CN112280296A

CN112280296A - Resin composition

Info

Publication number: CN112280296A
Application number: CN202010697352.2A
Authority: CN
Inventors: 鹤井一彦
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2019-07-24
Filing date: 2020-07-20
Publication date: 2021-01-29
Also published as: JP2021020982A; JP7575865B2; KR20210012935A; JP2023033346A; JP7409473B2; TW202116924A

Abstract

The present invention addresses the problem of providing a resin composition that enables the production of a cured product that has a low coefficient of thermal expansion and is suppressed in warpage. The solution of the present invention is a resin composition comprising (A) a polyimide resin and (B) a siloxane-containing polycarbonate resin.

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 has been paid to a flexible substrate used as a base substrate for a semiconductor device. The flexible substrate may be thinner and lighter than the rigid substrate. In addition, the flexible substrate is flexible and deformable, and thus can be mounted in a bendable manner.

Flexible substrates are typically manufactured by performing the following steps: preparing a three-layer film formed by a polyimide film, a copper foil and an adhesive, or a two-layer film formed by a polyimide film and a conductor layer; and forming a circuit by etching the conductor layer by a subtractive process. Conventionally, three-layer films have been used in many cases because they can be produced at a relatively low cost. However, in a circuit board having high-density wiring, two layers of films are sometimes used in order to solve the problems of heat resistance and electrical insulation of the adhesive. However, the two-layer film has problems in terms of cost and productivity. In order to solve the above problems, patent documents 1 to 3 disclose insulating materials for multilayer flexible substrates. Further, patent documents 4 and 5 describe polyimide resins. Further, patent document 6 describes a siloxane-containing polycarbonate resin.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2006-37083

Patent document 2: japanese patent laid-open publication No. 2016-41797

Patent document 3: japanese patent No. 6387181

Patent document 4: japanese patent No. 6240798

Patent document 5: japanese patent No. 6240799

Patent document 6: japanese patent No. 6343680.

Disclosure of Invention

Problems to be solved by the invention

Generally, polyimide resins and polycarbonate resins used for flexible substrates have a low coefficient of thermal expansion, but have a problem that they are likely to cause large warpage. On the other hand, it is known that a silicone resin has a high thermal expansion coefficient and low compatibility, although warpage is suppressed.

The invention aims to provide a resin composition and the like capable of obtaining a cured product with low thermal expansion coefficient and restrained warping.

Means for solving the problems

As a result of intensive studies to achieve the object of the present invention, the present inventors have unexpectedly found that a cured product having a low coefficient of thermal expansion and suppressed warpage can be obtained by using a resin composition comprising (a) a polyimide resin and (B) a siloxane-containing polycarbonate resin, and have completed the present invention.

That is, the present invention includes the following items,

[1] a resin composition comprising (a) a polyimide resin and (B) a siloxane-containing polycarbonate resin;

[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 component (B) is a polycarbonate-polysiloxane copolymer comprising a polycarbonate block having a polycarbonate structure and a polysiloxane block having a polysiloxane structure;

[4] the resin composition according to the above [3], wherein the polysiloxane structure is a polydialkylsiloxane structure;

[5] the resin composition according to the above [3] or [4], wherein the polycarbonate structure is an aromatic polycarbonate structure;

[6] the resin composition according to any one of the above [3] to [5], wherein the content of the polysiloxane structure in the component (B) is 1% by mass or more and 30% by mass or less, assuming that the component (B) is 100% by mass;

[7] the resin composition according to any one of the above [1] to [6], wherein the viscosity-average molecular weight of the component (B) is 13,000 or more and 25,000 or less;

[8] the resin composition according to any one of the above [1] to [7], wherein the mass ratio of the component (A) to the component (B), (component (A)/component (B)), is 1 or more and 5 or less;

[9] the resin composition according to any one of the above [1] to [8], further comprising (C) an inorganic filler;

[10] the resin composition according to the above [9], wherein the component (C) is silica;

[11] the resin composition according to the above [9] or [10], wherein the content of the component (C) is 30% by mass or more and 60% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass;

[12] the resin composition according to any one of the above [1] to [11], further comprising (D) an epoxy resin and (E) a curing agent;

[13] the resin composition according to the above [12], wherein the component (E) comprises an active ester-based curing agent;

[14] the resin composition according to any one of the above [1] to [13], which is used for forming an insulating layer of a multilayer flexible substrate;

[15] a cured product of the resin composition according to any one of the above [1] to [14 ];

[16] a resin sheet comprising a support and, provided on the support, a resin composition layer formed of the resin composition according to any one of the above [1] to [14 ];

[17] a multilayer flexible substrate comprising an insulating layer formed by curing the resin composition according to any one of [1] to [14 ];

[18] a semiconductor device comprising the multilayer flexible substrate according to [17 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The resin composition of the present invention can provide a cured product having a low coefficient of thermal expansion and suppressed warpage.

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 may be modified and implemented as desired within the scope of the claims and their equivalents.

< resin composition >

The resin composition of the present invention comprises (a) a polyimide resin and (B) a siloxane-containing polycarbonate resin. By using such a resin composition, a cured product having a low thermal expansion coefficient and suppressed warpage can be obtained. In addition, the compatibility of each component is also excellent.

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

(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 may generally include a resin obtained by imidization of a diamine compound with tetracarboxylic anhydride. (A) The polyimide resin may also include a modified polyimide resin such as a siloxane-modified polyimide resin.

(A) The polyimide resin is not particularly limited, and may include, for example, a structure represented by formula (1).

[ chemical formula 1]

[ in the formula, X¹The tetravalent group obtained by removing 2-CO-O-CO-atoms from tetracarboxylic dianhydride may be an organic group having 2 to 100 (preferably 2 to 50) skeleton atoms selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms. X²Represents the removal of 2-NH groups from a diamine compound₂The divalent group obtained may be, for example, an organic group formed of 2 to 100 (preferably 2 to 50) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom. n represents a whole of 2 or moreAnd (4) counting.]

X in the formula (1)¹And X²The organic group (b) is not particularly limited as long as it is within a chemically stable structure, and may be a structure that can be 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 formula (1), the structure represented by formula (1) is preferably contained in an amount of 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by 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-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 by aminomethyl (-CH)₂-NH₂) Or amino (-NH)₂) A diamine compound obtained by substitution. 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 is easily obtained, particularly, from a dimer acid containing 36 carbon atoms, which is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid, which is inexpensive and easily available, as a main component. Further, dimer acid may be purified by the production methodThe degree of conversion and the like may contain an arbitrary amount of a monomer acid, a trimer acid, other polymerized fatty acid 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-type diamines are available, and examples thereof include PRIAMINE1073, PRIAMINE1074, and PRIAMINE1075 manufactured by Croda Japan, VERSAMINE551 and VERSAMINE552 manufactured by Cognis Japan.

Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, and a diphenylamine compound.

The phenylenediamine compound is a compound formed of a benzene ring having 2 amino groups, and the benzene ring may optionally have 1 to 3 substituents. The substituent of the benzene ring is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an arylcarbonyl group, an aryloxycarbonyl group, an arylcarbonyloxy group, an aralkyl group, a combination thereof, and the like.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and the like. The term "alkyl" refers to a straight, branched or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkyl group" is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the "alkyl group" include methyl, ethyl, propyl, isopropyl, cyclopentyl, and cyclohexyl. The "alkoxy group" refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. The "alkoxy group" is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of the "alkoxy group" include methoxy, ethoxy, propoxy, isopropoxy, cyclopentyloxy, and cyclohexyloxy. The "alkylcarbonyl group" refers to a monovalent group (alkyl-CO-) formed by bonding an alkyl group to a carbonyl group. The "alkylcarbonyl group" is preferably an alkylcarbonyl group having 2 to 7 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 4 carbon atoms. Examples of the "alkylcarbonyl group" include acetyl, propionyl, butyryl, and 2-methylpropionyl. The "alkoxycarbonyl group" refers to a monovalent group (alkyl-O-CO-) formed by bonding an alkoxy group to a carbonyl group. The "alkoxycarbonyl group" is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms, and more preferably an alkoxycarbonyl group having 2 to 4 carbon atoms. Examples of the "alkoxycarbonyl group" include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. The "alkylcarbonyloxy" group means a monovalent group (alkyl-CO-O-) formed by bonding an alkylcarbonyl group to an oxygen atom. The "alkylcarbonyloxy group" is preferably an alkylcarbonyloxy group having 2 to 7 carbon atoms, and more preferably an alkylcarbonyloxy group having 2 to 4 carbon atoms. Examples of the "alkylcarbonyloxy group" include acetyloxy group, propionyloxy group, butyryloxy group and the like. By "aryl" is meant a monovalent aromatic hydrocarbon radical. The "aryl group" is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of the "aryl group" include phenyl, 1-naphthyl and 2-naphthyl groups, and a phenyl group is preferable. The "aryloxy group" refers to a monovalent group (aryl-O-) formed by bonding an aryl group to an oxygen atom. The "aryloxy group" is preferably an aryloxy group having 6 to 14 carbon atoms, and more preferably an aryloxy group having 6 to 10 carbon atoms. Examples of the "aryloxy group" include phenoxy, 1-naphthoxy and 2-naphthoxy. The term "arylcarbonyl" refers to a monovalent group (aryl-CO-) formed by bonding an aryl group to a carbonyl group. The "arylcarbonyl group" is preferably an arylcarbonyl group having 7 to 15 carbon atoms, and more preferably an arylcarbonyl group having 7 to 11 carbon atoms. Examples of the "arylcarbonyl group" include a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. The "aryloxycarbonyl group" refers to a monovalent group (aryl-O-CO-) formed by combining an aryloxy group with a carbonyl group. The "aryloxycarbonyl group" is preferably an aryloxycarbonyl group having 7 to 15 carbon atoms, and more preferably an aryloxycarbonyl group having 7 to 11 carbon atoms. Examples of the "aryloxycarbonyl group" include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, and a 2-naphthyloxycarbonyl group. The "arylcarbonyloxy" refers to a monovalent group (aryl-CO-O-) formed by bonding an arylcarbonyl group to an oxygen atom. The "arylcarbonyloxy group" is preferably an arylcarbonyloxy group having 7 to 15 carbon atoms, and more preferably an arylcarbonyloxy group having 7 to 11 carbon atoms. Examples of the "arylcarbonyloxy group" include benzoyloxy group, 1-naphthoyloxy group, and 2-naphthoyloxy group. The "aralkyl group" refers to an alkyl group substituted with 1 or 2 or more aryl groups. The "aralkyl group" is preferably an aralkyl group having 7 to 15 carbon atoms, and more preferably an aralkyl group having 7 to 11 carbon atoms. Examples of the "aralkyl group" include a benzyl group, a phenethyl group, a 2-naphthylmethyl group and the like.

Specific examples of the phenylenediamine compound include 1, 4-phenylenediamine, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 3, 5-diaminobiphenyl, 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine and the like.

The naphthalene diamine compound is a compound formed of a naphthalene ring having 2 amino groups, and the naphthalene ring may optionally have 1 to 3 substituents. The substituent of the naphthalene ring is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound can be mentioned. Specific examples of the naphthalenediamine compound include 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 6-diaminonaphthalene, and 2, 3-diaminonaphthalene.

The diphenylamine compound is a compound having 2 aniline structures in a molecule, and 2 benzene rings in each of the 2 aniline structures may optionally have 1 to 3 substituents. The substituent is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound are exemplified. The 2 aniline structures in the diphenylamine compound may be bonded directly and/or through 1 or 2 divalent linking groups having 1 to 100 (preferably 1 to 50, more preferably 1 to 20) skeleton atoms selected from a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom. The diphenylamine compound also contains a compound in which 2 aniline structures are bonded at two positions.

Examples of the "divalent linking group" in the diphenylamine compound include: -NHCO-, -OCO-, -O-, -S-, -CO-, -SO₂-, -SO-, -NH-, - (alkylene) -, - (haloalkylene) -, -CH＝CH-、-Ph-、-Ph-Ph-、-Ph-O-Ph-、-Ph-S-Ph-、-Ph-CO-Ph-、-Ph-SO₂-Ph-, -Ph-SO-Ph-, -Ph-NH-Ph-, -Ph- (alkylene) -Ph-, - (alkylene) -Ph- (alkylene) -, -Ph- (haloalkylene) -Ph-, - (haloalkylene) -Ph- (haloalkylene) -, -O-Ph-O-, -O-Ph-CO-Ph-O-, -O-Ph-SO-Ph-Ph-, -O-Ph-SO-, -₂-Ph-O-, -O-Ph- (alkylene) -Ph-O-, -O- (alkylene) -Ph- (alkylene) -O-, -O-Ph- (haloalkylene) -Ph-O-, -O- (haloalkylene) -Ph- (haloalkylene) -O-.

May also be mentioned

[ chemical formula 2]

(wherein a represents a binding site.) and the like.

"Ph" represents 1, 4-phenylene, 1, 3-phenylene or 1, 2-phenylene. The term "alkylene" refers to a straight, branched or cyclic divalent aliphatic saturated hydrocarbon group. The "alkylene group" is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the "alkylene group" include, for example, -CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-CH₂-CH₂-CH₂-、-CH₂-CH(CH₃)-、-CH(CH₃)-CH₂-、-C(CH₃)₂-、-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH(CH₃)-、-CH₂-CH(CH₃)-CH₂-、-CH(CH₃)-CH₂-CH₂-、-CH₂-C(CH₃)₂-、-C(CH₃)₂-CH₂-、-CH₂-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-CH(CH₃)-、-CH₂-CH₂-CH(CH₃)-CH₂-、-CH₂-CH(CH₃)-CH₂-CH₂-、-CH(CH₃)-CH₂-CH₂-CH₂-、-CH₂-CH₂-C(CH₃)₂-、-CH₂-C(CH₃)₂-CH₂-、-C(CH₃)₂-CH₂-CH₂-、-C(CH₂CH₃)₂-, 1-cyclohexylene, 3, 5-trimethyl-1, 1-cyclohexylene, etc. The "haloalkylene group" refers to an alkylene group in which a part or all of hydrogen atoms are replaced with halogen atoms. The "haloalkylene group" is preferably a haloalkylene group having 1 to 6 carbon atoms, and more preferably a haloalkylene group having 1 to 3 carbon atoms. Examples of the "halogenated alkylene group" include those obtained by substituting all hydrogen atoms in the alkylene groups exemplified above with fluorine atoms.

Specific examples of the diphenylamine compound include 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, 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, 1 '-biphenyl, 9' -bis (3-methyl-4-aminophenyl) fluorene, 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl ] -1,1, 3-trimethylindane, 4-aminobenzoic acid 5-amino-1, 1 '-biphenyl-2-yl ester, etc., preferably 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl ] -1,1, 3-trimethylindane, and 4-aminobenzoic acid 5-amino-1, 1' -biphenyl-2-yl ester.

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

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, anthracene tetracarboxylic acid dianhydride, and diphthalic acid dianhydride is preferable.

The pyromellitic dianhydride is a dianhydride of benzene having 4 carboxyl groups, and the benzene ring herein may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound can be given. Specific examples of the pyromellitic dianhydride include pyromellitic dianhydride and 1,2,3, 4-pyromellitic dianhydride.

The naphthalene tetracarboxylic dianhydride is a dianhydride of naphthalene having 4 carboxyl groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound can be given. Specific examples of the naphthalene tetracarboxylic dianhydride include 1,4,5, 8-naphthalene tetracarboxylic dianhydride, and 2,3,6, 7-naphthalene tetracarboxylic dianhydride.

The anthracenetetracarboxylic dianhydride is an anthracene dianhydride having 4 carboxyl groups, and the anthracene ring herein may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound can be given. There is no particular limitation. Specific examples of the anthracenetetracarboxylic dianhydride include 2,3,6, 7-anthracenetetracarboxylic dianhydride and the like.

The diphthalic dianhydride is a compound containing 2 phthalic anhydride structures in the molecule, and 2 benzene rings in the 2 phthalic anhydride structures may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound can be given. The 2 phthalic anhydrides in the diphthalic dianhydride may be bonded directly or via a divalent linking group having 1 to 100 (preferably 1 to 50, more preferably 1 to 20) backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

Examples of the "divalent linking group" in the diphthalic dianhydride include the same groups as those of the "divalent linking group" in the diphenylamine compound.

Specific examples of the diphthalic dianhydride include 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, and the like, 1, 1-ethynylene (ethylidene) -4,4 '-biphthalic dianhydride, 2-propylene (propylidene) -4,4' -biphthalic dianhydride, 1, 2-ethylene-4, 4 '-biphthalic dianhydride, 1, 3-trimethylene-4, 4' -biphthalic dianhydride, 1, 4-tetramethylene-4, 4 '-biphthalic dianhydride, 1, 5-pentamethylene-4, 4' -biphthalic 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, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 4'- (4,4' -isopropylidenediphenoxy) diphthalic dianhydride, and the like.

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

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

The content of the structure derived from an aromatic tetracarboxylic dianhydride with respect to the total structure derived from a 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, still more preferably 70 mol% or more, particularly preferably 90 mol% or more, and particularly preferably 100 mol%.

(A) The weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 1,000 or more, more preferably 5,000 or more, further preferably 8,000 or more, and particularly preferably 10,000 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.

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, and particularly preferably 15% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass. (A) The upper limit of the content of the polyimide resin is not particularly limited, and is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

< (B) siloxane-containing polycarbonate resin

The resin composition of the present invention comprises (B) a siloxane-containing polycarbonate resin. The siloxane-containing polycarbonate resin (B) is a polymer having a polysiloxane structure (preferably a polydiorganosiloxane structure) in the main chain or a side chain and a carbonate bond (-O-CO-O-) in a repeating unit of the main chain, and the main chain may have a branched structure. (B) The siloxane-containing polycarbonate resin may be, for example, a polycarbonate-polysiloxane copolymer obtained by polycarbonateting a dihydroxy compound and containing a polycarbonate block having a polycarbonate structure and a polysiloxane block having a polysiloxane structure (preferably a polydiorganosiloxane structure).

As the dihydroxy compound for obtaining the polycarbonate block, dihydroxy compounds generally used in obtaining polycarbonate resins can be widely used, and among them, aromatic diols are preferable. That is, the polycarbonate structure in the polycarbonate block is preferably an aromatic polycarbonate structure. Examples of the aromatic diol include a bisphenol (bisphenol) compound and a bisnaphthol compound.

The bisphenol compound is a compound containing 2 phenol structures in a molecule, and 2 benzene rings in each of the 2 phenol structures may further have 1 to 3 substituents. The substituent is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound are exemplified. The 2 phenol structures in the bisphenol compound may be bonded directly and/or via a divalent linking group having 1 to 100 (preferably 1 to 50, more preferably 1 to 20) skeleton atoms selected from a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom.

Examples of the "divalent linking group" in the bisphenol compound include the same groups as those in the "divalent linking group" in the diphenylamine compound.

Specific examples of the bisphenol compound include: 4,4 '-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 2-bis (4-hydroxy-3, 3' -biphenylyl) propane, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) octane, 2-bis (4-, 2, 2-bis (3-bromo-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) cyclopentane, 4 '-dihydroxydiphenyl ether, 4' -dihydroxy-3, 3 '-dimethyldiphenyl ether, 4' -dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxydiphenyl sulfide, 2' -dimethyl-4, 4 '-sulfonyldiphenol, 4' -dihydroxy-3, 3 '-dimethyldiphenyl sulfoxide, 4' -dihydroxy-3, 3 '-dimethyldiphenyl sulfide, 2' -diphenyl-4, 4 '-sulfonyldiphenol, 4' -dihydroxy-3, 3 '-diphenyldiphenyl sulfoxide, 4' -dihydroxy-3, 3 '-diphenyldiphenyl sulfide, 1, 3-bis {2- (4-hydroxyphenyl) -2-propyl } benzene, 1, 4-bis (4-hydroxyphenyl) cyclohexane, 2, 4' -sulfonyl diphenol, 4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfoxide, 4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfide, 1, 3-bis {, 1, 3-bis (4-hydroxyphenyl) cyclohexane, and the like.

The double naphthol compound is a compound containing 2 naphthol structures in the molecule, and 2 naphthalene rings in the 2 naphthol structures may further have 1 to 3 substituents, respectively. The substituent is not particularly limited, and the same substituents as exemplified as the substituents of the benzene ring in the phenylenediamine compound are exemplified. The 2 naphthol structures in the binaphthol compound may be bonded directly and/or via a divalent linking group having 1 to 100 (preferably 1 to 50, more preferably 1 to 20) skeleton atoms selected from a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom.

Examples of the "divalent linking group" in the bisnaphthol compound include the same groups as those in the "divalent linking group" in the diphenylamine compound.

Specific examples of the bis-naphthol compound include bis (2-hydroxy-1-naphthyl) methane, 2-bis (2-hydroxy-1-naphthyl) propane, and 9, 9-bis (6-hydroxy-2-naphthyl) fluorene.

(B) When the siloxane-containing polycarbonate resin has a branched structure in the main chain, for example, a dihydroxy compound and a branching agent may be polycarbonated together. Examples of the branching agent include trifunctional or higher hydroxyl compounds, and preferably trifunctional or higher aromatic hydroxyl compounds.

Examples of the trifunctional or higher aromatic hydroxy compound include: phloroglucinol, gambogucide (phloroglucide), 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -2-heptene, 2,4, 6-trimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, 1,1, 1-tris (4-hydroxyphenyl) ethane, 1,1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) ethane, 2, 6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and the like.

The polydiorganosiloxane structure is not particularly limited, and examples thereof include: polydialkylsiloxane structures such as polydimethylsiloxane structures; polydiarylsiloxane structures such as polydiphenylsiloxane structures; polyalkylaryl siloxane structures such as polymethylphenylsiloxane structures; polydialkyl-diarylsiloxane structures such as polydimethyl-diphenylsiloxane structures; a polydialkyl-alkylaryl siloxane structure such as a polydimethyl-methylphenyl siloxane structure; polydiaryl-alkylaryl siloxane structures such as polydiphenyl-methylphenyl siloxane structures, etc., polydialkylsiloxane structures are preferred, and polydimethylsiloxane structures are particularly preferred.

The polydiorganosiloxane structure may be, for example: modified polydiorganosiloxane structures having functional groups introduced into a part of the side chain, such as amino-modified polydiorganosiloxane structures, epoxy-modified polydiorganosiloxane structures, carboxyl-modified polydiorganosiloxane structures, acryl-modified polydiorganosiloxane structures, methacryl-modified polydiorganosiloxane structures, mercapto-modified polydiorganosiloxane structures, and phenol-modified polydiorganosiloxane structures, but non-modified polydiorganosiloxane structures are preferred.

In the siloxane-containing polycarbonate resin (B), the content of the polysiloxane structure may be preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, assuming that the siloxane-containing polycarbonate resin (B) is 100% by mass. The upper limit of the content may be, for example, 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, or the like.

(B) The siloxane-containing polycarbonate resin is preferably a polycarbonate-polysiloxane copolymer having polysiloxane domains (domains) with an average size (averagesize) of 5 to 18nm in a polycarbonate matrix. The average size of the polysiloxane region is more preferably 5 to 15nm, still more preferably 5 to 12nm, and particularly preferably 8 to 12 nm. As a method for evaluating and measuring the average size of the polysiloxane region, for example, the method described in japanese patent No. 6343680 can be used.

(B) The viscosity average molecular weight of the siloxane-containing polycarbonate resin is not particularly limited, but is preferably 13,000 or more, more preferably 14,000 or more, further preferably 15,000 or more, and particularly preferably 16,000 or more. (B) The upper limit of the viscosity average molecular weight of the siloxane-containing polycarbonate resin is not particularly limited, but is preferably 25,000 or less, more preferably 23,000 or less, further preferably 22,000 or less, and particularly preferably 21,000 or less. As a method for measuring and calculating the viscosity average molecular weight, for example, the method described in japanese patent No. 6343680 can be used.

(B) The siloxane-containing polycarbonate resin is particularly preferably a polycarbonate-polysiloxane copolymer comprising a polycarbonate block represented by the formula (2) and a polysiloxane block represented by the formula (3).

[ chemical formula 3]

[ in the formula, R¹Each independently represents a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an arylcarbonyl group, an aryloxycarbonyl group, an arylcarbonyloxy group, an aralkyl group, or a combination thereof. Each Y independently represents a direct bond or a divalent linking group having 1 to 100 (preferably 1 to 50, more preferably 1 to 20) skeleton atoms selected from a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom. a represents an integer of 0 to 3 independently of each other. s represents an integer of 1 or more.]。

[ chemical formula 4]

[ in the formula, R²Each independently represents a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an arylcarbonyl group, an aryloxycarbonyl group, an arylcarbonyloxy group, an aralkyl group, or a combination thereof. R³Each independently represents a hydrogen atom, an alkyl group, or an aryl group. Each Z independently represents an alkylene group. b independently represents an integer of 0 to 3. u represents an integer of 4 to 150. t represents an integer of 1 or more.]。

(B) When the siloxane-containing polycarbonate resin is a polycarbonate-polysiloxane copolymer comprising a polycarbonate block represented by formula (2) and a polysiloxane block represented by formula (3), component (B) preferably comprises the polycarbonate block represented by formula (2) and the polysiloxane block represented by formula (3) in a total amount of 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.

In the above formula (2), examples of the "divalent linking group" represented by Y include the same groups as those of the "divalent linking group" in the diphenylamine compound. Each Y is independently preferably a direct bond, or an alkylene group, more preferably an alkylene group. a is preferably 0 or 1, particularly preferably 0.

In the above formula (3), R³Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group, and particularly preferably a methyl group. b is preferably 0 or 1, particularly preferably 0. u is preferably an integer of 4 to 120, more preferably an integer of 30 to 120, further preferably an integer of 30 to 100, and particularly preferably an integer of 30 to 60.

The content of the siloxane-containing polycarbonate resin (B) in the resin composition is not particularly limited, and is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 7% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass. (B) The upper limit of the content of the siloxane-containing polycarbonate resin is not particularly limited, and is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

(A) The mass ratio of the polyimide resin to the siloxane-containing polycarbonate resin (B) (component (a)/component (B)) 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 1.5 or more. The upper limit of the mass ratio is preferably 20 or less, preferably 10 or less, preferably 5 or less, preferably 3 or less.

(C) inorganic filler

The resin composition of the present invention may contain (C) an inorganic filler as an optional component. (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, 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, or may be used in combination in 2 or more kinds at an arbitrary ratio.

Examples of commercially available products of (C) the inorganic filler include: UFP-30 manufactured by electrochemical chemical industry; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Yadu Ma (Admatechs) of Kabushiki Kaisha; "UFP-30" manufactured by Denka corporation; "Silfil (シルフィル) NSS-3N", "SilfilNSS-4N" and "SilfilNSS-5N" manufactured by Deshan (トクヤマ, Ltd.); "SC 2500 SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Yadu Ma, K.K.; "DAW-03" and "FB-105 FD" manufactured by Denka corporation, and the like.

(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 0.05 μm or more, further preferably 0.1 μm or more, further more preferably 0.3 μm or more, and particularly preferably 0.4 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 (flowcell) method using a laser diffraction type particle size distribution measuring apparatus with the wavelength of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. 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 set to50m²A 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. The specific surface area of the inorganic filler material can be obtained by: according to the BET method, a specific surface area measuring apparatus (MacsorbHM-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.

The inorganic filler (C) is preferably surface-treated with an appropriate 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-butene) 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; 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, also can be used in any ratio of combination using 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 within a predetermined range. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass%, more preferably 0.2 to 3 mass%, and still more preferably 0.3 to 2 mass% of a surface treating agent with respect to 100 mass% of the inorganic filler.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler material. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, 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 melt viscosity in the form of a sheet from increasing, it is preferably 1.0mg/m²The 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 washed 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, "EMIA-320V" manufactured by horiba, Ltd., can be used.

When the resin composition contains the (C) inorganic filler, the content of the (C) inorganic filler in the resin composition is not particularly limited, and is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass. (C) The upper limit of the content of the inorganic filler is not particularly limited, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less, 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 resin having an epoxy group.

Examples of the epoxy resin (D) include: bixylenol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, t-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidyl amine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing a spiro ring, cyclohexane-type epoxy resin, cyclohexane dimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, Tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, and the like. Among them, cyclohexane type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, and bisphenol AF type epoxy resins are particularly preferable. (D) The epoxy resin may be used alone in 1 kind, or in combination of 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, and preferably a liquid epoxy resin and a solid epoxy resin are contained in combination.

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, and among them, cyclohexane type epoxy resin is particularly 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 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, JP-100 "and JP-200" manufactured by Nippon Caoda (a butadiene-structured epoxy resin); "ZX 1658" and "ZX 1658 GS" (cyclohexane type epoxy resins) manufactured by Nippon iron and gold 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 cresol novolak-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, and a tetraphenylethane-type epoxy resin are preferable, and among them, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, and a bisphenol AF-type epoxy resin are particularly 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" and "HP-7200H" (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" (naphthol type epoxy resin) manufactured by NIPPON steel chemical & materials co., Ltd.); ESN485 (naphthol type epoxy resin) manufactured by Nippon iron chemical & materials Co., Ltd; ESN375 (dihydroxynaphthalene type epoxy resin) manufactured by Nippon chemical and materials Co., Ltd; "YX 4000H", "YX 4000", "YL 6121", "YL 7890" and "YX 4000 HK" (biphenyl type epoxy resins) manufactured by Mitsubishi chemical company; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; "YX 7700" (novolac-type epoxy resin containing a xylene structure) 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" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. 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 epoxy resin (D), the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably in the range of 100:1 to 1:100, more preferably in the range of 20:1 to 1:50, and still more preferably in the range of 1:1 to 1: 30.

(D) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 70g/eq to 2,000g/eq, still more preferably 90g/eq to 1,000g/eq, and still more preferably 100g/eq to 400g/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).

When the resin composition contains the epoxy resin (D), the content of the epoxy resin (D) 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, and particularly preferably 15% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass. (D) The upper limit of the content of the epoxy resin is not particularly limited, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

(E) curing agent

When the resin composition of the present invention contains (D) an epoxy resin, (E) a curing agent having a function of curing (D) the epoxy resin may be contained.

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

As the phenol curing agent and the naphthol curing agent, a phenol curing agent having a novolac (novolak) structure or a naphthol curing agent having a novolac 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, "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", and "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD 2090", "TD-2090-60M" manufactured by Nippon iron chemical and materials Co.

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-based 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, phenolphthalein, 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, phenol novolac resin, and the like. 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 (phenonolnovolac), 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 divalent structural unit formed from phenylene-dicyclopentanyl-ene (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), which are active ester-based curing agents that are benzoylates 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; HFB2006M manufactured by Showa Polymer Co., Ltd, "P-d", "F-a" manufactured by four national chemical industries, Ltd.

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.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo chemical Co., Ltd.

When the resin composition contains (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 groups of E) curing agent ] is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and still more preferably 1:0.4 to 1: 1.4. Here, regarding the reactive group of the (E) curing agent, for example, when the curing agent is a phenol-based curing agent or a naphthol-based curing agent, the reactive group is an aromatic hydroxyl group; when the curing agent is an active ester curing agent, the reactive group is an active ester group, and the reactive group differs depending on the kind of the curing agent.

(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% by mass, the content is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more.

When the resin composition contains the (E) curing agent, the content of the (E) curing agent 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 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. (E) The upper limit of the content of the curing agent is not particularly limited, and is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

(F) curing Accelerator

When the resin composition of the present invention contains (D) an epoxy resin, (F) a curing accelerator having a function of accelerating curing of (D) the epoxy resin may be contained as an optional component.

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, metal-based curing accelerators, and the like. Among them, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an amine-based curing accelerator is particularly preferable. The curing accelerator may be used alone in 1 kind, or 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 hydrogen salt, tetrabutylphosphonium cresol novolak resin trimer salt, di-t-butylmethylphosphonium tetraphenylborate salt; 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.

When the resin composition contains the (F) curing accelerator, the content of the (F) curing accelerator in the resin composition is not particularly limited, and is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further 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%. (F) The upper limit of the content of the curing accelerator is not particularly limited, and is preferably 5% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

< (G) other additives

The resin composition of the present invention may further contain an optional additive as a nonvolatile component. Examples of such additives include: organic fillers such as rubber particles, polyamide fine particles, and silicone particles; (B) thermoplastic resins other than the above components, such as polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether 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 other than non-reactive phosphazene compounds such as phosphorus flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g., antimony trioxide), and the like. 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 contain an arbitrary 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 (ethylene digylcoloacetate), 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 product imidized in advance), (B) a siloxane-containing polycarbonate resin (a product carbonated in advance), (C) an inorganic filler used as needed, (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 all 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 continuously. 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 contains (a) a polyimide resin and (B) a siloxane-containing polycarbonate resin, and therefore can provide a cured product having a low coefficient of thermal expansion and suppressed warpage. In addition, the compatibility of each component can be made excellent.

The cured product of the resin composition of the present invention may have a linear thermal expansion coefficient (ppm) of 25 to 150 ℃ as measured at a temperature rise rate of 5 ℃/min, preferably less than 80ppm, more preferably less than 70ppm, still more preferably less than 65ppm, yet still more preferably less than 62ppm, and particularly preferably less than 60ppm, in view of low thermal expansion coefficient, for example, a cured product obtained by curing the resin composition under curing conditions of 190 ℃ and 90 minutes.

The cured product of the resin composition of the present invention has a warpage-suppressing effect, and for example, the amount of warpage when the resin composition is cured under the curing conditions of 190 ℃ and 90 minutes to obtain a cured product having a width of 160mm and a length of 120mm, and the remaining 1-point warpage is measured while fixing 3 points of the cured product may be preferably less than 30mm, more preferably less than 25mm, still more preferably less than 20mm, and particularly preferably less than 17 mm.

In the resin composition of the present invention, it is preferable that the generation of a separated product is not observed even when the resin composition is stored in a refrigerator at 5 ℃ for 3 days and then observed with an optical microscope, for example, from the viewpoint of excellent compatibility.

< 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 laminates such as resin sheets and prepregs, for example.

< 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: polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), acrylic polymer such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. 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: examples of the PET film having a release layer containing an alkyd resin-based release agent as a main component include "SK-1", "AL-5" and "AL-7" manufactured by Lindcaceae, "LumirrorT 60" manufactured by Toray, Purex "manufactured by Ditikon, 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 is directly applied to the support using a die coater or the like, or a resin varnish in which the resin composition is dissolved in an organic solvent is prepared and applied to the support using a die coater or the like, and then dried to form a resin composition layer.

Examples of the organic solvent that can be used when applying the coating composition to the support include the same organic solvents as those listed 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 of 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. Although the boiling point of the organic solvent in the resin composition or the resin varnish varies, 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 is 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 producing the laminated sheet corresponds to the number of insulating layers contained 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 is a sheet 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 or through holes in the multilayer flexible substrate.

The laminated sheet may further contain 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 layers 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 metals (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, and the like, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal; 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 two 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) a step of 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 content of the resin composition, for example, after the multilayer resin composition layers are all stacked, the stacked multilayer resin composition layers may be collectively cured. For example, each time another resin composition layer is laminated on a certain resin composition layer, the laminated resin composition layer may be cured.

Hereinafter, a preferred embodiment of the step (b) will be described. In the embodiments described below, the resin composition layers are appropriately denoted by "first resin composition layer" and "second resin composition layer" for the sake of distinction, and the insulating layers obtained by curing these resin composition layers are also denoted by "first insulating layer" and "second insulating layer" as in the case of 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 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) a step of forming a hole in the first insulating layer,

(IV) a step of roughening the first insulating layer,

(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-Materials, a vacuum applicator manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

When the resin sheet is used, the lamination of the sheet-like support base material and the first resin composition layer can be performed, for example, by: the resin sheet is pressed from the support side, and the first resin composition layer of the resin sheet is heat-pressure bonded 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, may be 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 first resin composition layer can be subjected to smoothing treatment by pressing under normal pressure (atmospheric pressure), for example, with a heat-pressure bonding 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 from the support side with the heating and pressure-bonding member. 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 continuously performed 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. The first resin composition layer can be cured by drying it, but when it contains a thermosetting resin such as an epoxy resin, it can be cured by heat curing in addition to drying.

In general, when the epoxy resin is contained, specific heat curing conditions differ depending on the kind of the resin composition. 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.

In the case of containing an epoxy resin, 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), the removal of the scum is also performed. 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 an aqueous sodium hydroxide solution and an aqueous potassium hydroxide 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 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. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

The first insulating layer is obtained in step (II), and step (VI) is performed after step (III), step (IV), and step (V) are performed, if necessary. 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 two resin composition layers, that is, the first resin composition layer and the second resin composition layer, has been described, but the laminated sheet may be produced by laminating and curing three 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 in the steps (VI) to (VII), and the drilling of the insulating layer, the roughening treatment of the insulating layer, and the formation of the conductor layer on the insulating layer in the steps (VIII) to (X) which are used as necessary may be repeated to manufacture the laminated sheet. Thus, a laminated sheet including three or more insulating layers can be obtained.

The method according to the above embodiment may include any process other than the above process. 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 the above-described method of manufacturing a laminated sheet. Therefore, 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 not only the above-described steps but also any other steps. For example, the method for manufacturing a multilayer flexible substrate provided with an electronic component may include a step of bonding the electronic component to the laminated sheet. The bonding condition between the laminated sheet and the electronic component can be any condition that allows the terminal electrode of the electronic component to be conductively connected to a conductor layer provided as a wiring on the laminated sheet. 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 bending a laminated sheet included in the multilayer flexible substrate so that one surface faces each other. For example, the multilayer flexible substrate is housed in a case of a semiconductor device in a state of being bent and reduced in size. In addition, for example, in a semiconductor device having a flexible movable portion, a multilayer flexible substrate is provided in the movable 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 can be stored in a case of a semiconductor device by being bent so that one surface of a laminated sheet included in the multilayer flexible substrate faces each other.

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, for example, by a manufacturing method including 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 described in detail 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.

< Synthesis example 1: synthesis of polyimide resin 1

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 discharging toluene halfway out of the system under a nitrogen atmosphere at 180 ℃ to obtain a polyimide solution containing polyimide resin 1 (nonvolatile content: 20 mass%). In the polyimide solution, no precipitation of the synthesized polyimide resin 1 was observed.

< Synthesis example 2: synthesis of polyimide resin 2

65.0g of aromatic tetracarboxylic dianhydride (BisDA-1000 manufactured by SABICIapan, 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) and 5.4g of 1, 3-bis (aminomethyl) cyclohexane were added dropwise thereto, and imidization was carried out at 140 ℃ for 1 hour. Thus, a polyimide solution (nonvolatile content: 30% by mass) containing the polyimide resin 2 was obtained. In addition, the weight average molecular weight of the polyimide resin 2 was 25,000.

< Synthesis example 3: synthesis of polyimide resin 3

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 the condensation water was azeotropically removed together with toluene under a nitrogen stream. The results of "a predetermined amount of water was stored in the quantitative water receiver" and "no outflow of water was observed" were confirmed. After confirmation, the reaction solution was further heated and stirred at 200 ℃ for 1 hour. Then, cooling was performed to obtain a polyimide solution (nonvolatile content: 20 mass%) containing a polyimide resin 3 having a 1,1, 3-trimethylindan skeleton. The obtained polyimide resin 3 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 3 was 12,000.

[ chemical formula 5]

[ chemical formula 6]

< Synthesis example 4: synthesis of polycarbonate-polydimethylsiloxane copolymer resin

21591 parts of ion exchange water and 3674 parts of a 48.5% aqueous sodium hydroxide solution were charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser, 3880 parts of 2, 2-bis (4-hydroxyphenyl) propane (bisphenol a) and 7.6 parts of dithionite were dissolved, 14565 parts of methylene chloride was added, and 1900 parts of phosgene was blown into the reactor at 22 to 30 ℃ for 60 minutes under stirring. Next, a solution prepared by dissolving 48.5% aqueous sodium hydroxide solution 1131 parts and p-tert-butylphenol 105 parts in methylene chloride 800 parts was added, and while stirring, a solution prepared by dissolving diorthohydroxyphenyl-terminated polydimethylsiloxane compound represented by the following formula (4) (the average number of repetitions p in the formula is about 37)430 parts in methylene chloride 1600 parts was added at a rate of 0.0008 mol/min per 1 mol of 2, 2-bis (4-hydroxyphenyl) propane, and the mixture was emulsified, and then vigorously stirred again. Under the above stirring, 4.3 parts of triethylamine was added to the reaction mixture at 26 ℃ and the mixture was stirred at 26 to 31 ℃ for 45 minutes to complete the reaction. After the reaction, the organic phase was separated, diluted with dichloromethane and washed with water, then acidified with hydrochloric acid and washed with water, and the conductivity of the aqueous phase was substantially the same as that of ion-exchanged water, and then the aqueous phase was put into a kneader filled with warm water, and the dichloromethane was evaporated while stirring to obtain a powder of a polycarbonate-polydimethylsiloxane copolymer resin. After dehydration, the resulting mixture was dried at 120 ℃ for 12 hours by means of a hot air circulation dryer to obtain a polycarbonate-polydimethylsiloxane copolymer resin powder (polydimethylsiloxane structure content: 8.2%, average size of polydimethylsiloxane domains: 9nm, viscosity-average molecular weight: 19,400).

[ chemical formula 7]

< 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), 100 parts of the polyimide solution (having a nonvolatile content of 20 mass%) obtained in synthetic example 1, and 10 parts of cyclohexanone was heated and dissolved while stirring. After cooling to room temperature, 50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (nonvolatile matter: 20% by mass, toluene solution) obtained in Synthesis example 4,4 parts of a triazine skeleton-containing cresol novolak-type curing agent ("LA 3018-50P" manufactured by DIC having a hydroxyl equivalent of about 151 and a solid content of 50% 2-methoxypropanol solution), 4 parts of an active ester-type curing agent ("EXB-8000L-65M" manufactured by DIC having an active group equivalent of about 220 and a nonvolatile matter of 65% toluene: 1 solution of MEK), 6 parts of a spherical silica (Sc 2500SQ manufactured by Yadmax having an average particle diameter of 0.5 μ M and a specific surface area of 11.2M) were mixed therewith²Per g, 100 parts of silica was uniformly dispersed in 50 parts of N-phenyl-3-aminopropyltrimethoxysilane (product obtained by surface treatment of 1 part of KBM573 manufactured by shin-Etsu chemical Co., Ltd.) and 0.2 part of amine-based curing accelerator (4-Dimethylaminopyridine (DMAP)) by a high-speed rotary mixer, and then the mixture was filtered by a drum filter (SHP 020 manufactured by ROKITECHNO Co., Ltd.)Filtration was carried out 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 66.7 parts of the polyimide solution (nonvolatile component: 30 mass%) obtained in synthesis example 2 was used instead of 100 parts of the polyimide solution (nonvolatile component: 20 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 100 parts of the polyimide solution (nonvolatile component: 20 mass%) obtained in synthesis example 3 was used instead of 100 parts of the polyimide solution (nonvolatile component: 20 mass%) obtained in synthesis example 1.

< comparative example 1: preparation of resin composition 4

A resin composition 4 was prepared in the same manner as in example 1, except that 50 parts of a polycarbonate resin ("FPC 2136" manufactured by mitsubishi gas chemical corporation, with a nonvolatile content of 20 mass%) was used instead of 50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (with a nonvolatile content of 20 mass%, toluene solution) obtained in synthesis example 4.

Comparative example 2: preparation of resin composition 5

A resin composition 5 was prepared in the same manner as in example 1, except that 50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (nonvolatile component: 20% by mass, toluene solution) obtained in synthesis example 4 was not used, and 10 parts of an epoxy-modified silicone oil ("KF-105" manufactured by shin-Etsu chemical Co., Ltd.) was used.

< comparative example 3: preparation of resin composition 6

A resin composition 6 was prepared in the same manner as in example 1, except that 50 parts of a polycarbonate resin ("FPC 2136" manufactured by mitsubishi gas chemical company, nonvolatile components of 20 mass%) was used instead of 50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (nonvolatile components of 20 mass%, toluene solution) obtained in synthesis example 4 and 10 parts of an epoxy-modified silicone oil ("KF-105" manufactured by shin-shi chemical company) was used.

< comparative example 4: preparation of resin composition 7

A resin composition 7 was prepared in the same manner as in example 1 except that 66.67 parts of a phenoxy resin ("YX 7553BH 30" manufactured by mitsubishi chemical corporation, nonvolatile content of which is 30 mass%, and a 1:1 solution of MEK and cyclohexanone) was used instead of 100 parts of the polyimide solution (nonvolatile content of which is 20 mass%) obtained in synthesis example 1.

< measurement of average particle diameter of inorganic Filler >

100mg of the inorganic filler and 10g of methyl ethyl ketone were weighed into a vial, and dispersed for 10 minutes by ultrasonic waves. The particle size distribution of the inorganic filler was measured on a volume basis by a flow cell system using a laser diffraction type particle size distribution measuring apparatus ("LA-960" manufactured by horiba ltd.) with the wavelengths of the light source used being blue and red. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as a median particle size.

< determination of specific surface area of inorganic Filler >

The specific surface area of the inorganic filler was measured by adsorbing nitrogen gas on the surface of the sample using a BET full-automatic specific surface area measuring apparatus (Macsorb HM-1210, Mountech corporation) and calculating the specific surface area by the BET multipoint method.

< test example 1: confirmation of compatibility in resin composition

The prepared resin compositions 1 to 7 were stored in a refrigerator at 5 ℃ for 3 days, and then the resin compositions were applied to a glass plate, followed by observing the presence or absence of separation in the resin compositions with an optical microscope ("KH 8700" manufactured by HIROX). The case where the production of the isolate was not confirmed by the optical microscope was evaluated as "o", and the case where the production of the isolate was confirmed by the optical microscope was evaluated as "x".

< test example 2: measurement and evaluation of Linear thermal expansion coefficient

The resin compositions of examples and comparative examples were uniformly applied to the release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater so that the thickness of the dried resin composition layer became 40 μm, and dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes to obtain a resin sheet 1.

The obtained resin sheet 1 was laminated on a polyimide film (UPILEX S, manufactured by Utsu corporation) using a batch vacuum pressure laminator (MVLP-500, manufactured by Kabushiki Kaisha Co., Ltd.). For lamination, the pressure was reduced for 30 seconds to 13hPa or less, and then the laminate was pressure-bonded at 120 ℃ for 30 seconds at a pressure of 0.74 MPa. Then, the PET film was peeled off, and the resin composition was cured under curing conditions of 190 ℃ for 90 minutes to peel off the polyimide film, thereby obtaining a cured product sample.

The obtained cured product sample was cut into a test piece having a width of 5mm and a length of 15mm, and subjected to thermomechanical analysis by a tensile load method using a thermomechanical analyzer ("Thermo Plus TMA 8310" manufactured by Rigaku corporation). After the sample was mounted on the apparatus, the measurement was continuously performed 2 times under the measurement conditions of a load of 1g and a temperature rise rate of 5 ℃/min. The average linear thermal expansion coefficient (ppm) at 25 ℃ to 150 ℃ in 2 measurements was calculated. The case where the linear thermal expansion coefficient was less than 60ppm was evaluated as "O", and the case where the linear thermal expansion coefficient was 60ppm or more was evaluated as "X".

< test example 3: measurement and evaluation of warpage

The resin compositions of examples and comparative examples were uniformly applied to the release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater so that the thickness of the dried resin composition layer became 30 μm, and dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes to obtain a resin sheet 2.

The obtained resin sheet 2 was laminated on a laminate (an etched (etchrout) copper foil product of MCL-E-700G manufactured by Hitachi chemical Co., Ltd.) using a batch vacuum pressure laminator ("MVLP-500" manufactured by Kaisha corporation). For lamination, the pressure was reduced for 30 seconds to 13hPa or less, and then the laminate was pressure-bonded at 120 ℃ for 30 seconds at a pressure of 0.74 MPa. Then, the PET film was peeled off, and the resin composition was cured under curing conditions of 190 ℃ for 90 minutes to peel off the polyimide film, thereby obtaining a cured product sample. The obtained cured product was cut into test pieces having a width of 160mm and a length of 120mm, and the amount of warpage at the remaining 1 point was measured while fixing 3 points. The evaluation was "good" when the warpage amount was less than 20mm, and "poor" when the warpage amount was 20mm or more.

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 by using a resin composition comprising (a) a polyimide resin and (B) a siloxane-containing polycarbonate resin, a cured product having a low coefficient of thermal expansion and suppressed warpage can be obtained.

Claims

1. A resin composition comprising (A) a polyimide resin and (B) a siloxane-containing polycarbonate resin.

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 component (B) is a polycarbonate-polysiloxane copolymer comprising a polycarbonate block having a polycarbonate structure and a polysiloxane block having a polysiloxane structure.

4. The resin composition according to claim 3, wherein the polysiloxane structure is a polydialkylsiloxane structure.

5. The resin composition according to claim 3, wherein the polycarbonate structure is an aromatic polycarbonate structure.

6. The resin composition according to claim 3, wherein the content of the polysiloxane structure in component (B) is 1% by mass or more and 30% by mass or less, assuming that component (B) is 100% by mass.

7. The resin composition according to claim 1, wherein the viscosity average molecular weight of component (B) is 13,000 or more and 25,000 or less.

8. The resin composition according to claim 1, wherein the mass ratio of component (A) to component (B), (component (A)/component (B)), is 1 or more and 5 or less.

9. The resin composition according to claim 1, further comprising (C) an inorganic filler.

10. The resin composition according to claim 9, wherein the component (C) is silica.

11. The resin composition according to claim 9, wherein the content of the component (C) is 30% by mass or more and 60% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

12. The resin composition according to claim 1, further comprising (D) an epoxy resin and (E) a curing agent.

13. The resin composition according to claim 12, wherein the component (E) comprises an active ester-based curing agent.

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

15. A cured product of the resin composition according to any one of claims 1 to 14.

16. A resin sheet, comprising:

support body, and

a resin composition layer formed of the resin composition according to any one of claims 1 to 14, provided on the support.

17. A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition according to any one of claims 1 to 14.

18. A semiconductor device comprising the multilayer flexible substrate according to claim 17.