained in synthesis example 3 was used in place of 40 parts of the polyimide resin 1 (nonvolatile component: 50 mass%) obtained in synthesis example 1.

< example 4: preparation of resin composition 4

A resin composition 4 was prepared in the same manner as in example 1, except that 100 parts of the polyimide resin 4 (nonvolatile component: 20 mass%) obtained in synthesis example 4 was used instead of 40 parts of the polyimide resin 1 (nonvolatile component: 50 mass%) obtained in synthesis example 1.

< comparative example 1: preparation of resin composition 5

A resin composition 5 was prepared in the same manner as in example 1 except that 10 parts of the carbodiimide resin (manufactured by Nisshinbo Co., Ltd. "V-03", polycarbodiimide, a toluene solution having a nonvolatile content of 50%) in example 1 was not used.

Comparative example 2: preparation of resin composition 6

A resin composition 6 was prepared in the same manner as in example 1, except that 66 parts of a phenoxy resin ("YX 7553BH 30" manufactured by mitsubishi chemical corporation, solid content: 30 mass%) was used instead of 40 parts of the polyimide resin 1 (nonvolatile content: 50 mass%) obtained in synthesis example 1.

< test example 1: evaluation of halo suppression Property >

(1) Copper-clad laminated board

As a copper-clad laminate, a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil 3 μm thick, substrate 0.15mm thick, "HL 832NSF LCA" manufactured by Mitsubishi gas chemical corporation, 255X 340mm in size) in which copper foil layers were laminated on both sides was prepared.

(2) Lamination of resin sheet with support

The resin sheets with supports (comparative example, resin sheet a or resin sheet B) produced in examples were laminated on both sides of a copper-clad laminate so that the resin composition layer was in contact with the copper-clad laminate using a batch vacuum press laminator (CVP 700, manufactured by Nikko Materials). The lamination was carried out by: the pressure was reduced for 30 seconds to a pressure of 13hPa or less, and the pressure was bonded at 130 ℃ and a pressure of 0.74MPa for 45 seconds. Next, hot pressing was performed at 120 ℃ for 75 seconds under a pressure of 0.5 MPa.

(3) Thermal curing of resin composition layers

The copper-clad laminate laminated with the resin composition layer is put into an oven at 100 ℃ and then thermally cured for 30 minutes, and then is moved to an oven at 180 ℃ and then thermally cured for 30 minutes to form an insulating layer. This was used as a cured substrate a.

(4) Laser via machining (laser drilling machining) (formation of via)

Using CO manufactured by Mitsubishi Motor Co₂A laser processing machine "605 GTWIII (-P)" irradiates laser light from the support to form a through hole having a top diameter (diameter) of 75 μm in the insulating layer. The irradiation conditions of the laser were: the mask diameter was 1mm, the pulse width was 16. mu.s, the energy was 0.2 mJ/shot (shot), the number of shots was 2, burst mode (10 kHz).

(5) Roughening treatment

The support of the cured substrate a having the through-hole formed in the insulating layer was peeled off, and then desmear treatment as roughening treatment was performed. As the desmear treatment, the following wet desmear treatment was performed.

Wet type decontamination treatment

The resulting membrane was immersed in a Swelling Solution ("Swelling Dip Securiganth P" manufactured by Amatt Japan K.K., an aqueous Solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ℃ for 10 minutes, then immersed in an oxidizing agent Solution ("Concentrate Compact CP" manufactured by Amatt Japan K.K., an aqueous Solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ℃ for 20 minutes, and finally immersed in a neutralizing Solution ("Reduction Solution Securiganth P" manufactured by Amatt Japan K.K., an aqueous Solution of sulfuric acid) at 40 ℃ for 5 minutes, and then dried at 80 ℃ for 15 minutes. This was used as a roughened substrate A.

(6) Determination of the diameter of the through-hole after desmear treatment

The roughened substrate a was observed in cross section using an FIB-SEM fusion apparatus ("SMI 3050 SE" manufactured by SII nanotechnology). Specifically, a cross section of the laser via hole in the vertical direction was cut by FIB (focused ion beam), and the diameter of the via hole after desmear treatment was measured from the cross-sectional SEM image. For each sample, the via top diameter after desmear treatment was measured from a randomly selected cross-sectional SEM image at 5, and the average value thereof was taken as the via top diameter Lt (μm) shown in table 1 below.

(7) Measurement of halo distance after roughening treatment

The roughened substrate A was observed with an optical microscope (KH 8700, manufactured by HIROX). Specifically, the insulating layer around the through-hole was observed from the upper portion of the roughened substrate a using an optical microscope (CCD). This observation was made by focusing the light microscope on the top of the via. As a result of the observation, a halo portion in a ring shape was observed in which the insulating layer continued from the edge of the via top of the via was discolored to white around the via. Therefore, from the observed image, the radius r1 of the top of the through-hole (corresponding to the inner peripheral radius of the halo portion) and the outer peripheral radius r2 of the halo portion of the through-hole were measured, and the difference r2 to r1 between the radius r1 and the radius r2 was calculated as the halo distance from the edge of the top of the through-hole at the measurement position.

The foregoing measurements were performed for 5 randomly selected through holes. The average of the measured values of the halo distances of the 5 through holes is shown in table 1 below as the halo distance Wt (μm) from the edge of the top of the through hole of the sample.

The halo ratio Ht was calculated based on the via top diameter Lt and the halo distance Wt, and is shown in table 1 below. The halo ratio Ht represents a ratio (Wt/(Lt/2)) of a halo distance Wt from an edge of the top of the through-hole after the roughening treatment to a radius (Lt/2) of the top of the through-hole after the roughening treatment. When the halo ratio Ht is 35% or less, it is determined as "o", and when the halo ratio Ht is more than 35%, it is determined as "x".

< test example 2: evaluation of Heat resistance >

(1) Preparation of cured product for evaluation

The release PET film was placed on the double-sided copper-clad glass cloth substrate epoxy resin laminate (R5715 ES, manufactured by Sonchio electric Co., Ltd., thickness of 0.7mm, square 255 mm) so that the untreated surface of the release PET film ("501010", manufactured by Lingdeko Co., Ltd., thickness of 38 μm, square 240 mm) was in contact with the double-sided copper-clad glass cloth substrate epoxy resin laminate, and the four sides of the release PET film were fixed with a polyimide tape (width of 10 mm).

The resin sheets (167 × 107mm square) with supports produced in examples and comparative examples were each subjected to a lamination process at the center using a batch vacuum press laminator (CVP 700, 2-stage stack laminator, manufactured by Nikko Materials corporation) so that the resin composition layer was in contact with the release surface of the release PET film. The lamination process is carried out by: the pressure was reduced to 13hPa or less for 30 seconds, and then pressure-bonded at 100 ℃ for 30 seconds at a pressure of 0.74 MPa.

Next, the support was peeled off, and the resin composition layer was thermally cured under curing conditions of 180 ℃ for 90 minutes.

After thermosetting, the polyimide tape was peeled off, and the cured product layer was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled from the cured product layer to obtain a sheet-like cured product (cured product a for evaluation). Further, after the cured product layer was further heated at 200 ℃ for 5 hours, the cured product layer was peeled from the release PET film in the same manner as the cured product a for evaluation, to obtain a sheet-like cured product (cured product B for evaluation).

(2) Determination of elongation (elongation at Break)

The evaluation cured products A and B were cut into a dumbbell-shaped No. 1 to obtain test pieces. The test piece was subjected to a tensile test of a cured product for evaluation using a Tensilon Universal tester (manufactured by A & D) in accordance with the Japanese Industrial Standard (JIS K7127), and the elongation at break (%) at 23 ℃ was measured. This operation was performed 3 times, and the average values of the operations are shown in table 1 below. Obtaining a change rate of an average value A of elongation at break (%) of a cured product A for evaluation and an average value B of elongation at break (%) of a cured product B for evaluation by using the following formula (1);

elongation at break (%) = { (B-A)/A }. times.100 (1)

When the elongation at break change rate was 80% or more, the specimen was judged as "good", and when the elongation at break change rate was 80% or less, the specimen was judged as "x".

< test example 3: evaluation of flexibility (MIT folding endurance)

The cured product A for evaluation obtained in test example 2 was cut into test pieces having a width of 15mm and a length of 110mm, and the number of folding resistances until the cured product broke was measured according to JIS C-5016 under the measurement conditions of a load of 2.5N, a folding angle of 90 degrees, a folding radius of 1.0mm, and a folding speed of 175 times/minute using an MIT tester (MIT-DA), manufactured by Toyo Seiki Seisaku-Sho Ltd. The measurement was performed on 5 samples, and the average value of the samples at the first 3 positions from the top to the bottom was calculated. The case where the folding endurance was less than 8,000 was evaluated as "x", and the case where the folding endurance was 8,000 or more was evaluated as "O".

The amounts of nonvolatile components used, the measurement results of the test examples, the evaluation results, and the like of the resin compositions of examples and comparative examples are shown in table 1 below.

[ Table 1]

。

It is found that a cured product excellent in flexibility, halo phenomenon suppression characteristics, and heat resistance can be obtained by using a resin composition comprising (a) a polyimide resin, (B) a carbodiimide resin, and (C) an inorganic filler, wherein the content of the component (C) is less than 40% by mass.

Claims

1. A resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler,

wherein the content of the component (C) is less than 40% by mass, based on 100% by mass of nonvolatile components in the resin composition.

2. The resin composition according to claim 1, wherein the weight average molecular weight of component (A) is 1,000 or more and 100,000 or less.

3. The resin composition according to claim 1, wherein the content of the component (A) is 15% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

4. The resin composition according to claim 1, wherein the content of the component (A) is 35% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

5. The resin composition according to claim 1, wherein the component (B) is polycarbodiimide.

6. The resin composition according to claim 1, wherein the content of the isocyanoyl group in the molecule of the component (B) is 0.2% by mass or less.

7. The resin composition according to claim 1, wherein the content of the component (B) is 3% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

8. The resin composition according to claim 1, wherein the content of the component (B) is 15% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

9. The resin composition according to claim 1, wherein the mass ratio of component (B) to component (A), (component (B)/component (A)), is 0.1 or more.

10. The resin composition according to claim 1, wherein the mass ratio of component (B) to component (A), (component (B)/component (A)), is 0.5 or less.

11. The resin composition according to claim 1, wherein the component (C) is silica.

12. The resin composition according to claim 1, wherein the average particle diameter of the component (C) is 1 μm or less.

13. The resin composition of claim 1, further comprising (D) an epoxy resin.

14. The resin composition according to claim 1, further comprising (E) a curing agent.

15. The resin composition according to claim 14, wherein the component (E) comprises an active ester-based curing agent.

16. The resin composition according to claim 1, which is used for forming an insulating layer of a multilayer flexible substrate.

17. A cured product of the resin composition according to any one of claims 1 to 16.

18. A resin sheet, comprising:

a support, and

a resin composition layer formed of the resin composition according to any one of claims 1 to 16, provided on the support.

19. A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition according to any one of claims 1 to 16.

20. A semiconductor device comprising the multilayer flexible substrate according to claim 19.