JP2021020982A - Resin composition - Google Patents

Abstract

To provide a resin composition that can give a cured product having low thermal expansibility as well as a suppressed warp.SOLUTION: A resin composition contains (A) a polyimide resin and (B) a siloxane-containing polycarbonate resin.SELECTED DRAWING: None

Description

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

In recent years, there has been an increasing demand for semiconductor components that are thinner, lighter, and have a higher mounting density. In order to meet this demand, attention is being paid to using a flexible substrate as a substrate substrate used for semiconductor components. The flexible substrate can be thinner and lighter than the rigid substrate. Further, since the flexible substrate is flexible and deformable, it can be bent and mounted.

The flexible substrate is generally a circuit obtained by producing a three-layer film made of a polyimide film, a copper foil and an adhesive, or a two-layer film made of a polyimide film and a conductor layer, and etching the conductor layer according to a subtractive method. It is manufactured by forming and doing. Conventionally, a three-layer film is often used because it can be produced at a relatively low cost. However, in a circuit board having high-density wiring, a two-layer film may be used in order to solve the problems of heat resistance and electrical insulation of the adhesive. However, the two-layer film has problems in cost and productivity. Therefore, in order to solve this problem, Patent Documents 1 to 3 disclose insulating materials for multilayer flexible substrates. Further, Patent Documents 4 and 5 describe a polyimide resin. Further, Patent Document 6 describes a siloxane-containing polycarbonate resin.

Japanese Unexamined Patent Publication No. 2006-37083 Japanese Unexamined Patent Publication No. 2016-41797 Japanese Patent No. 6387181 Japanese Patent No. 6240798 Japanese Patent No. 6240799 Japanese Patent No. 6343680

In general, polyimide resins and polycarbonate resins used for flexible substrates have a low coefficient of thermal expansion, but have a problem that large warpage is likely to occur. On the other hand, the polysiloxane resin is known to have a high coefficient of thermal expansion and low compatibility, although it suppresses warpage.

An object of the present invention is to provide a resin composition or the like capable of obtaining a cured product having a low coefficient of thermal expansion and suppressed warpage.

As a result of diligent studies to achieve the object of the present invention, surprisingly, by using a resin composition containing (A) a polyimide resin and (B) a siloxane-containing polycarbonate resin, the thermal expansion rate We have found that it is possible to obtain a cured product having a low value and suppressed warpage, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (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 above-mentioned [1] or [2], wherein the component (B) is a polycarbonate-polysiloxane copolymer containing a polycarbonate block having a polycarbonate structure and a polysiloxane block having a polysiloxane structure. Resin composition.
[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] Any 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 when the component (B) is 100% by mass. The resin composition described in Crab.
[7] The resin composition according to any one of [1] to [6] above, wherein the viscosity average molecular weight of the component (B) is 13,000 or more and 25,000 or less.
[8] The resin according to any one of [1] to [7] above, wherein the mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 1 or more and 5 or less. Composition.
[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 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 when the non-volatile component in the resin composition is 100% by mass. Composition.
[12] The resin composition according to any one of [1] to [11] above, further comprising (D) an epoxy resin and (E) a curing agent.
[13] The resin composition according to the above [12], wherein the component (E) contains 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 a resin composition layer provided on the support and formed of the resin composition according to any one of the above [1] to [14].
[17] A multilayer flexible substrate including an insulating layer formed by curing the resin composition according to any one of the above [1] to [14].
[18] A semiconductor device including the multilayer flexible substrate according to the above [17].

According to the resin composition of the present invention, it is possible to obtain a cured product having a low coefficient of thermal expansion and suppressed warpage.

Hereinafter, the present invention will be described in detail according to its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

<Resin composition>
The resin composition of the present invention contains (A) a polyimide resin and (B) a siloxane-containing polycarbonate resin. By using such a resin composition, it is possible to obtain a cured product having a low coefficient of thermal expansion and suppressed warpage. In addition, the compatibility of each component can be excellent.

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

<(A) Polyimide resin>
The resin composition of the present invention contains (A) a polyimide resin. The (A) polyimide resin is a resin having an imide bond in the repeating unit. The polyimide resin (A) may generally contain a resin obtained by an imidization reaction of a diamine compound and a tetracarboxylic acid anhydride. The (A) polyimide resin also includes a modified polyimide resin such as a siloxane-modified polyimide resin.

The polyimide resin (A) is not particularly limited, but for example, the formula (1):

[In the formula, X ¹ represents a tetravalent group obtained by removing two -CO-O-CO- from tetracarboxylic acid dianhydride, for example, from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. It can be an organic group consisting of 2 to 100 (preferably 2 to 50) skeleton atoms selected. X ² represents a divalent group obtained by removing two -NH ₂ from the diamine compound, for example, 2 to 100 (preferably 2 to 50) selected from carbon atom, oxygen atom, nitrogen atom, and sulfur atom. It can be an organic group consisting of skeleton atoms. n represents an integer of 2 or more. ] Can be included. The organic groups of X ¹ and X ² in the formula (1) are not particularly limited as long as they are within the range of a chemically stable structure, and have a structure appropriately selected by those skilled in the art. For example, a known polyimide resin. It can be the structure of. When the polyimide resin (A) contains a structure represented by the formula (1), the structure represented by the formula (1) is preferably contained in an amount of 80% by mass or more, more preferably 85% by mass or more, and 90% by mass. It is more preferably contained in an amount of% or more, and particularly preferably 95% by mass or more.

The diamine compound for preparing the (A) polyimide resin is not particularly limited, and examples thereof include an aliphatic diamine compound and an aromatic diamine compound.

Examples of the aliphatic diamine compound include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-diaminopentane. , 1,10-Diaminodecane and other linear aliphatic diamine compounds; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched chain aliphatic diamine compounds such as diaminopentane; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexyl) An alicyclic diamine compound such as amine); dimer acid type diamine (hereinafter, also referred to as “dimer diamine”) and the like can be mentioned.

The diamine-type diamine means a diamine compound obtained by substituting two terminal carboxy groups (-COOH) of dimer acid with an aminomethyl group (-CH _2- NH ₂ ) or an amino group (-NH ₂ ). To do. Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, particularly preferably those having 18 carbon atoms), and its industrial production process is almost the same in the industry. It is standardized. As the dimer acid, a dimer acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid, which are particularly inexpensive and easily available, can be easily obtained. Further, the dimer acid may contain an arbitrary amount of monomeric acid, trimer acid, other polymerized fatty acids and the like depending on the production method, the degree of purification and the like. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in the present specification, hydrogenated substances whose degree of unsaturation is lowered by further hydrogenation reaction are also included in dimer acid. Commercially available products of the dimer acid type diamine are available, and examples thereof include PRIAMINE 1073, PRIAMINE 1074, and PRIAMINE 1075 manufactured by Croda Japan, and Versamine 551 and Versamine 552 manufactured by Cognis Japan.

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

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

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and the like. The "alkyl group" refers to a straight chain, branched chain 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group and the like. 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 a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a cyclopentoxy group, a cyclohexyloxy group and the like. The "alkylcarbonyl group" refers to a monovalent group (alkyl-CO-) formed by bonding an alkyl group to a carbonyl. 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 an acetyl group, a propanoyl group, a butanoyl group, a 2-methylpropanoyl group and the like. The "alkoxycarbonyl group" refers to a monovalent group (alkyl-O-CO-) formed by bonding an alkoxy group to a carbonyl. 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, a propoxycarbonyl group and the like. The "alkylcarbonyloxy group" refers to 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 an acetyloxy group, a propanoyloxy group, a butanoyloxy group and the like. The "aryl group" refers to a monovalent aromatic hydrocarbon group. 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 a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, 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 a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group and the like. The "arylcarbonyl group" refers to a monovalent group (aryl-CO-) formed by bonding an aryl group to a carbonyl. 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, a 2-naphthoyl group and the like. The "aryloxycarbonyl group" refers to a monovalent group (aryl-O-CO-) formed by bonding an aryloxy group to a carbonyl. 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-naphthoxycarbonyl group, a 2-naphthoxycarbonyl group and the like. The "arylcarbonyloxy group" 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 a benzoyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group and the like. The "aralkyl group" refers to an alkyl group substituted with one 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, and 3,5-diamino. Examples thereof include biphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine and the like.

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

The dianiline compound means a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures further optionally has 1 to 3 substituents. Can be done. The substituent here is not particularly limited, and examples thereof include the same as those exemplified as the substituent of the benzene ring in the phenylenediamine compound. The two aniline structures in the dianiline compound are directly bonded and / or 1 to 100 selected from carbon, oxygen, sulfur and nitrogen atoms (preferably 1 to 50, more preferably 1 to 20). It can be attached via one or two divalent linking groups having the skeleton atom of. Dianiline compounds also include those in which two aniline structures are bonded in two places.

As "divalent linking group" in dianiline compounds, for example, -NHCO -, - OCO -, - O -, - S -, - CO -, - SO 2 -, - SO -, - NH -, - ( Alkylene group)-,-(haloalkylene group)-, -CH = CH-, -Ph-, -Ph-Ph-, -Ph-O-Ph-, -Ph-S-Ph-, -Ph-CO- Ph-, -Ph-SO _2- Ph-, -Ph-SO-Ph-, -Ph-NH-Ph-, -Ph- (alkylene group) -Ph-,-(alkylene group) -Ph- (alkylene group) )-, -Ph- (haloalkylene group) -Ph-,-(haloalkylene group) -Ph- (haloalkylene group)-, -O-Ph-O-, -O-Ph-Ph-O-,- O-Ph-O-Ph-O-, -O-Ph-CO-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph- (alkylene group) -Ph-O- , -O- (alkylene group) -Ph- (alkylene group) -O-, -O-Ph- (haloalkylene group) -Ph-O-, -O- (haloalkylene group) -Ph- (haloalkylene group) ) -O-,

(In the formula, * indicates the binding site.)
And so on.

"Ph" represents a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group. By "alkylene group" is meant a straight chain, branched chain 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. The "alkylene group", for _{example, -CH 2 -, - CH 2} -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) _{-, - CH (CH 3)} -CH 2 -, - C (CH 3) 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, −CH ₂ −CH (CH ₃ ) −CH ₂ −, −CH (CH ₃ ) −CH ₂ −CH ₂ −, −CH ₂ −C (CH ₃ ) ₂ −, −C (CH ₃ ) ₂ −CH _{2 -, - CH 2 -CH 2 -CH} 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -CH (CH 3) -, - CH 2 -CH 2 -CH (CH 3) -CH ₂ −, −CH ₂ −CH (CH ₃ ) −CH ₂ −CH ₂ −, −CH (CH ₃ ) −CH ₂ −CH ₂ −CH ₂ −, −CH ₂ −CH ₂ −C (CH ₃ ) _{2 -, - CH 2 -C (CH} 3) 2 -CH 2 -, - C (CH 3) 2 -CH 2 -CH 2 -, - C (CH 2 CH 3) 2 -, 1,1- cyclohexylene, Examples thereof include 3,3,5-trimethyl-1,1-cyclohexylene. By "haloalkylene group" is meant an alkylene group in which some or all of the hydrogen atoms have been replaced by 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 "haloalkylene group" include those in which all the hydrogen atoms are replaced with fluorine atoms in the alkylene group exemplified above.

Specific examples of the dianiline compound include 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4-aminophenyl4-aminobenzoate, 1,3-bis (3-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenyl) propane, 4,4'-(hexafluoroisopropyridene) dianiline, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, α, α-bis [4- (4-aminophenoxy) ) Phenyl] -1,3-diisopropylbenzene, α, α-bis [4- (4-aminophenoxy) phenyl] -1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene) dianiline, 2,2 -Bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3-methyl-4-aminophenyl) benzene, 4,4'-diamino-3,3'-dimethyl-1,1'- Biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis (3-methyl-4-aminophenyl) fluorene, 5- (4-aminophenoxy)- Examples thereof include 3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindan, 5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate, and the like, preferably. 5- (4-Aminophenoxy) -3- [4- (4-Aminophenoxy) phenyl] -1,1,3-trimethylindan, and 4-aminobenzoate 5-amino-1,1'-biphenyl-2 -Il.

As the diamine compound, a commercially available one may be used, or a compound synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

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

Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic acid dianhydride and the like, and preferred examples thereof. It is a diphthalic dianhydride.

The benzenetetracarboxylic dianhydride means a benzene dianhydride having 4 carboxy groups, and the benzene ring here may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited, and examples thereof include the same as those exemplified as the substituent of the benzene ring in the phenylenediamine compound. Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

The naphthalenetetracarboxylic dianhydride means a naphthalene dianhydride having 4 carboxy groups, and the naphthalene ring here may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited, and examples thereof include the same as those exemplified as the substituent of the benzene ring in the phenylenediamine compound. Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

The anthracene tetracarboxylic dianhydride means an anthracene dianhydride having 4 carboxy groups, and the anthracene ring here may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited, and examples thereof include the same as those exemplified as the substituent of the benzene ring in the phenylenediamine compound. There is no particular limitation. Specific examples of the anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride.

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

Examples of the "divalent linking group" in the diphthalic acid dianhydride include the same as the "divalent linking group" in the dianiline compound.

Specific examples of the diphthalic acid dianhydride include 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,. 3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride Anhydroide, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether Tetetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic dianhydride 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfonate dianhydride, methylene-4, 4'-diphthalic acid dianhydride, 1,1-ethinilidene-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4 , 4'-Diphthalic dianhydride, 1,3-trimethylethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-penta Methylene-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride , 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,2-bis (2,3-di) Carboxiphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4'-(4,5pyridenediphenoxy) bisphthalic acid dianhydride, etc. Can be mentioned.

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

As the tetracarboxylic dianhydride, a commercially available product may be used, or a product synthesized by a known method or a method similar thereto may be used. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

The content of the structure derived from the aromatic tetracarboxylic dianhydride with respect to the total structure derived from the tetracarboxylic dianhydride constituting the (A) polyimide resin is preferably 10 mol% or more, preferably 30 mol%. The above is more preferable, 50 mol% or more is further preferable, 70 mol% or more is further preferable, 90 mol% or more is even more preferable, and 100 mol% is more preferable. Is particularly preferable.

The weight average molecular weight of the polyimide resin (A) is not particularly limited, but is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 8,000 or more, and particularly preferably 10,000 or more. Is. The upper limit of the weight average molecular weight of the (A) polyimide resin is not particularly limited, but is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50. It is 000 or less.

The content of the (A) polyimide resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 5. It is by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. The upper limit of the content of the polyimide resin (A) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass or less. It is more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

<(B) Siloxane-containing polycarbonate resin>
The resin composition of the present invention contains (B) a siloxane-containing polycarbonate resin. (B) The siloxane-containing polycarbonate resin has a polysiloxane structure (preferably a polydiorganosiloxane structure) in the main chain or side chain and a carbonic acid ester bond (-O-CO-O-) in the repeating unit of the main chain. It means a polymer, and the main chain may have a branched structure. (B) The siloxane-containing polycarbonate resin includes, for example, a polycarbonate block having a polycarbonate structure obtained by polycarbonate esterifying a dihydroxy compound, and a polysiloxane block having a polysiloxane structure (preferably a polydiorganosiloxane structure). It can be a polycarbonate-polysiloxane copolymer.

As the dihydroxy compound for obtaining the polycarbonate block, a wide range of dihydroxy compounds generally used for obtaining the polycarbonate resin can be 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 bisphenol compounds and bisnaphthol compounds.

The bisphenol compound means a compound containing two phenolic structures in the molecule, and each of the two benzene rings in the two phenolic structures further optionally has 1 to 3 substituents. Can be. The substituent here is not particularly limited, and examples thereof include the same as those exemplified as the substituent of the benzene ring in the phenylenediamine compound. The two phenolic structures in the bisphenol compound are directly bonded and / or 1 to 100 selected from carbon, oxygen, sulfur and nitrogen atoms (preferably 1 to 50, more preferably 1 to 20). It can be bonded via a divalent linking group having a skeleton atom of.

Examples of the "divalent linking group" in the bisphenol compound include the same as the "divalent linking group" in the dianiline compound.

Specific examples of the bisphenol compound include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-) 3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-) 4-Hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxy) Phenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4' -Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4'-sulfonyl Diphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl)- 2-propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) -2-propyl} benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) ) Cyclohexane and the like.

The bisnaphthol compound means a compound containing two naphthol structures in the molecule, and each of the two naphthalene rings in the two naphthol structures further optionally has 1 to 3 substituents. Can have. The substituent here is not particularly limited, and examples thereof include the same as those exemplified as the substituent of the benzene ring in the phenylenediamine compound. The two naphthol structures in the bisnaphthol compound are directly bonded and / or 1 to 100 (preferably 1 to 50, more preferably 1 to 20) selected from carbon, oxygen, sulfur and nitrogen atoms. ) Can be attached via a divalent linking group having a skeleton atom.

Examples of the "divalent linking group" in the bisnaphthol compound include the same as the "divalent linking group" in the dianiline compound.

Specific examples of the bisnaphthol compound include bis (2-hydroxy-1-naphthyl) methane, 2,2-bis (2-hydroxy-1-naphthyl) propane, and 9,9-bis (6-hydroxy-2-). Naftil) Fluorene and the like.

(B) When the main chain of the siloxane-containing polycarbonate resin has a branched structure, for example, the dihydroxy compound can be polycarbonated with a branching agent. Examples of the branching agent include trifunctional or higher functional hydroxy compounds, and trifunctional or higher aromatic hydroxy compounds are preferable.

Examples of trifunctional or higher aromatic hydroxy compounds include fluoroglucolcin, fluoroglucolside, 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 ( Examples thereof include 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, but for example, a polydialkylsiloxane structure such as a polydimethylsiloxane structure; a polydiarylsiloxane structure such as a polydiphenylsiloxane structure; a polyalkylaryl such as a polymethylphenylsiloxane structure. Siloxane structure; polydialkyl-diarylsiloxane structure such as polydimethyl-diphenylsiloxane structure; polydialkyl-alkylarylsiloxane structure such as polydimethyl-methylphenylsiloxane structure; polydiaryl-alkylarylsiloxane structure such as polydiphenyl-methylphenylsiloxane structure Examples thereof include a polydialkylsiloxane structure, and a polydimethylsiloxane structure is particularly preferable.

The polydiorganosiloxane structure includes, for example, an amino-modified polydiorganosiloxane structure, an epoxy-modified polydiorganosiloxane structure, a carboxy-modified polydiorganosiloxane structure, an acrylic-modified polydiorganosiloxane structure, a methacryl-modified polydiorganosiloxane structure, and a mercapto-modified polydiorganosiloxane structure. A modified polydiorganosiloxane structure in which a functional group is introduced into a part of a side chain such as a phenol-modified polydiorganosiloxane structure may be used, but a non-modified polydiorganosiloxane structure is preferable.

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

The (B) siloxane-containing polycarbonate resin is preferably a polycarbonate-polysiloxane copolymer in which a polysiloxane domain having an average size of 5 to 18 nm is present in the polycarbonate matrix. The average size of the polysiloxane domain is more preferably 5 to 15 nm, even more preferably 5 to 12 nm, and particularly preferably 8 to 12 nm. As a method for evaluating and measuring the average size of the polysiloxane domain, for example, the method described in Japanese Patent No. 6343680 can be used.

The viscosity average molecular weight of the (B) siloxane-containing polycarbonate resin is not particularly limited, but is preferably 13,000 or more, more preferably 14,000 or more, still more preferably 15,000 or more, and particularly preferably 16. It is over 000. The upper limit of the viscosity average molecular weight of the (B) siloxane-containing polycarbonate resin is not particularly limited, but is preferably 25,000 or less, more preferably 23,000 or less, still more preferably 22,000 or less, and particularly preferably 22,000 or less. It is 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.

The siloxane-containing polycarbonate resin (B) is, for example, the formula (2):

[In the formula, R ¹ is an independent halogen atom, alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, aryl group, aryloxy group, arylcarbonyl group, aryloxycarbonyl group. , Arylcarbonyloxy group, Alkoxy group, or a combination thereof. Y is an independent direct bond or 1 to 100 (preferably 1 to 50, more preferably 1 to 20) skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The divalent linking group having is shown. a independently represents an integer of 0 to 3. s represents an integer of 1 or more. ] And the formula (3):

[In the formula, R ² is an independent halogen atom, alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, aryl group, aryloxy group, arylcarbonyl group, aryloxycarbonyl group. , Arylcarbonyloxy group, Alkoxy group, or a combination thereof. R ³ independently represents a hydrogen atom, an alkyl group, or an aryl group. Z each independently represents an alkylene group. b represents an integer of 0 to 3 independently of each other. u represents an integer from 4 to 150. t represents an integer of 1 or more. ] Is particularly preferable, it is a polycarbonate-polysiloxane copolymer containing the polysiloxane block represented by.

When the siloxane-containing polycarbonate resin (B) is a polycarbonate-polysiloxane copolymer containing a polycarbonate block represented by the formula (2) and a polysiloxane block represented by the formula (3), the component (B) is of the formula. The polycarbonate block represented by (2) and the polysiloxane block represented by the formula (3) are preferably contained in an amount of 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more. Is more preferable, and 95% by mass or more is particularly preferable.

In the above formula (2), examples of the "divalent linking group" represented by Y include the same as the "divalent linking group" in the dianiline compound. Y is independently bonded, preferably a direct bond, or an alkylene group, more preferably an alkylene group. As for a, 0 or 1 is preferable, and 0 is particularly preferable.

In the above formula (3), R ³ is independently and 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, and 0 is particularly preferable. u is preferably an integer of 4 to 120, more preferably an integer of 30 to 120, even more preferably an integer of 30 to 100, and particularly preferably an integer of 30 to 60.

The content of the (B) siloxane-containing polycarbonate resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably. Is 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 7% by mass or more. The upper limit of the content of the siloxane-containing polycarbonate resin (B) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 40% by mass or less, more preferably 30% by mass. % Or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

The mass ratio (component (A) / component (B)) of the polyimide resin (A) to the polycarbonate resin containing (B) siloxane is not particularly limited, but is preferably 0.1 or more, more preferably 0. It is 5 or more, more 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, and preferably 3 or less.

<(C) Inorganic filler>
The resin composition of the present invention may contain (C) an inorganic filler as an arbitrary component. (C) The inorganic filler is contained in the resin composition in the form of particles.

(C) An inorganic compound is used as the material of the inorganic filler. 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, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium 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 titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) As the inorganic filler, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

(C) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd .; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; manufactured by Admatex Co., Ltd. "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-" manufactured by Tokuyama Corporation. 5N ”;“ SC2500SQ ”,“ SO-C4 ”,“ SO-C2 ”,“ SO-C1 ”manufactured by Admatex;“ DAW-03 ”,“ FB-105FD ”manufactured by Denka, and the like.

The average particle size of the inorganic filler (C) is not particularly limited, but is preferably 40 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 3 μm or less, and particularly preferably 1 μm or less. Is. The lower limit of the average particle size of the inorganic filler (C) is not particularly limited, but is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, still more preferably 0. .1 μm or more, even more preferably 0.3 μm or more, particularly preferably 0.4 μm or more. (C) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the wavelengths of the light sources used were blue and red, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method, and from the obtained particle size distribution. The average particle size was calculated as the median diameter. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

The specific surface area of the inorganic filler (C) is not particularly limited, but is preferably 0.1 m ² / g or more, more preferably 0.5 m ² / g or more, still more preferably 1 m ² / g or more. Particularly preferably, it is 5 m ² / g or more. The upper limit of the specific surface area of the inorganic filler (C) is not particularly limited, but is preferably 50 m ² / g or less, more preferably 30 m ² / g or less, still more preferably 20 m ² / g or less, and particularly preferably. Is 15 m ² / g or less. For the specific surface area of the inorganic filler, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. You can get it.

The inorganic filler (C) is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, the moisture resistance and dispersibility of the (C) inorganic filler can be improved. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styryl-based Silane coupling agents; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N Amino-based silane coupling agents such as −phenyl-8-aminooctyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; tris- (trimethoxysilylpropyl) isocyanurate, etc. Isocyanurate-based silane coupling agent; ureido-based silane coupling agent such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. An isocyanate-based silane coupling agent such as 3-isocyanoxide propyltriethoxysilane; an acid anhydride-based silane coupling agent such as 3-trimethoxysilylpropyl succinate; a silane coupling agent such as; methyltrimethoxysilane, Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimeth Examples thereof include non-silane coupling-alkoxysilane compounds such as xysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. Of these, an amino silane coupling agent is preferable. As the surface treatment agent, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of commercially available surface treatment agents include "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Industry Co., Ltd .; "KBM-303", "KBM-402", and " KBM-403 "," KBE-402 "," KBE-403 "(epoxy-based silane coupling agent);" KBM-1403 "(styryl-based silane coupling agent);" KBM-502 "," KBM-503 " , "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-" 903 ”,“ KBE-903 ”,“ KBE-9103P ”,“ KBM-573 ”,“ KBM-575 ”(amino silane coupling agent);“ KBM-9459 ”(isocyanurate silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "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-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( Non-silane coupling-alkoxysilane compound) and the like.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% by mass to 5% by mass of a surface treatment agent, and is surface-treated with 0.2% by mass to 3% by mass. It is more preferable that the surface is treated with 0.3% by mass to 2% by mass.

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. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity at the melt viscosity or sheet form a resin composition, preferably from 1.0 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, 0.5 mg / ^{m 2} The following is more preferable.

(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 is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like 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, but the non-volatile component in the resin composition is 100% by mass. In the case of, it is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more. The upper limit of the content of the inorganic filler (C) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 90% by mass or less, more preferably 80% by mass. Below, it is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

<(D) Epoxy resin>
The resin composition of the present invention may contain (D) epoxy resin as an arbitrary component. (D) The epoxy resin means a resin having an epoxy group.

Examples of the (D) epoxy resin include bixilenol 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, and trisphenol type. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and isocyanurate type epoxy resin. Of these, cyclohexane type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and bisphenol AF type epoxy resin are particularly preferable. The epoxy resin (D) may be used alone or in combination of two or more.

The resin composition preferably contains, as the (D) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile component of the epoxy resin (D) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably. Is 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as "liquid epoxy resin") or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "solid epoxy resin"). ). The resin composition of the present invention may contain only the liquid epoxy resin as the epoxy resin, or may contain only the solid epoxy resin, but contains the liquid epoxy resin and the solid epoxy resin in combination. It is preferable to be.

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

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. The alicyclic epoxy resin, the cyclohexane type epoxy resin, the cyclohexanedimethanol type epoxy resin, and the epoxy resin having a butadiene structure are preferable, and the cyclohexane type epoxy resin is particularly preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycylol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (bisphenol A type epoxy resin and bisphenol F type) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (Epoxy resin mixture); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda Co., Ltd .; "ZX1658", "ZX1658GS" (cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. And so on. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and among them, naphthol type epoxy resin, biphenyl type epoxy resin, and bisphenol. AF type epoxy resin is particularly preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200", "HP-7200HH", "HP" -7200H "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(made by DIC) Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd .; "ESN485" (naphthol type epoxy resin); "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nittetsu Chemical &Materials; "YX4000H", "YX4000", "YL6121", "YL7890" manufactured by Mitsubishi Chemical Co., Ltd. , "YX4000HK" (biphenyl type epoxy resin); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX7700" (xylene structure-containing novolac type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "JER1010" (solid bisphenol A type epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(D) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 100: 1 to 1: 100, 20 The range of 1: 1 to 1:50 is more preferable, and the range of 1: 1 to 1:30 is even more preferable.

The epoxy equivalent of the epoxy resin (D) is preferably 50 g / eq. ~ 5,000 g / eq. , More preferably 70 g / eq. ~ 2,000 g / eq. , More preferably 90 g / eq. ~ 1,000 g / eq. , Even more preferably 100 g / eq. ~ 400 g / eq. Is. Epoxy equivalent is the mass of resin per epoxy group equivalent. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (D) is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

When the resin composition contains the (D) epoxy resin, the content of the (D) epoxy resin in the resin composition is not particularly limited, but the non-volatile component in the resin composition is 100% by mass. In this case, it is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 15% by mass or more. The upper limit of the content of the epoxy resin (D) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less. More preferably, it is 30% by mass or less, and particularly preferably 25% by mass or less.

<(E) Hardener>
When the resin composition of the present invention contains (D) an epoxy resin, it may contain (E) a curing agent having a function of curing the (D) epoxy resin.

The curing agent (E) is not particularly limited, but for example, a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. Examples thereof include a system curing agent and a carbodiimide system curing agent. The curing agent may be used alone or in combination of two or more. It is particularly preferable that the curing agent (E) contains an active ester-based curing agent.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495" manufactured by Nittetsu Chemical & Materials Co., Ltd. , "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", manufactured by DIC Corporation. Examples thereof include "TD2090" and "TD-2090-60M".

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride. Anhydride, trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trihydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like. Examples of commercially available acid anhydride-based curing agents include "HNA-100" and "MH-700" manufactured by New Japan Chemical Co., Ltd.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy 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 hydroxy 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

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 acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, 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" represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", and "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000H", as active ester compounds containing a dicyclopentadiene type diphenol structure. HPC-8000-65T ”,“ HPC-8000H-65TM ”,“ EXB-8000L ”,“ EXB-8000L-65M ”,“ EXB-8000L-65TM ”(manufactured by DIC); as an active ester compound containing a naphthalene structure "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC); as an active ester-based curing agent which is an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical); "YLH1026" (manufactured by Mitsubishi Chemical), "YLH1030" (manufactured by Mitsubishi Chemical), "YLH1048" (manufactured by Mitsubishi Chemical) as active ester-based curing agents that are benzoylates of phenol novolac. Made); etc.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals; "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" manufactured by Shikoku Chemicals Corporation. Examples include "FA".

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A disicanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which all of them are triazined to form a trimer) and the like can be mentioned.

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 the (D) epoxy resin to the (E) curing agent is [(D) number of epoxy groups in the epoxy resin]: [(E) number of reactive groups in the curing agent. ], It is preferably 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and even more preferably 1: 0.4 to 1: 1.4. Here, the reactive group of the (E) curing agent is, for example, an aromatic hydroxyl group for a phenol-based curing agent and a naphthol-based curing agent, and an active ester group for an active ester-based curing agent, depending on the type of curing agent. different.

The reaction group equivalent of the curing agent (E) is preferably 50 g / eq. ~ 3,000 g / eq. , More preferably 100 g / eq. ~ 1,000 g / eq. , More preferably 100 g / eq. ~ 500 g / eq. , Particularly preferably 100 g / eq. ~ 300 g / eq. Is. The reaction group equivalent is the mass of the curing agent per reaction group equivalent.

When the (E) curing agent contains an active ester-based curing agent, the content thereof is not particularly limited, but when the total amount of the (E) curing agent is 100% by mass, it is preferably 10% by mass. As mentioned above, it is 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, but the non-volatile component in the resin composition is 100% by mass. In this case, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content of the curing agent (E) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 40% by mass or less, more preferably 30% by mass or less. More preferably, it is 20% by mass or less, and particularly preferably 10% by mass or less.

<(F) Curing accelerator>
When the resin composition of the present invention contains (D) an epoxy resin, it may contain (F) a curing accelerator having a function of accelerating the curing of the (D) epoxy resin as an optional component.

The (F) curing accelerator is not particularly limited, but for example, a phosphorus-based curing accelerator, a urea-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and the like. Examples include metal-based curing accelerators. Of these, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators are particularly preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromeritate, and tetrabutylphosphonium hydro. An aliphatic phosphonium salt such as genhexahydrophthalate, tetrabutylphosphonium cresol novolac trimeric salt, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, Butytriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-triltriphenylphosphonium tetra-p-trilborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrap-trilborate, triphenylethylphosphonium Triphenylphosphine, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiosianate, tetraphenylphosphonium thiosianate, butyltriphenylphosphonium Arophenylphosphine salts such as thiosphineate; aromatic phosphine / borane complex such as triphenylphosphine / triphenylborane; aromatic phosphine / quinone addition reactants such as triphenylphosphine / p-benzoquinone addition reaction; tributylphosphine, tri Aliphatic phosphines such as -tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, tricyclohexylphosphine; dibutylphenylphosphine , Di-tert-butylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclophenylphosphine, triphenylphosphine, tri-o-triphenylphosphine, tri-m-trilphosphine, tri-p-trilphosphine, Tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-isopropylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (4-tert-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris ( 2,5-Diphenylphosphine, tris (2,6-dimethylphenyl) phosphine, tris (3,5-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-- Diphenyl-4-ethoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris (4-tert-butoxyphenyl) phosphine, diphenyl-2 -Pyridylphosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (diphenylphosphino) Examples thereof include aromatic phosphine such as acetylene and 2,2'-bis (diphenylphosphine) diphenyl ether.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-. Aliphatic dimethylurea such as 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- (4- Methylphenyl) -1,1-dimethylurea, 3- (3,4-dimethylphenyl) -1,1-dimethylurea, 3- (4-isopropylphenyl) -1,1-dimethylurea, 3- (4-) Methoxyphenyl) -1,1-dimethylurea, 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, N- (1,4-phenylene) Aromatic dimethylurea such as bis (N', N'-dimethylurea), N, N- (4-methyl-1,3-phenylene) bis (N', N'-dimethylurea) [toluenebis dimethylurea] And so on.

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, Examples thereof include 8-diazabicyclo (5,4,0) -undecene, and 4-dimethylaminopyridine is preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-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 trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (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-4,5-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 , 2-Imidazole compounds such as phenylimidazolin and adducts of imidazole compounds and epoxy resins can be mentioned.

As the imidazole-based curing accelerator, a commercially available product may 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, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned.

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 an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc 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, zinc stearate and the like.

When the resin composition contains the (F) curing accelerator, the content of the (F) curing accelerator in the resin composition is not particularly limited, but 100% by mass of the non-volatile component in the resin composition. In the case of, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit of the content of the curing accelerator (F) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably 1% by mass. Below, it is more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

<(G) Other additives>
The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include organic fillers such as rubber particles, polyamide fine particles, and silicone particles; polycarbonate resins other than the component (B), phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, and polyether sulfone resins. , Polyphenylene ether resin, polyether ether ketone resin, polyester resin and other thermoplastic resins; organic copper compounds, organic zinc compounds, organic cobalt compounds and other organic metal compounds; phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal Colorants such as violet, titanium oxide, carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine; Leveling agents such as silicone leveling agents and acrylic polymer leveling agents; Thickeners such as Benton and montmorillonite; Silicone Defoaming agents such as defoaming agents, acrylic defoaming agents, fluorine defoaming agents, vinyl resin defoaming agents; UV absorbers such as benzotriazole UV absorbers; Adhesive improvers such as ureasilane; 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-based antioxidants and hindered amine-based antioxidants; Fluorescent whitening agent; Surface active agent such as fluorine-based surfactant, silicone-based surfactant; Phosphorus-based flame retardant (for example, phosphoric acid ester compound, phosphazene compound, phosphinic acid compound, red phosphorus), nitrogen-based flame retardant (for example) Examples thereof include flame retardants other than non-reactive phosphazene compounds such as melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (for example, antimony trioxide). As the additive, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio. The content of (G) other additives can be appropriately set by those skilled in the art.

<(H) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component. As the organic solvent (H), known ones can be appropriately used, and the type 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; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-. Ester solvents such as 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, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate Ester alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N, N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethylsulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other fats Group hydrocarbon-based solvent; Examples thereof include aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent (H) may be used alone or in combination of two or more at an arbitrary ratio.

<Manufacturing method of resin composition>
The resin composition of the present invention requires, for example, (A) a polyimide resin (preliminized), (B) a siloxane-containing polycarbonate resin (previously carbonated) in an arbitrary reaction vessel. Addition of (C) inorganic filler if necessary, (D) epoxy resin if necessary, (E) curing agent if necessary, (F) curing accelerator if necessary, (G) other addition if necessary It can be produced by adding and mixing the agent and, if necessary, the (H) organic solvent in any order and / or partially or all at the same time. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or from beginning to end. Further, stirring or shaking may be performed in the process of adding and mixing each component. Further, the resin composition may be stirred at the time of additional mixing or thereafter using a stirring device such as a mixer to uniformly disperse the resin composition.

<Characteristics of resin composition>
Since the resin composition of the present invention contains (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. In addition, the compatibility of each component can be excellent.

Since the cured product of the resin composition of the present invention has a low coefficient of thermal expansion, for example, at a heating rate of 5 ° C./min of the cured product obtained by curing the resin composition under curing conditions of 190 ° C. for 90 minutes. The coefficient of linear thermal expansion (ppm) from 25 ° C. to 150 ° C. is preferably less than 80 ppm, more preferably less than 70 ppm, still more preferably less than 65 ppm, still more preferably less than 62 ppm, and particularly preferably less than 60 ppm.

Since the cured product of the resin composition of the present invention suppresses warpage, for example, a cured product having a width of 160 mm and a length of 120 mm obtained by curing the resin composition under curing conditions of 190 ° C. for 90 minutes 3 The amount of warpage when the warp of the remaining one point is measured with the points fixed may be preferably less than 30 mm, more preferably less than 25 mm, still more preferably less than 20 mm, and particularly preferably less than 17 mm.

Since the resin composition of the present invention can be excellent in compatibility, for example, even if the resin composition is stored in a refrigerator at 5 ° C. for 3 days and then observed with an optical microscope, the generation of separated substances is preferably confirmed. Can't be done.

<Use of resin composition>
The resin composition of the present invention can be widely used for insulating materials such as printed wiring boards and multilayer flexible substrates, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component filling resins and the like. The printed wiring board, the multilayer flexible substrate, and the like can be manufactured by using, for example, a sheet-like laminated material such as a resin sheet or a prepreg.

<Resin sheet>
The resin sheet of the present invention includes 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, but 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 paper pattern, and a film made of a plastic material and a metal leaf are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The surface of the support to be joined to the resin composition layer may be matted, corona-treated, or antistatic-treated.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "AL-5" and "AL-7", "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm 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 contain other layers, if desired. Examples of such other layers include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and the like to the surface of the resin composition layer and scratches.

For the resin sheet, a resin varnish prepared by dissolving the resin composition as it is or by dissolving the resin composition in an organic solvent, for example, is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. It can be manufactured by making it.

Examples of the organic solvent that can be used when coating on the support include those similar to those mentioned in the description of the organic solvent as a component of the resin composition. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the temperature is 50 ° C to 150 ° C for 3 minutes to 10 to 10. The resin composition layer can be formed by drying for a minute.

The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

<Laminated sheet>
The laminated sheet is a sheet produced by laminating and curing a plurality of resin composition layers. The laminated sheet contains a plurality of insulating layers as a cured product of the resin composition layer. Usually, the number of resin composition layers laminated to produce a laminated sheet corresponds to the number of insulating layers contained in the laminated sheet. The specific number of insulating layers per 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, and particularly preferably 10 or less. ..

The laminated sheet is a sheet used by bending so that one of the surfaces faces each other. The minimum bending radius for bending the laminated sheet is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, and preferably 5 mm or less. It is preferably 4 mm or less, and particularly preferably 3 mm or less.

Holes may be formed in each insulating layer included in the laminated sheet. This hole can function as a via hole or a through hole 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 optional element. The conductor layer is usually partially formed on the surface of the insulating layer or between the insulating layers. This conductor layer typically functions as wiring in a multilayer flexible substrate.

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

The conductor layer may have a single-layer structure, or may have a single-metal layer made of different types of metals or alloys, or a multi-layer structure including two or more alloy layers. When the conductor layer has a multi-layer 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 to function as wiring.

The thickness of the conductor layer depends on the design of the multilayer flexible substrate, but 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.

<Manufacturing method of laminated sheet>
The laminated sheet can be produced by a manufacturing method including (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 laminating and curing the resin composition layer is arbitrary as long as a desired laminated sheet is obtained. Depending on the components contained in the resin composition, for example, after all the plurality of resin composition layers are laminated, the laminated plurality of resin composition layers may be cured at once. Further, for example, each time another resin composition layer is laminated on one resin composition layer, the laminated resin composition layer may be cured.

Hereinafter, a preferred embodiment of step (b) will be described. In the embodiments described below, for the sake of distinction, the resin composition layers are appropriately numbered such as "first resin composition layer" and "second resin composition layer", and further, they are indicated. The insulating layer obtained by curing the resin composition layer of No. 1 is also numbered like "first insulating layer" and "second insulating layer" in the same manner as the resin composition layer.

In one preferred embodiment, step (b) is
(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,
including. Further, in step (b), if necessary,
(I) Step of laminating the first resin composition layer on the sheet support base material,
(III) The process of drilling holes in the first insulating layer,
(IV) Step of roughening the first insulating layer,
(V) It may include an arbitrary step such as a step of forming a conductor layer on the first insulating layer. Hereinafter, each step will be described.

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

Lamination of the sheet support base material and the first resin composition layer may be carried out by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

When a resin sheet is used, the lamination of the sheet support base material and the first resin composition layer is performed, for example, by pressing the resin sheet from the support side and using the first resin composition layer of the resin sheet as the sheet support base material. This can be done by heat crimping. Examples of the member for heat-pressing the resin sheet to the sheet support base material (hereinafter, also appropriately referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). And so on. Rather than pressing the heat-bonded member directly onto the resin sheet, it is preferable to press the heat-bonded member through an elastic material such as heat-resistant rubber so that the first resin composition layer sufficiently follows the surface irregularities of the sheet-supporting base material.

After laminating, the first resin composition layer may be smoothed by pressing under normal pressure (under atmospheric pressure), for example, with a heat-bonding member. For example, when a resin sheet is used, the first resin composition layer of the resin sheet can be smoothed by pressing the resin sheet from the support side with a heat-bonding member. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The laminating and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

Step (II) is a step of curing the first resin composition layer to form the first insulating layer. The curing conditions of the first resin composition layer are not particularly limited, and the conditions adopted when forming the insulating layer of the printed wiring board can be arbitrarily applied. The first resin composition layer can be cured by drying, but when it contains a thermosetting resin such as an epoxy resin, it can be cured by thermosetting in addition to drying.

Usually, when an epoxy resin is contained, the specific thermosetting conditions differ depending on the type of resin composition. For example, the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., and even more preferably 170 ° C. to 210 ° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and even more preferably 20 minutes to 100 minutes.

When the epoxy resin is contained, 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, prior to thermosetting the first resin composition layer, the first resin is at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). The composition layer may be preheated for 5 minutes or longer (preferably 5 to 150 minutes, more preferably 15 to 120 minutes, even more preferably 15 to 100 minutes).

Step (III) is a step of drilling a hole in the first insulating layer. By this step (III), holes such as via holes and through holes can be formed in the first insulating layer. Drilling may be performed using, for example, a drill, a laser, plasma, or the like, 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.

Step (IV) is a step of roughening the first insulating layer. Usually, smear removal is also performed in this step (IV). Therefore, the roughening treatment is sometimes called a desmear treatment. Examples of the roughening treatment include a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

The swelling liquid is not particularly limited, and examples thereof include alkaline aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid can be performed, for example, by immersing the cured product in the swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.

The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which a permanganate solution is dissolved in a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact P", "Concentrate Compact CP", and "Dosing Solution Security P" manufactured by Atotech Japan. .. The roughening treatment with an oxidizing agent can be performed by immersing the cured product in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes.

An acidic aqueous solution is used as the neutralizing solution. Examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the cured product in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the cured product in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes.

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

The step (V) is a step of forming a conductor layer on the first insulating layer, if necessary. Examples of the method for forming the conductor layer include a plating method, a sputtering method, and a vapor deposition method, and the plating method is particularly preferable. Preferable examples include a method of plating the surface of the first insulating layer by an appropriate method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Above all, the semi-additive method is preferable from the viewpoint of ease of production.

Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown. First, a plating seed layer is formed on the surface of the first insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by a treatment such as etching to form a conductor layer having a desired wiring pattern.

The first insulating layer is obtained in the step (II), and the step (III), the step (IV), and the step (V) are performed as necessary, and then the step (VI) is performed. The step (VI) is a step of laminating the 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 support base material and the first resin composition layer in the step (I).

However, when the first resin composition layer is formed using the 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 the step (II), between the steps (II) and the step (III), and between the steps (III) and the step (IV). ), Or between step (IV) and step (V).

After the step (VI), the step (VII) is performed. The 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 in the same manner as the curing of the first resin composition layer in the step (II). Thereby, a laminated sheet including a plurality of insulating layers such as a first insulating layer and a second insulating layer can be obtained.

Further, in the method according to the above-described embodiment, if necessary, (VIII) a step of drilling a hole in the second insulating layer, (IX) a step of roughening the second insulating layer, and (X) a second insulating layer. A step of forming a conductor layer on the layer may be performed. The drilling of the second insulating layer in the step (VIII) can be performed in the same manner as the drilling of the first insulating layer in the step (III). Further, 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 in the same manner as the formation of the conductor layer on the first insulating layer in the step (V).

In the above-described embodiment, an embodiment in which a laminated sheet is produced by laminating and curing two resin composition layers, that is, a first resin composition layer and a second resin composition layer, has been described, but a resin composition having three or more layers has been described. A laminated sheet may be manufactured by laminating and curing a material layer. For example, in the method according to the above-described embodiment, the resin composition layer is laminated and cured by steps (VI) to (VII), and if necessary, holes are drilled in the insulating layer by steps (VIII) to (X). , The roughening treatment of the insulating layer and the formation of the conductor layer on the insulating layer may be repeatedly carried out to produce a laminated sheet. As a result, a laminated sheet containing three or more insulating layers can be obtained.

Furthermore, the method according to the above-described embodiment may include any step other than the above-mentioned steps. For example, when the step (I) is performed, the step of removing the sheet supporting base material may be performed.

<Multilayer flexible substrate>
The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may include only a laminated sheet, or may include an arbitrary member in combination with the laminated sheet. Examples of the optional member include an electronic component, a coverlay film, and the like.

The multilayer flexible substrate can be manufactured by a manufacturing method including the above-mentioned method for manufacturing a laminated sheet. Therefore, the multilayer flexible substrate can be manufactured by a manufacturing method including (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 the multilayer flexible substrate may further include an arbitrary step in combination with the above steps. For example, a method for manufacturing a multilayer flexible substrate including electronic components may include a step of joining electronic components to a laminated sheet. As the joining condition between the laminated sheet and the electronic component, any condition can be adopted in which the terminal electrode of the electronic component and the conductor layer as wiring provided on the laminated sheet can be connected by a conductor. Further, for example, a method for manufacturing a multilayer flexible substrate including a coverlay film may include a step of laminating a laminated sheet and a coverlay film.

The multilayer flexible substrate can be usually used by being bent so that one surface of the laminated sheet included in the multilayer flexible substrate faces each other. For example, a multilayer flexible substrate is housed in a housing of a semiconductor device in a state of being bent to reduce its size. Further, for example, a multilayer flexible substrate is provided in a movable portion of a semiconductor device having a bendable movable portion.

<Semiconductor device>
The semiconductor device includes the multilayer flexible substrate described above. The semiconductor device includes, for example, a multilayer flexible substrate and a semiconductor chip mounted on the multilayer flexible substrate. In many semiconductor devices, the multilayer flexible substrate can be stored in the housing of the semiconductor device by being bent so that one surface of the laminated sheet included in the multilayer flexible substrate faces each other.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.). Be done.

The semiconductor device includes, for example, 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 storing the bent multilayer flexible substrate in a housing. It can be manufactured by a manufacturing method including.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Synthesis Example 1: Synthesis of Polyimide Resin 1>
9.13 g (30 mmol) of 4-aminobenzoate 5-amino-1,1'-biphenyl-2-yl, 4,4'-(4,) in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. 4'-Isopropyridene diphenoxy) Bisphthalic acid dianhydride 15.61 g (30 mmol), N-methyl-2-pyrrolidone 94.64 g, pyridine 0.47 g (6 mmol), toluene 10 g were added, and under a nitrogen atmosphere. A polyimide solution containing the polyimide resin 1 (nonvolatile content: 20% by mass) was obtained by performing an imidization reaction at 180 ° C. for 4 hours while peeping toluene out of the system. No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution.

<Synthesis Example 2: Synthesis of Polyimide Resin 2>
Aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan, 4,4'-(4,4') in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. -Isopropyridenediphenoxy) bisphthalic dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged, and the solution was heated to 60 ° C. Next, 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bis (aminomethyl) cyclohexane were added dropwise, and then an imidization reaction was carried out at 140 ° C. for 1 hour. As a result, a polyimide solution containing the polyimide resin 2 (nonvolatile content: 30% by mass) was obtained. The weight average molecular weight of the polyimide resin 2 was 25,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3>
A 500 mL separable flask equipped with a moisture metering receiver connected to a reflux condenser, a nitrogen introduction pipe, and a stirrer was prepared. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) [Phenyl] -1,1,3-trimethylindan 29.6 g was added, and the reaction was carried out by stirring at 45 ° C. for 2 hours under a nitrogen stream. Next, the temperature of the reaction solution was raised and the condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. It was confirmed that a predetermined amount of water had accumulated in the moisture metering receiver and that no outflow of water was observed. After confirmation, the temperature of the reaction solution was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Then, it was cooled to obtain a polyimide solution (nonvolatile content 20% by mass) containing a polyimide resin 3 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 3 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the polyimide resin 3 was 12,000.

<Synthesis Example 4: Synthesis of Polycarbonate-Polydimethylsiloxane Copolymer Resin>
21591 parts of ion-exchanged water and 3674 parts of 48.5% sodium hydroxide aqueous solution were put into a reactor with a thermometer, a stirrer and a reflux condenser, and 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). After dissolving 7.6 parts of hydroxide and hydrosulfite, 14565 parts of methylene chloride was added, and 1900 parts of phosgen was blown in at 22 to 30 ° C. over 60 minutes with stirring. Next, a solution prepared by dissolving 1131 parts of a 48.5% sodium hydroxide aqueous solution and 105 parts of p-tert-butylphenol in 800 parts of methylene chloride was added, and the dio-hydroxyphenyl represented by the following formula (4) was added with stirring. A solution prepared by dissolving 430 parts of a terminal polydimethylsiloxane compound (average number of repetitions p in the formula: about 37) in 1600 parts of methylene chloride was 0.0008 mol / mol / mol of 2,2-bis (4-hydroxyphenyl) propane. After adding at a rate of minutes to make it emulsified, the mixture was vigorously stirred again. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued at a temperature of 26 to 31 ° C. for 45 minutes to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, it was poured into a kneader filled with warm water. The methylene chloride was evaporated with stirring to obtain a powder of a polycarbonate-polydimethylsiloxane copolymer resin. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate-polydimethylsiloxane copolymer resin powder (polydimethylsiloxane structure content 8.2%, average size of polydimethylsiloxane domain 9 nm). , Viscosity average molecular weight 19,400).

<Example 1: Preparation of resin composition 1>
Vixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent about 185) 5 parts, Naphthalene type epoxy resin (Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ESN475V", epoxy equivalent about 332) 5 parts, bisphenol AF type epoxy resin ( 10 parts of "YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 238), 2 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 135), polyimide solution obtained in Synthesis Example 1 (20 mass of non-volatile component) %) 100 parts and 10 parts of cyclohexanone were dissolved by heating in a mixed solvent with stirring. After cooling to room temperature, 50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (nonvolatile component 20% by mass, toluene solution) obtained in Synthesis Example 4 and a triazine skeleton-containing cresol novolac curing agent (manufactured by DIC) are placed therein. "LA3018-50P", hydroxyl group equivalent about 151, solid content 50% 2-methoxypropanol solution) 4 parts, active ester curing agent (DIC "EXB-8000L-65M", active group equivalent about 220, non-volatile component 6 parts of 65% by mass of toluene: 1: 1 solution of MEK), spherical silica ("SC2500SQ" manufactured by Admatex, average particle size 0.5 μm, specific surface area 11.2 m ² / g, N for 100 parts of silica -Phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM573) 50 parts, and 0.2 parts of amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) After mixing and uniformly dispersing with a high-speed rotary mixer, the resin composition 1 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKICHNO).

<Example 2: Preparation of resin composition 2>
Examples except that 66.7 parts of the polyimide solution (30% by mass of non-volatile component) obtained in Synthesis Example 2 was used instead of 100 parts of the polyimide solution (20% by mass of non-volatile component) obtained in Synthesis Example 1. The same operation as in 1 was carried out to prepare the resin composition 2.

<Example 3: Preparation of resin composition 3>
Example 1 and Example 1 except that 100 parts of the polyimide solution (20% by mass of non-volatile component) obtained in Synthesis Example 3 was used instead of 100 parts of the polyimide solution (20% by mass of non-volatile component) obtained in Synthesis Example 3. The same operation was carried out to prepare the resin composition 3.

<Comparative Example 1: Preparation of Resin Composition 4>
Instead of using 50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (nonvolatile component 20% by mass, toluene solution) obtained in Synthesis Example 4, the polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Company, Inc., nonvolatile content 20% by mass) ) The resin composition 4 was prepared by performing the same operation as in Example 1 except that 50 parts were used.

<Comparative Example 2: Preparation of Resin Composition 5>
50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (nonvolatile component 20% by mass, toluene solution) obtained in Synthesis Example 4 was not used, and epoxy-modified silicone oil (“KF-105” manufactured by Shin-Etsu Chemical Co., Ltd.). The resin composition 5 was prepared by performing the same operation as in Example 1 except that 10 parts were used.

<Comparative Example 3: Preparation of Resin Composition 6>
Instead of using 50 parts of the polycarbonate-polydimethylsiloxane copolymer resin (nonvolatile component 20% by mass, toluene solution) obtained in Synthesis Example 4, the polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Company, Inc., nonvolatile content 20% by mass) ) 50 parts were used, and 10 parts of epoxy-modified silicone oil (“KF-105” manufactured by Shin-Etsu Chemical Co., Ltd.) was used, but the same operation as in Example 1 was carried out to prepare the resin composition 6. ..

<Comparative Example 4: Preparation of Resin Composition 7>
Instead of using 100 parts of the polyimide solution (20% by mass of non-volatile component) obtained in Synthesis Example 1, phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., 30% by mass of non-volatile component, 1: 1 solution of MEK and cyclohexanone) 66 The resin composition 7 was prepared by performing the same operation as in Example 1 except that .67 parts were used.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction type particle size distribution measuring device (“LA-960” manufactured by Horiba Seisakusho Co., Ltd.), the wavelengths of the light sources used were blue and red, and the particle size distribution of the inorganic filler was measured on a volume basis by the flow cell method. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median diameter.

<Measurement of specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Maxorb HM-1210 manufactured by Mountech), nitrogen gas is adsorbed on the sample surface, and the specific surface area is calculated using the BET multipoint method to calculate the specific surface area of the inorganic filler. Was measured.

<Test Example 1: Confirmation of compatibility in resin composition>
The prepared resin compositions 1 to 6 are stored in a refrigerator at 5 ° C. for 3 days, and then the resin composition is applied onto a glass plate, and then the presence or absence of separation in the fat composition is determined by an optical microscope (manufactured by Hirox). It was observed with "KH8700"). The case where the generation of the separated product could not be confirmed by the optical microscope was evaluated as "◯", and the case where the generation of the separated product could be confirmed was evaluated as "x".

<Test Example 2: Measurement and evaluation of coefficient of linear thermal expansion>
The thickness of the resin composition layer after drying is 40 μm on the release-treated surface of the PET film (thickness 38 μm) in which the resin compositions of each Example and Comparative Example are treated with an alkyd-based mold release agent. , Was uniformly applied with a die coater and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet 1.

The obtained resin sheet 1 was laminated on a polyimide film (Ube Industries, Ltd., Upirex S) using a batch type vacuum pressurizing laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). The laminate was depressurized for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimped at 120 ° C. for 30 seconds at a pressure of 0.74 MPa. Then, the PET film was peeled off, the resin composition was cured under curing conditions of 190 ° C. for 90 minutes, and the polyimide film was peeled off to obtain a cured product sample.

The obtained cured product sample is cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis is performed by a tensile weight method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Co., Ltd.). went. After mounting the sample on the apparatus, the sample was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average coefficient of linear thermal expansion (ppm) from 25 ° C to 150 ° C in the two measurements was calculated. When the value of the coefficient of linear thermal expansion was less than 60 ppm, it was evaluated as “◯”, and when it was 60 ppm or more, it was evaluated as “x”.

<Test Example 3: Warpage measurement and evaluation>
The thickness of the resin composition layer after drying is 30 μm on the release-treated surface of the PET film (thickness 38 μm) in which the resin compositions of each Example and Comparative Example are treated with an alkyd-based mold release agent. , And uniformly applied with a die coater and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet 2.

The obtained resin sheet 2 is etched out of a laminated plate (MCL-E-700G manufactured by Hitachi Kasei Co., Ltd.) using a batch type vacuum pressurizing laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). It was laminated on the product). The laminate was depressurized for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimped at 120 ° C. for 30 seconds at a pressure of 0.74 MPa. Then, the PET film was peeled off, the resin composition was cured under curing conditions of 190 ° C. for 90 minutes, and the polyimide film was peeled off to obtain a cured product sample. The obtained cured product was cut into test pieces having a width of 160 mm and a length of 120 mm, and the amount of warpage of the remaining one point was measured with the three points fixed. When the amount of warpage was less than 20 mm, it was evaluated as "◯", and when it was 20 mm or more, it was evaluated as "x".

Table 1 below shows the amounts of non-volatile components used in the resin compositions of Examples and Comparative Examples, the measurement results of Test Examples, the evaluation results, and the like.

It was found that by using a resin composition containing (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 (18)

A resin composition containing (A) a polyimide resin and (B) a siloxane-containing polycarbonate resin. The resin composition according to claim 1, wherein the component (A) has a weight average molecular weight of 1,000 or more and 100,000 or less. The resin composition according to claim 1 or 2, wherein the component (B) is a polycarbonate-polysiloxane copolymer containing a polycarbonate block having a polycarbonate structure and a polysiloxane block having a polysiloxane structure. The resin composition according to claim 3, wherein the polysiloxane structure is a polydialkylsiloxane structure. The resin composition according to claim 3 or 4, wherein the polycarbonate structure is an aromatic polycarbonate structure. The content of the polysiloxane structure in the component (B) is 1% by mass or more and 30% by mass or less when the component (B) is 100% by mass, according to any one of claims 3 to 5. Resin composition. The resin composition according to any one of claims 1 to 6, wherein the viscosity average molecular weight of the component (B) is 13,000 or more and 25,000 or less. The resin composition according to any one of claims 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. The resin composition according to any one of claims 1 to 8, further comprising (C) an inorganic filler. The resin composition according to claim 9, wherein the component (C) is silica. The resin composition according to claim 9 or 10, wherein the content of the component (C) is 30% by mass or more and 60% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 11, further comprising (D) an epoxy resin and (E) a curing agent. The resin composition according to claim 12, wherein the component (E) contains an active ester-based curing agent. The resin composition according to any one of claims 1 to 13, which is used for forming an insulating layer of a multilayer flexible substrate. The cured product of the resin composition according to any one of claims 1 to 14. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 14 provided on the support. A multilayer flexible substrate including an insulating layer formed by curing the resin composition according to any one of claims 1 to 14. A semiconductor device comprising the multilayer flexible substrate according to claim 17.