JP2001279116A - Curable resin composition and insulator comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition capable of producing an insulator excellent in thermal shock resistance and dielectric characteristics. SOLUTION: This curable resin composition comprises (A) a resin bearing at least two crosslinkable functional groups in the molecule and (B) a low molecular weight compound bearing at least two crosslinkable functional groups of the same kind as those in (A), the weight-average mol.wt. of (A) being 3,000-1,000,000 and the weight-average mol.wt. of (B) being 170-3,000, and gives after cure a dielectric constant of not more than 3.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable resin composition and an insulator comprising the same. More specifically, the present invention relates to a curable resin composition suitable as an overcoat material or an interlayer insulating material for a circuit board used for various electric devices, electronic components, semiconductor devices, and the like, and an insulator made of the same.

[0002]

2. Description of the Related Art Defects such as an epoxy resin composition and a polyimide resin as insulating materials and dielectric properties in a high frequency range, and a heat resistance and a solvent resistance of a polyolefin resin and a polyphenylene ether resin as an insulating material. In order to solve the drawbacks such as the properties, for example, a copolymer of norbornene-type monomer and ethylene, sulfur cross-linking, organic oxide cross-linking,
Example of electron beam crosslinking or radiation crosslinking (JP-A-62-34)
No. 924) and examples using polyphenylene ether substituted with a propargyl group or an allyl group, polyphenylene ether containing a double bond, unsaturated carboxylic acid or an acid anhydride-modified polyphenylene ether thereof, and the like (JP-A-1-69628). JP, JP-A-1-69629, JP-A-1-113425, JP-A-1-113
No. 426, Japanese Unexamined Patent Publication No. 1-239017) and the like are known.

[0003]

However, the former has a problem in application to an insulating material such as an overcoat material or an interlayer insulating material since the dielectric constant is as high as 3.7 or more. Also,
In the latter, the use of an allyl group, an olefinically unsaturated group or an unsaturated carboxylic acid as a curing functional group results in poor curing reactivity, especially in oxygen (in air), and poor thermal shock resistance. Run short. That is, an object of the present invention is to provide a curable resin composition capable of producing an insulator having excellent thermal shock resistance and dielectric properties.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention. That is, the curable resin composition of the present invention is characterized in that a resin (A) having at least two crosslinkable functional groups in a molecule, and at least two crosslinkable functional groups of the same type as (A) in a molecule. (B) comprising a low molecular compound (B)
Has a weight average molecular weight of 3,000 to 1,000,000, (B) has a weight average molecular weight of 170 to 3,000, and has a dielectric constant of 3.5 or less after curing.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the crosslinkable functional group of (A) include an epoxy group, a (meth) acryloyl group,
Vinyl group, allyl group, propenyl group, primary amino group,
Secondary amino groups, nitrile groups, carboxyl groups, hydroxyl groups, isocyanate groups and the like can be used. Examples of the epoxy group include a glycidyl group and a cyclohexenyl monooxide group. (Meth) acryloyl means a methacryl group and an acryloyl group, and a primary amino group is -N
It refers to H _2.

The secondary amino group means an N-alkylamino group, and the alkyl group is an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. And an isobutyl group. Among these crosslinkable functional groups, an epoxy group, a (meth) acryloyl group, a vinyl group, an allyl group, a propenyl group, and a nitrile group are preferable from the viewpoint of electrical properties, and from the viewpoint of heat resistance, an epoxy group, a (meth) acryloyl Groups are more preferred, with glycidyl and cyclohexenyl oxide being particularly preferred.

The number of crosslinkable functional groups in (A) is at least 2, preferably 2 to 5,000, more preferably 3 to 3,000, and particularly preferably 5 to 1,000.
0, more preferably 7 to 500, most preferably 10 to 200. The weight average molecular weight of (A) is from 3,000 to 1,000,000, preferably from 30,000 to 600,000, and more preferably from 50,000 to 400,000. If the weight average molecular weight is less than 3,000, the resin strength tends to be weak, and if it exceeds 1,000,000, resin processing such as formation of a curable resin composition into a film tends to be difficult.
The weight average molecular weight is measured by gel permeation chromatography (hereinafter, abbreviated as GPC), and is hereinafter abbreviated as Mw.

[0008] (A) is a method of (co) polymerizing a monomer having a crosslinkable functional group, or reacting a monomer having a crosslinkable functional group with a resin having a crosslinkable functional group to perform crosslinking. It can be easily produced by a method of converting a functional functional group. The monomer having a crosslinkable functional group is not limited as long as it has at least two crosslinkable functional groups.
(Meth) acryloyl group, vinyl group, allyl group, propenyl group, primary amino group, secondary amino group, nitrile group, carboxyl group, hydroxyl group and at least one functional group selected from the group consisting of isocyanate group And the like.

For example, a monomer (a) having only an epoxy group as a crosslinkable functional group, a monomer (b) having only a (meth) acryloyl group, and a monomer having only a vinyl group ( c) a monomer (d) having only an allyl group, a monomer (e) having only a propenyl group, a monomer (f) having a primary amino group, and a secondary amino group. A monomer having only a carboxyl group (h), a monomer having only a hydroxyl group (i), a monomer having only an isocyanate group (j), and a nitrile group. A monomer (k) having a vinyl group, a monomer (m) having a nitrile group and a (meth) acryloyl group, a monomer (n) having a hydroxyl group and a (meth) acryloyl group, and an epoxy group. A monomer (o) having a (meth) acryloyl group, a monomer (p) having an epoxy group and a vinyl group, (T) a monomer (q) having an acryloyl group and a vinyl group, a monomer (r) having a (meth) acryloyl group and an isocyanate group, a monomer (r) having a (meth) acryloyl group and a carboxyl group ( s), a monomer (t) having a (meth) acryloyl group and an allyl group,
A monomer (u) having a (meth) acryloyl group and a propenyl group, a monomer (v) having a secondary amino group and an allyl group, and a monomer having a secondary amino group and a propenyl group A body (w) or the like is used.

The monomer (a) having only an epoxy group as a crosslinkable functional group includes an epoxy group in the molecule of 2 to 7
Or more polyepoxides, such as (a1) glycidyl ether type polyepoxide,
(A2) glycidyl ester type polyepoxide, (a
3) glycidylamine type polyepoxide, and (a4)
An alicyclic polyepoxide or the like is used.

(A1) Examples of the glycidyl ether type polyepoxide include the following (a11) to (a14)
Etc. can be used. (A11) Diglycidyl ether of dihydric phenol (C6 to C30) For example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B
Diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether,
Halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether,
1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro-4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyldiglycidyl ether, 9,9'-bis (4-hydroxyphenyl)
Flow orange glycidyl ether and bisphenol A
Examples include diglycidyl ether obtained from the reaction of 2 moles and 3 moles of epichlorohydrin.

(A12) Polyhydric phenol @ 6 to 5 carbon atoms
0 or more, trivalent of Mw 110 to 5,000 to 6
Polyglycidyl ethers having a valency or higher そ れ, for example, pyrogallol triglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether,
Tetrakis (4-hydroxyphenyl) ethane tetraglycidyl ether, trismethyl-tert-butyl-
Butylhydroxymethane triglycidyl ether, 4,
Examples include 4′-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) phenyl glycidyl ether, and bis (dihydroxynaphthalene) tetraglycidyl ether.

(A13) Dihydric alcohol (C2 to C1)
00 or more, Mw 62-5,000) [C2
To 6 or more alkylene glycols or alkylene oxides (2 to 4 carbon atoms) of dihydric phenols (6 to 24 carbon atoms) (hereinafter alkylene oxides having 2 to 4 carbon atoms are abbreviated as AO) 1 to 90. Mol adduct], for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (Mw 150-4,000) diglycidyl Ether, polypropylene glycol (Mw 180 to 5,000
0) Diglycidyl ether, polytetramethylene glycol (Mw 200 to 5,000) diglycidyl ether, neopentyl glycol diglycidyl ether, and ethylene oxide of bisphenol A (hereinafter, ethylene oxide is abbreviated as EO) and / or propylene oxide (hereinafter, propylene oxide) , Propylene oxide is abbreviated as PO.) (1 to 20 mol) adduct diglycidyl ether and the like.

(A14) Polyhydric alcohol having 3 to 7 or more valences (having 3 to 50 or more carbon atoms and having a Mw of 76
Polyglycidyl ethers such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, and poly (polymerization degree 2 to 5) glycerin polyglycidyl ether. .

(A2) Examples of the glycidyl ester type polyepoxide include the following (a21) to (a22)
Etc. can be used. (A21) Polyglycidyl ester of a divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms) For example, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate And trimellitic acid triglycidyl ester. (A22) a polyglycidyl ester of a divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acid (having 6 to 20 or more carbon atoms), for example, an aromatic nucleus water additive of (a21), a dimer acid dimer Examples include glycidyl ester, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimerate, and triglycidyl tricarballylate.

(A3) As the glycidylamine type polyepoxide, for example, the following (a31) to (a34) can be used. (A31) Polyglycidyl aromatic amine having 2 to 10 or more glycidyl groups (aromatic amine having 6 to 20 or more carbon atoms) For example, N, N-diglycidylaniline, N, N-diglycidyl Toluidine, N, N, N ', N'-tetraglycidyldiaminodiphenylmethane, N, N, N', N '
-Tetraglycidyl diaminodiphenyl sulfone, N,
N, N ', N'-tetraglycidyldiethyldiphenylmethane and N, N, O-triglycidylaminophenol are exemplified.

(A32) Polyglycidyl aliphatic or araliphatic amines having 2 to 10 or more glycidyl groups (aliphatic or araliphatic amines having 6 to 20 or more carbon atoms) For example, N, N , N ', N'-tetraglycidylxylylenediamine and N, N, N', N'-tetraglycidylhexamethylenediamine. (A33) Polyglycidyl alicyclic amine having 2 to 10 or more glycidyl groups (carbon number of 6 to 20 or more of alicyclic amine) For example, N, N, N ′, N′-tetraglycidyl And hydrogenated compounds of xylylenediamine. (A34) Polyglycidyl heterocyclic amine having 2 to 10 or more glycidyl groups (heterocyclic amine having 6 to 20 or more carbon atoms) For example, trisglycidylmelamine and the like can be mentioned.

(A4) As the alicyclic polyepoxide,
For example, when the number of carbon atoms is 6 to 50 or more,
5,000, alicyclic epoxides having 2 to 4 or more epoxy groups can be used. For example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, 3,4 epoxy-6-methylcyclohexylmethyl 3 ', 4 '-Epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-
Epoxy-6-methylcyclohexylmethyl) adipate and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine.

As the monomer (b) having only a (meth) acryloyl group as a crosslinkable functional group, (b1) diglycidyl ether of a dihydric phenol (C6 to C30),
(B2) polyhydric phenol {trivalent to hexavalent or higher poly (meth) acrylate having 6 to 50 or more carbon atoms and Mw of 110 to 5,000}, (b3) dihydric alcohol (2 to 6 carbon atoms) 100 or more, Mw 62 to 5,
000) [AO1 of alkylene glycol having 2 to 6 or more carbon atoms or dihydric phenol (6 to 24 carbon atoms)
And (b4) a trivalent to heptavalent or higher polyhydric alcohol (having 3 to 50 or more carbon atoms and having a Mw of 76 to 10,000,
0) Poly (meth) acrylate or the like is used.

(B1) (meth) acrylate of dihydric phenol For example, bisphenol F di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol B di (meth) acrylate, bisphenol AD di (meth) acrylate, bisphenol S Di (meth) acrylate, halogenated bisphenol A di (meth) acrylate (for example, tetrachlorobisphenol A di (meth) acrylate, etc.), catechin di (meth) acrylate, resorcinol di (meth) acrylate, hydroquinone di (meth) acrylate, 1,5-dihydroxynaphthalenedi (meth) acrylate, dihydroxybiphenyldi (meth) acrylate, octachloro-
4,4′-dihydroxybiphenyldi (meth) acrylate, tetramethylbiphenyldi (meth) acrylate, and 9,9′-bis (4-hydroxyphenyl) furo orange (meth) acrylate.

(B2) Poly (meth) acrylate of polyhydric phenol, for example, pyrogallol tri (meth) acrylate, dihydroxynaphthylcresol tri (meth) acrylate, tris (hydroxyphenyl) methane tri (meth) acrylate
Acrylate, dinaphthyltriol tri (meth) acrylate, tetrakis (4-hydroxyphenyl) ethanetetra (meth) acrylate, trismethyl-ter
t-butyl-butylhydroxymethane tri (meth) acrylate, 4,4′-oxybis (1,4-phenylethyl) tetracresol (meth) acrylate, 4,
Examples include 4′-oxybis (1,4-phenylethyl) phenyl (meth) acrylate and bis (dihydroxynaphthalene) tetra (meth) acrylate.

(B3) (meth) acrylate of dihydric alcohol, for example, ethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, polyethylene glycol (Mw 150-4,000) di (meth) acrylate, polypropylene glycol (Mw 180-
(5,000) di (meth) acrylate, polytetramethylene glycol (Mw 200-5,000) di (meth)
Acrylate, neopentyl glycol di (meth) acrylate and bisphenol A EO and / or PO
(1 to 20 mol) adduct di (meth) acrylate and the like.

(B4) Poly (meth) acrylate of a trihydric to heptavalent or higher polyhydric alcohol, for example, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Sorbitol hexa (meth) acrylate and poly (polymerization degree 2
5) Glycerin poly (meth) acrylate and the like.

Examples of the monomer (c) having only a vinyl group as a crosslinkable functional group include hydrocarbon compounds having 4 to 20 carbon atoms, such as butadiene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, and trivinylketone. Examples thereof include vinylbenzene and methoxybutadiene. In addition to these, divinyl sulfide, divinyl sulfone, divinyl sulfoxide, and the like can also be used.

Examples of the monomer (d) having only an allyl group as a crosslinkable functional group include (d1) diallyl ether of a dihydric phenol (C6 to C30) and (d2) polyhydric phenol ｛C6 ~ 50 or more, Mw 110
5,000 trivalent to hexavalent or higher polyallyl ether, (d3) dihydric alcohol (2 to 100 or more carbon atoms, Mw 62 to 5,000) [2 to 6 or more carbon atoms] Alkylene glycol or a dihydric phenol (6 to 24 carbon atoms, AO 1 to 90 mol adduct)] diallyl ether; (d4) a trihydric to heptavalent or higher polyhydric alcohol (3 to 50 or more carbon atoms) , Mw76
(D5) divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 carbon atoms)
-20 or more), and (d)
6) Polyvalent esters of divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acids (6 to 20 or more carbon atoms) are used.

(D1) Diallyl ether of dihydric phenol For example, bisphenol F diallyl ether, bisphenol A diallyl ether, bisphenol B diallyl ether, bisphenol AD diallyl ether, bisphenol S diallyl ether, halogenated bisphenol A diallyl ether, tetrachlorobisphenol A Diallyl ether, catechin diallyl ether, resorcinol diallyl ether, hydroquinone diallyl ether, 1,5-dihydroxynaphthalene diallyl ether, dihydroxybiphenyl diallyl ether, octachloro-4,4'-dihydroxybiphenyl diallyl ether, tetramethylbiphenyl diallyl ether and 9,9 '-Bis (4-hydroxyphenyl) fluoro orange allyl Le, and the like.

(D2) Polyallyl ether of polyhydric phenol For example, pyrogallol triallyl ether, dihydroxynaphthylcresol triallyl ether, tris (hydroxyphenyl) methanetriallyl ether, dinaphthyltriol triallyl ether, tetrakis (4-
(Hydroxyphenyl) ethane tetraallyl ether, trismethyl-tert-butyl-butylhydroxymethanetriallyl ether, 4,4′-oxybis (1,4
-Phenylethyl) tetracresol allyl ether,
4,4'-oxybis (1,4-phenylethyl) phenyl allyl ether and bis (dihydroxynaphthalene) tetraallyl ether are exemplified.

(D3) Diallyl ether of dihydric alcohol For example, ethylene glycol diallyl ether, propylene glycol diallyl ether, tetramethylene glycol diallyl ether, 1,6-hexanediol diallyl ether, polyethylene glycol (Mw 150
4,000) diallyl ether, polypropylene glycol (Mw 180-5,000) diallyl ether,
Polytetramethylene glycol (Mw 200 to 5,000
0) EO and / or P of diallyl ether, neopentyl glycol diallyl ether and bisphenol A
And diallyl ether of O (1 to 20 mol) adduct.

(D4) Polyallyl ether of a trihydric to heptavalent or higher polyhydric alcohol such as trimethylolpropane
Examples include glycerin triallyl ether, pentaerythritol tetraallyl ether, sorbitol hexaallyl ether, and poly (degree of polymerization 2 to 5) glycerin polyallyl ether.

(D5) Polyallyl ester of aromatic polycarboxylic acid Examples thereof include diallyl phthalate, diallyl isophthalate, diallyl terephthalate and triallyl trimellitate. (D6) Polyallyl ester of aliphatic or alicyclic polycarboxylic acid For example, aromatic nucleus water additive of (d5), diallyl ester of dimer acid, diallyl oxalate, diallyl maleate, diallyl succinate, diallyl glutarate, Diallyl adipate, diallyl pimerate and triallyl triaryl ester.

Examples of the monomer (e) having only a propenyl group as a crosslinkable functional group include (e1) dipropenyl ether of dihydric phenol (C6 to C30) and (e2)
Polyhydric phenols having 6 to 50 or more carbon atoms,
(E3) dihydric alcohol (2 to 100 or more carbon atoms, Mw 62 to 5,000) [trivalent to hexavalent or more trivalent to hexavalent or more than 110 to 5,000] [2 to 6 or more carbon atoms The above alkylene glycol or 2
(E4) a trihydric to heptavalent or higher polyhydric alcohol (having 3 to 50 or more carbon atoms and having a Mw of 76 to 1). 10,000) polypropenyl ether; (e5) a polypropenyl ester of a divalent to hexavalent or higher valent aromatic polycarboxylic acid (C6 to 20 or more); and (e6) a divalent to hexavalent carboxylic acid. Alternatively, a polypropenyl ester of an aliphatic or alicyclic polycarboxylic acid (having 6 to 20 or more carbon atoms) or the like is used.

(E1) Dipropenyl ether of dihydric phenol, for example, bisphenol F dipropenyl ether, bisphenol A dipropenyl ether, bisphenol B
Dipropenyl ether, bisphenol AD dipropenyl ether, bisphenol S dipropenyl ether,
Halogenated bisphenol A dipropenyl ether, tetrachlorobisphenol A dipropenyl ether, catechin dipropenyl ether, resorcinol dipropenyl ether, hydroquinone dipropenyl ether,
1,5-dihydroxynaphthalenedipropenyl ether, dihydroxybiphenyldipropenyl ether, octachloro-4,4'-dihydroxybiphenyldipropenyl ether, tetramethylbiphenyldipropenyl ether and 9,9'-bis (4-hydroxyphenyl) fluoro orange And propenyl ether.

(E2) Polypropenyl ether of polyhydric phenol, for example, pyrogallol tripropenyl ether, dihydroxynaphthyl cresol tripropenyl ether, tris (hydroxyphenyl) methane tripropenyl ether, dinaphthyl triol tripropenyl ether,
Tetrakis (4-hydroxyphenyl) ethanetetrapropenyl ether, trismethyl-tert-butyl-
Butylhydroxymethanetripropenyl ether, 4,
Examples thereof include 4'-oxybis (1,4-phenylethyl) tetracresolpropenyl ether, 4,4'-oxybis (1,4-phenylethyl) phenylpropenylether and bis (dihydroxynaphthalene) tetrapropenylether.

(E3) Dipropenyl ether of dihydric alcohol For example, ethylene glycol dipropenyl ether, propylene glycol dipropenyl ether, tetramethylene glycol dipropenyl ether, 1,6-hexanediol dipropenyl ether, polyethylene glycol (Mw 150-4) , 000) dipropenyl ether, polypropylene glycol (Mw 180-5,000)
0) Dipropenyl ether, polytetramethylene glycol (Mw 200 to 5,000) dipropenyl ether, neopentyl glycol dipropenyl ether, and dipropenyl ether of EO and / or PO (1 to 20 mol) adduct of bisphenol A No.

(E4) Polypropenyl ethers of polyhydric alcohols having 3 to 7 or more valences such as trimethylolpropane tripropenyl ether, glycerin tripropenyl ether, pentaerythritol tetrapropenyl ether, sorbitol hexapropenyl ether and poly (polymerization Degree 2 to 5) glycerin polypropenyl ether and the like.

(E5) Polypropenyl ester of aromatic polycarboxylic acid Examples thereof include dipropenyl phthalate, dipropenyl isophthalate, dipropenyl terephthalate, and tripropenyl trimellitate. (E6) Polypropenyl ester of an aliphatic or alicyclic polycarboxylic acid For example, an aromatic nucleus water additive of (d5), dipropenyl dimer ester, dipropenyl oxalate, dipropenyl malate, dipropenyl succinate, And dipropenyl glutarate, dipropenyl adipate, dipropenyl pimerate and tripropenyl tripropenyl ester.

Examples of the monomer (f) having a primary amino group as a crosslinkable functional group include (f1) an aliphatic polyamine (having 2 to 18 carbon atoms and 2 to 7 amino groups), and (f2) an alicyclic ring. Formula polyamine (4 to 15 carbon atoms, 2 to 3 amino groups),
(F3) Polyamide polyamine and (f4) polyether polyamine are used.

(F1) As the aliphatic polyamine, alkylene diamine having 2 to 6 carbon atoms, polyalkylene (2 to 6 carbon atoms) polyamine, alkyl (1 to 4 carbon atoms) or hydroxyalkyl (carbon number of the above polyamine) is used. Two
4) Substitutes, alicyclic or heterocyclic-containing aliphatic polyamines (5 to 18 carbon atoms), aromatic ring-containing aliphatic polyamines (8 to 15 carbon atoms) and the like can be used. Examples of the alkylenediamine include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine. Examples of the polyalkylene polyamine include diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

Examples of the alkyl or hydroxyalkyl-substituted polyamine include dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine and methyliminobispropylamine. Examples of the alicyclic or heterocyclic-containing aliphatic polyamine include 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane. Examples of the aromatic ring-containing aliphatic polyamine include xylylenediamine and tetrachloro-p-xylylenediamine.

(F2) Examples of the alicyclic polyamine include 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, and 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline). (F3) Examples of the polyamide polyamine include, for example, Mw obtained by condensation of a dicarboxylic acid (such as dimer acid) and an excess of polyamine (such as the above-mentioned alkylenediamine and polyalkylene polyamine) in excess (at least 2 moles per mole of acid).
80 to 2,000 polyamide polyamines and the like are used. Specifically, for example, commercially available tomide (manufactured by Fuji Kasei), versamide (manufactured by Henkel Hakusui), lakermide (manufactured by Dainippon Ink), and sunmide (manufactured by Sanwa Chemical)
And polyamide (manufactured by Sanyo Chemical Industries, Ltd.).

(F4) Examples of the polyether polyamine include polyether polyols (2 to 6 valent, Mw
90 to 2,000) [e.g., hydrides of cyanoethylated polyalkylenes (eg, glycols having 2 to 8 carbon atoms)].

The monomer (g) having a secondary amino group as a crosslinkable functional group includes the primary amino group (-) of (f).
NH ₂ group) is -NH-R (R can be used those replaced by an alkyl group) having 1 to 4 carbon atoms, for example, di (methylamino) ethylene, di (ethylamino) hexane and 1,3-di (Methylamino) cyclohexane and the like.

The monomer (h) having only a carboxyl group as a crosslinkable functional group includes (h1) a divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms). And (h2) a divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acid (having 6 to 20 or more carbon atoms) and the like. (H1) Aromatic polycarboxylic acid Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, hymic acid and trimellitic acid. (H2) Aliphatic or alicyclic polycarboxylic acid For example, aromatic nucleus water additive of (h1), dimer acid, oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, tricarbaryl Acid and dodecenyl succinic acid.

The monomer (i) having only a hydroxyl group as a crosslinkable functional group includes (i1) a dihydric phenol having 6 to 30 carbon atoms, and (i2) a polyhydric phenol (having 6 to 50 or more carbon atoms). And trivalent to hexavalent or more of Mw 110 to 5,000), (i3) dihydric alcohol (C 2 to C 1)
00 or more, Mw 62-5,000) [C2
1 to 90 moles of AO of 6 to 6 or more alkylene glycols or dihydric phenols (6 to 24 carbon atoms), and (i4) polyhydric alcohols of 3 to 7 or more (3 to 50 carbon atoms) Or more, Mw 76-1
000).

(I1) Examples of the dihydric phenol include bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A (eg, tetrachlorobisphenol A, etc.), catechin, resorcinol, hydroquinone, , 5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4'-dihydroxybiphenyl, tetramethylbiphenyl and 9,9'-bis (4-hydroxyphenyl) fluorene.

(I2) Examples of the polyhydric phenol include pyrogallol, dihydroxynaphthylcresol,
Tris (hydroxyphenyl) methane, dinaphthyltriol, tetrakis (4-hydroxyphenyl) ethane, trismethyl-tert-butyl-butylhydroxymethane, 4,4′-oxybis (1,4-phenylethyl) tetracresol, 4,4 '-Oxybis (1,
4-phenylethyl) phenyl and bis (dihydroxynaphthalene).

(I3) Examples of the dihydric alcohol include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol (Mw 150 to 4,000), and polypropylene glycol (Mw 180 to 5,000). ,
Polytetramethylene glycol (Mw 200 to 5,000
0), neopentyl glycol and bisphenol A
Of EO and / or PO (1 to 20 mol).

(I4) Polyhydric alcohols include, for example, trimethylolpropane, ditrimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, sorbitol and poly (polymerization degree 2-5) glycerin.

The monomer (j) having only an isocyanate group as a crosslinkable functional group includes (j1) a carbon number (NC
Excludes carbon in O groups. The same applies hereinafter. 6) aromatic polyisocyanate having 6 to 20; (j2) aliphatic polyisocyanate having 2 to 18 carbon atoms; (j3) alicyclic polyisocyanate having 4 to 15 carbon atoms; (j4) aromatic fat having 8 to 15 carbon atoms Group polyisocyanates, and (j5) modified products of the above polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretimine group, isocyanurate group,
Oxazolidone group-containing modified products).

(J1) Examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4 ′ Or 4,4'-diphenylmethane diisocyanate (M
DI), 4,4'-diisocyanatobiphenyl, 3,
3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI [crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) or the same] A condensation product with a mixture; a mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine]] phosgenate: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and m- and p-isocyanatophenylsulfonyl isocyanate.

(J2) Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate,
6,11-undecane triisocyanate, 2,2,4
-Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6- Diisocyanatohexanoate and the like.

(J3) As the alicyclic polyisocyanate, for example, isophorone diisocyanate (IPD
I), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-diene Carboxylate and 2,5-
Alternatively, 2,6-norbornane diisocyanate and the like can be mentioned. (J4) As the araliphatic polyisocyanate, for example, m- or p-xylylene diisocyanate (X
DI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

(J5) Examples of the modified polyisocyanate include modified MDI (urethane-modified MDI,
Modified polyisocyanates such as carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, and mixtures of two or more of these [eg, modified MDI and urethane-modified Combination with TDI (isocyanate-containing prepolymer)]. The urethane-modified polyisocyanate [excess polyisocyanate (TDI, MDI
Etc.) and a polyol and a free isocyanate-containing prepolymer obtained by reacting the polyol], a polyol having an equivalent weight of 30 to 200 can be used,
For example, glycols (such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol), triols (such as trimethylolpropane and glycerin), high-functional polyols (such as pentaerythritol and sorbitol) and their AOs (EOs)
And / or 1 to 20 mol of PO) adducts.

Examples of the monomer (k) having a nitrile group and a vinyl group as a crosslinkable functional group include cyanobutene and cyanostyrene. Examples of the monomer (m) having a nitrile group and a (meth) acryloyl group as a crosslinkable functional group include (meth) acrylonitrile and cyanoethyl (meth) acrylate.

As the monomer (n) having a hydroxyl group and a (meth) acryloyl group as a crosslinkable functional group, a mono (meth) acrylate having a polyalkylene (2-8 carbon atoms) glycol chain (Mw 300-3, 000) can be used. For example, polyethylene glycol (Mw300) mono (meth) acrylate, polypropylene glycol (Mw500) mono (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate ) Acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth)
Acrylate and polyglycerin (degree of polymerization same as above)
Mono (meth) acrylate and the like can be mentioned.

An epoxy group and (meth) as a crosslinkable functional group
Examples of the monomer (o) having an acryloyl group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. Examples of the monomer (p) having an epoxy group and a vinyl group as a crosslinkable functional group include vinylcyclohexene monooxide and butadiene monooxide. Examples of the monomer (q) having a (meth) acryloyl group and a vinyl group as a crosslinkable functional group include vinyl methacrylate and vinyloxyethyl (meth) acrylate.

As the monomer (r) having a (meth) acryloyl group and an isocyanate group as a crosslinkable functional group,
Examples include 2- (meth) acryloylethyl isocyanate and (meth) acryloylpropyl isocyanate. As a monomer (s) having a (meth) acryloyl group and a carboxyl group as a crosslinkable functional group,
For example, (meth) acrylate, maleic acid, maleic anhydride and the like can be mentioned. (Meth) as a crosslinkable functional group
Examples of the monomer (t) having an acryloyl group and an allyl group include allyl methacrylate and allyloxyethyl (meth) acrylate. Examples of the monomer (u) having a (meth) acryloyl group and a propenyl group as a crosslinkable functional group include, for example, propenyl methacrylate and propenylethyl (meth) acrylate.

As the monomer (v) having a secondary amino group and an allyl group as a crosslinkable functional group, at least a part of the primary amino group (—NH ₂ group) of (f) is —NH ₂ -R
(R is an allyl group) can be used. For example, di (allylamino) ethylene, di (allylamino)
Hexane and 1,3-di (allylamino) cyclohexane are exemplified.

As the monomer (w) having a secondary amino group and a propenyl group as a crosslinkable functional group, at least a part of the primary amino group (—NH ₂ group) in (f) is —NH ₂ −
R (R is a propenyl group) can be used, and examples thereof include di (propenylamino) ethylene, di (propenylamino) hexane, and 1,3-di (propenylamino) cyclohexane.

Among these monomers having a crosslinkable functional group, (n), (o), (p), (q), (s), (t)
And (u) are preferred, and more preferably (n),
(O), (p) and (s), particularly preferably (n) and (o). These monomers are each independently represented by 2
More than one species may be used in combination and / or with other copolymerizable monomers.

When two or more of these are combined, the combinations of monomers that can be copolymerized are as follows. (A)
The monomers copolymerizable with (f), (g),
(H), (i), (j), (n), (o), (p),
(R), (s), (v) and (w) are used.
The monomers copolymerizable with (b) include (c),
(D), (e), (k), (m), (n), (o),
(P), (q), (r), (s), (t), (u),
(V) and (w) are used.

The monomers copolymerizable with (c) include:
(B), (d), (e), (k), (m), (n),
(O), (p), (q), (r), (s), (t),
(U), (v) and (w) are used. The monomers copolymerizable with (d) include (b), (c), (e),
(K), (m), (n), (o), (p), (q),
(R), (s), (t), (u), (v) and (w) can be used. The monomers copolymerizable with (e) include:
(B), (c), (d), (k), (m), (n),
(O), (p), (q), (r), (s), (t),
(U), (v) and (w) are used.

The monomers copolymerizable with (f) include:
(A), (g), (h), (i), (j), (n),
(O), (p), (r), (s), (v) and (w) are used. As the monomer copolymerizable with (g),
(A), (f), (h), (i), (j), (n),
(O), (p), (r), (s), (v) and (w) are used. Examples of monomers copolymerizable with (h) include:
(A), (f), (g), (i), (j), (n),
(O), (p), (r), (s), (v) and (w) are used.

The monomers copolymerizable with (i) include:
(A), (f), (g), (h), (j), (n),
(O), (p), (r), (s), (v) and (w) are used. As the monomer copolymerizable with (j),
(A), (f), (g), (h), (i), (n),
(O), (p), (s), (v) and (w) are used. The monomers copolymerizable with (k) include (b)
(C), (d), (e), (m), (n), (o),
(P), (q), (r), (s), (t), (u),
(V) and (w) are used.

The monomers copolymerizable with (m) include:
(B), (c), (d), (e), (k), (n),
(O), (p), (q), (r), (s), (t),
(U), (v) and (w) are used. The monomers copolymerizable with (n) include (a), (b), (c),
(D), (e), (f), (g), (h), (i),
(J), (k), (m), (o), (p), (q),
(R), (s), (t), (u), (v) and (w) are used.

The monomers copolymerizable with (o) include:
(A), (b), (c), (d), (e), (f),
(G), (h), (i), (j), (k), (m),
(N), (p), (q), (r), (s), (t),
(U), (v) and (w) are used. The monomers copolymerizable with (p) include (a), (b), (c),
(D), (e), (f), (g), (h), (i),
(J), (k), (m), (n), (o), (q),
(R), (s), (t), (u), (v) and (w) are used.

The monomers copolymerizable with (q) include:
(B), (c), (d), (e), (k), (m),
(N), (o), (p), (r), (s), (t),
(U), (v) and (w) are used. The monomers copolymerizable with (r) include (a), (b), (c),
(D), (e), (f), (g), (h), (i),
(J), (k), (m), (n), (o), (p),
(Q), (s), (t), (u), (v) and (w) are used.

The monomers copolymerizable with (s) include:
(A), (b), (c), (d), (e), (f),
(G), (h), (i), (j), (k), (m),
(N), (o), (p), (q), (r), (t),
(U), (v) and (w) are used. The monomers copolymerizable with (t) include (b), (c), (d),
(E), (k), (m), (n), (o), (p),
(Q), (r), (s), (u), (v) and (w) are used. As the monomer copolymerizable with (u),
(B), (c), (d), (e), (k), (m),
(N), (o), (p), (q), (r), (s),
(T), (v) and (w) are used.

The monomers copolymerizable with (v) include:
(A), (b), (c), (d), (e), (f),
(G), (h), (i), (j), (k), (m),
(N), (o), (p), (q), (r), (s),
(T), (u) and (w) are used. The monomers copolymerizable with (w) include (a), (b), (c),
(D), (e), (f), (g), (h), (i),
(J), (k), (m), (n), (o), (p),
(Q), (r), (s), (t), (u) and (v) are used.

As other copolymerizable monomers, the following (aa) to (ww) can be used. Examples of the monomer (aa) copolymerizable with (a) include a hydrocarbon oxide (aa1) having 4 to 24 carbon atoms, a monoglycidyl ether (aa2) of a hydrocarbon (3 to 21 carbon atoms), and a carbon atom having 1 to 24 carbon atoms. Aliphatic carboxylic acid (aa3) having 18 carbon atoms, aromatic carboxylic acid having 7 to 18 carbon atoms (aa4), alcohol having 1 to 18 carbon atoms (aa5), phenol having 6 to 18 carbon atoms (aa)
6), an aliphatic amine having 1 to 18 carbon atoms (aa7), an aromatic amine having 6 to 18 carbon atoms (aa8) and the like are used.

(Aa1) Examples of the hydrocarbon oxide include EO, PO, butene oxide and α-olefin oxide having 5 to 18 carbon atoms (for example, pentane oxide,
Decene oxide and octadecene oxide) and styrene oxide. (Aa2) Examples of the monoglycidyl ether of a hydrocarbon (having 4 to 21 carbon atoms) include methyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and octadecyl glycidyl ether. .

(Aa3) Examples of the aliphatic carboxylic acid include acetic acid, butanoic acid, 2-ethylhexanoic acid, undecanoic acid and octadecanoic acid. (Aa4) Examples of the aromatic carboxylic acid include benzoic acid, p-methylbenzoic acid, and naphthalene carboxylic acid. (Aa5) As the alcohol, for example, methanol,
Isopropanol, butanol, 2-ethylhexanol, tetradecyl alcohol, octadecyl alcohol, benzyl alcohol and the like. Examples of (aa6) phenol include phenol, o-, m- or p-cresol, and p-ethylphenol.

(Aa7) Examples of the aliphatic amine include methylamine, dimethylamine, methylbutylamine, undecylamine, decalylamine and octadecylamine. (Aa8) As the aromatic amine, for example, aniline,
p-Methylaniline, p-undecylaniline, m-methoxyaniline, naphthylamine and the like.

Examples of the monomer (bb) copolymerizable with (b) include an olefin having 4 to 20 carbon atoms (bb1) and an aromatic compound having 8 to 18 carbon atoms having a polymerizable unsaturated double bond (bb2). ), An alkyl (meth) acrylate having 5 to 22 carbon atoms (bb3) and a polymerizable fatty acid ester having 4 to 20 carbon atoms (bb4) are used. (Bb1) Examples of the olefin include ethylene, propylene, butene, 1-octene, 1-decene, 1-eicosene, 6-methyl-1,4: 5,8-dimethano-
1,4,4a, 5,6,7,8,8a-octahydronaphthalene, norbornene, dicyclopentadiene and 5
-Ethylidene-2-norbornene and the like.

(Bb2) Examples of the aromatic compound having a polymerizable unsaturated double bond include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene,
Examples include m-methylstyrene, p-decylstyrene, p-chlorostyrene, divinylbenzene, and the like. (Bb3) Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, undecyl (meth) acrylate and octadecyl (meth).
Acrylate and the like. (Bb4) Examples of the polymerizable fatty acid ester include vinyl acetate, vinyl propanoate, vinyl octadecanoate,
Allyl acetate, allyl butanoate, propenyl acetate, propenyl hexanoate and the like can be mentioned.

The monomers (cc) copolymerizable with (c) include (bb1), (bb2), (bb3) and (bb)
4) and the like are used. A monomer copolymerizable with (d) (d
As (d), (bb1), (bb2), (bb3) and (bb4) can be used. The monomer (ee) copolymerizable with (e) includes (bb1), (bb2), (b)
b3) and (bb4) are used. Examples of the monomer (ff) copolymerizable with (f) include (aa1) and (aa)
2), (aa3), (aa4), (aa5), (aa)
6), (aa7) and (aa8) are used.

The monomers (gg) copolymerizable with (g) include (aa1), (aa2), (aa3), (aa)
4), (aa5), (aa6), (aa7) and (aa)
8) and the like are used. A monomer copolymerizable with (h) (h)
h) includes (aa1), (aa2), (aa3),
(Aa4), (aa5), (aa6), (aa7) and (aa8) are used. Examples of the monomer (ii) copolymerizable with (i) include (aa1), (aa2), and (aa)
3), (aa4), (aa5), (aa6), (aa)
7) and (aa8) are used.

The monomers (jj) copolymerizable with (j) include (aa1), (aa2), (aa3) and (aa)
4), (aa5), (aa6), (aa7) and (aa)
8) and the like are used. A monomer copolymerizable with (k) (k
As (k), (bb1), (bb2), (bb3), and (bb4) are used. Monomers (mm) copolymerizable with (m) include (bb1), (bb2), (b)
b3) and (bb4) are used. Examples of the monomer (nn) copolymerizable with (n) include (aa1) and (aa)
2), (aa3), (aa4), (aa5), (aa)
6), (aa7), (aa8), (bb1), (bb)
2), (bb3) and (bb4) are used.

The monomers (oo) copolymerizable with (o) include (aa1), (aa2), (aa3), (aa)
4), (aa5), (aa6), (aa7), (aa)
8), (bb1), (bb2), (bb3) and (bb)
4) and the like are used. A monomer copolymerizable with (p) (p
p) includes (aa1), (aa2), (aa3),
(Aa4), (aa5), (aa6), (aa7),
(Aa8), (bb1), (bb2), (bb3) and (bb4) are used. The monomers (qq) copolymerizable with (q) include (bb1), (bb2), and (bb)
3) and (bb4) are used.

The monomers (qq) copolymerizable with (r) include (aa1), (aa2), (aa3), (aa)
4), (aa5), (aa6), (aa7), (aa)
8), (bb1), (bb2), (bb3) and (bb)
4) and the like are used. Monomer (s) copolymerizable with (s)
s) includes (aa1), (aa2), (aa3),
(Aa4), (aa5), (aa6), (aa7),
(Aa8), (bb1), (bb2), (bb3) and (bb4) are used. Monomers (tt) copolymerizable with (t) include (bb1), (bb2), (bb)
3) and (bb4) are used.

The monomers (u) copolymerizable with (u) include (bb1), (bb2), (bb3) and (bb)
4) and the like are used. A monomer copolymerizable with (v) (v
v) includes (aa1), (aa2), (aa3),
(Aa4), (aa5), (aa6), (aa7),
(Aa8), (bb1), (bb2), (bb3) and (bb4) are used. Examples of the monomer (ww) copolymerizable with (w) include (aa1), (aa2), and (aa)
3), (aa4), (aa5), (aa6), (aa)
7), (aa8), (bb1), (bb2), (bb
3) and (bb4) are used.

Among these other copolymerizable monomers, from the viewpoints of heat resistance, electric properties and resin strength, (nn),
(Oo), (pp), (qq), (ss), (tt) and (uu) are preferable, and (nn) is more preferable.
(Oo), (pp), (qq) and (ss), particularly preferably (nn) and (oo), most preferably styrene, ethylene, propylene, 6-methyl-1,4: 5.
8-octahydronaphthalene, norbornene, dicyclopentadiene and 5-ethylidene-2-norbornene. These other copolymerizable monomers can be used alone or in combination of two or more.

When using other copolymerizable monomers,
The amount of the other copolymerizable monomer is not particularly limited, but is preferably 20 to 80% by weight, more preferably, from the viewpoint of heat resistance and resin strength, based on the weight of all the monomers used. 35 to 70% by weight, particularly preferably 50 to 60%
% By weight.

The method for (co) polymerizing a monomer having a crosslinkable functional group is not particularly limited, and a usual method can be applied. For example, a crosslinkable monomer may be placed in a reaction vessel optionally substituted with nitrogen. A method of dropping a monomer having a functional group and, if necessary, a monomer copolymerizable therewith, followed by aging for an appropriate time can be applied. The reaction temperature is usually 0 to 180
° C, preferably 60 to 150 ° C. The aging time is usually 0 to 50 hours, preferably 4 to 15 hours. When two or more monomers are used, the polymerization type may be a block type or a random type.

For the polymerization, a solvent can be used. The solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the monomer and the resin to be formed. Toluene, xylene, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents (eg, diethyl ether, dioxane, tetrahydrofuran, etc.) and halogen solvents (eg, chloroform, carbon tetrachloride, dichloromethane, etc.), etc. Is used. If a solvent is used, the amount of solvent used is 20 based on the total weight of the monomers.
To 100% by weight, more preferably 25 to 8% by weight.
0% by weight, particularly preferably 30 to 60% by weight.

Further, a reaction initiator (C) can be used. The (C) is not particularly limited and those used in a usual reaction are used. Depending on the type of the crosslinkable functional group, a radical reaction may be used. Initiation catalyst (C1), cationic polymerization initiation catalyst (C2), esterification catalyst (C3), amidation catalyst (C
4), an epoxy ring-opening catalyst (C5) and an isocyanate reaction catalyst (C6). As the radical reaction initiation catalyst (C1), a thermal radical reaction initiation catalyst (C11)
And a photo-radical reaction initiation catalyst (C12). As the thermal radical reaction initiation catalyst (C11), those having a 10-hour half-life temperature of preferably 80 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint of storage stability, include peroxides and azo compounds. Used.

As the peroxide, for example, t-butylperoxyacetate, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexyne-3, cumene hydroperoxide,
Benzoyl peroxide, bis (t-butylperoxy) diisopropylbenzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, P-menthane hydroperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, dicumyl peroxide and the like.

As the azo compound, for example, 2,2′-
Azobis (2,4-dimethylvaleronitrile), 2,
2′-azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile) and the like can be mentioned. Examples of the photoradical reaction initiation catalyst (C12) include, for example, benzoin alkyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, and methylbenzoyl phenol. And isopropylthioxanthone.

A sensitizer can be used together with the photoradical reaction initiation catalyst (C12), and nitro compounds (for example, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,
carbonyl compounds such as p'-tetramethyldiaminobenzophenone and chloranil, nitrobenzene, p-dinitrobenzene, 2-nitrofluorene and the like, aromatic hydrocarbons (such as anthracene and chrysene), sulfur compounds (such as diphenyldisulfide) And nitrogen compounds (for example, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene, and the like).

The cationic polymerization catalyst (C2) includes a thermal cationic polymerization catalyst (C21) and a photocationic polymerization catalyst (C2).
22) can be used. Thermal cationic polymerization catalyst (C21)
Examples thereof include onium salt-based catalysts (eg, triarylsulfonium salts and diaryliodonium salts), and examples thereof include San Aid SI series (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.).

As the cationic photopolymerization catalyst (C22),
For example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate,
p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio)
Phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- ( Diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene]-
Fe-hexafluorophosphate and diallyliodonium hexafluoroantimonate.
These can be easily obtained from the market, for example, SP-150, SP-170 (trade name, manufactured by Asahi Denka Co., Ltd.), Irgacure 261 (trade name, manufactured by Ciba Geigy), UVR-6974, UVR-6990 (trade name, manufactured by Union Carbide Co., Ltd.), CI-2855 (trade name, manufactured by Nippon Soda Co., Ltd.) and CD-1012 (trade name, manufactured by Sartomer Co., Ltd.).

Examples of the esterification catalyst (C3) and the amidation catalyst (C4) include, for example, acid catalysts (such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoroborane), and alkalis (for example, Examples thereof include sodium hydroxide, potassium hydroxide, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU, manufactured by San Apro, registered trademark) and the like, and metal complexes (eg, tetrapropyltitanium and the like). Can be

Examples of the epoxy ring-opening catalyst (C5) include, for example, an imidazole catalyst (2-methylimidazole,
Ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, etc., tertiary amine (benzyl) Methylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine, DBU, and the like, and onium salts (Sanshin Chemical Industries, Ltd., San-Aid SI series, etc.) And the like.

As the isocyanate reaction catalyst (C6), organometallic compounds (for example, trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannasoctoate, dibutyltin maleate, Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octate, bismuth octoate, bismuth naphthenate, cobalt naphthenate and phenylmercuric propionate, and tertiary amines (e.g., DB
U, N-methylmorpholine, N-ethylmorpholine, methyldibutylamine, triethylamine, and their carbonates and organic acid salts having 1 to 8 carbon atoms (such as formate))
And the like. These reaction initiators (C) can be used alone or as a mixture of two or more. When the reaction initiator (C) is used, the amount of (C) used is preferably 0.001 to 3.0% by weight, more preferably 0.01 to 2.0% by weight, based on the total weight of the monomers. 0% by weight, particularly preferably 0.05 to 1.0% by weight.

In order to leave at least two crosslinkable functional groups in the resin (A), a polymerization inhibitor may be used. The polymerization inhibitor is not particularly limited and may be one used for ordinary reactions. For example, diphenylhydrazyl, tri-p-nitrphenylmethyl, N- (3-N-
(Oxyanilino-1,3-dimethylbutylidene) aniline oxide, p-benzoquinone, p-tert-butylcatechol, nitrobenzene, picric acid, dithiobenzoyl disulfide, copper (II) chloride and the like. When a polymerization inhibitor is used, the amount of the polymerization inhibitor used is preferably from 0.1 to 5.0% by weight, more preferably from 0.1 to 2.0% by weight, based on the total weight of the monomers. And particularly preferably 0.5 to 1.0.

The method for converting a crosslinkable functional group by reacting a monomer having a crosslinkable functional group with a resin having a crosslinkable functional group is not particularly limited, and ordinary methods can be applied.
For example, a method in which a monomer having a crosslinkable functional group is added dropwise to a resin having at least two crosslinkable functional groups produced by the method described above, followed by aging for an appropriate time can be applied. The reaction temperature, the aging time, the solvent, the reaction initiator and the polymerization inhibitor are the same as in the above method.

Further, it may be reacted with all the crosslinkable functional groups in the resin, or may be reacted only with a part thereof. The reaction with a part thereof can be easily achieved by limiting the amount of the monomer having a crosslinkable functional group. For example,
A resin obtained by copolymerizing hydroxyethyl (meth) acrylate (20 to 80 parts by weight) and styrene (80 to 20 parts by weight) is crosslinked with a (meth) acrylic acid by an esterification reaction to form a crosslinkable functional group. Can be converted from a hydroxyl group to a (meth) acryloyl group.

In place of the resin produced by the above method,
A monomer having a crosslinkable functional group can be introduced into a resin having no crosslinkable functional group by a graft reaction. For example, 30 mol parts of propylene and 70 mol parts of 5-ethylidene-2-norbornene and a solvent are charged in a reaction vessel purged with nitrogen, and a transition metal compound (for example, titanium compound) / aluminum compound catalyst is used. After a copolymer is obtained by addition copolymerization, a monomer having a cross-linking functional group such as glycidyl (meth) acrylate, vinylcyclohexene monooxide, or 3,4-epoxycyclohexylmethyl (meth) acrylate is grafted onto the polymer. By doing so, a crosslinkable functional group can be introduced.

The low molecular weight compound (B) has a Mw of from 170 to
3,000, from the viewpoint of the strength after curing of the resin composition of the present invention and the viscosity thereof, preferably from 200 to 1,50.
0. The crosslinking functional group of (B) is the same type as (A), and the preferred one is also the same. The number of crosslinkable functional groups of (B) is at least two, and preferably 2 to 2.
The number is 5,000, more preferably 3 to 3,000, particularly preferably 5 to 1,000, still more preferably 7 to 500, and most preferably 10 to 200.
As (B), for example, in addition to (a) to (w), as monomers having one crosslinkable functional group, (aa1) to (aa)
8) and (bb1) to (bb4) can be used, and in addition, the following monoepoxide (x), polyepoxide (y), and curing agent (z) can be used.

As the monoepoxide (x), a glycidyl ester of a monocarboxylic acid (C3 to C30) (x
1) and a compound (x2) containing a cyclohexene monooxide group are used. Examples of the glycidyl ester of a monocarboxylic acid (x1) include glycidyl (meth)
Examples include acrylates, epihalohydrins (eg, epichlorohydrin, epibromohydrin, etc.) and hydroxyl-containing oxides (eg, glycidol, etc.).

Examples of the compound (x2) containing a cyclohexene monooxide group include, for example, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxymethylcyclohexanecarboxylate and 3,4-epoxy-6-carboxylate
Methylcyclohexylmethyl-3 ', 4'-epoxy-
6'-methylcyclohexanecarboxylate and the like.

Examples of the polyepoxide (y) include vinylcyclohexene dioxide, bis (3,4-epoxy-6)
-Methylcyclohexylmethyl) adipate, phenol or cresol novolak resin (Mw 400-
3,000), glycidyl ether of limonene phenol novolak resin (Mw 400-3,000), polyphenol (Mw 400-3,000) obtained by condensation reaction of phenol with glyoxal, glutaraldehyde or formaldehyde.
0) polyglycidyl ether, polyglycidyl ether of polyphenol having a Mw of 400 to 3,000 obtained by condensation reaction of resorcinol and acetone, a (co) polymer of glycidyl (meth) acrylate (polymerization degree is, for example, 2 to 10), epoxy Epoxidized polybutadiene having an equivalent weight of 130 to 1,000 (Mw 170 to 3,000), epoxidized soybean oil (Mw 170 to 3,000), and the like.

As the curing agent (z), (h), (aa)
3) or (aa4) acid anhydride. Among these low molecular weight compounds (B), (a), (b),
(C), (d), (e), (m), (n), (o),
(P), (q), (r), (s), (t), (u),
(H), (aa3) and (aa4) are preferable, (a), (b), (n), (o), (p) and (s) are more preferable, and (a) and (b) are particularly preferable. ), (N) and (o).

When a monoepoxide (x), a polyepoxide (y), a curing agent (z), or the like is used, the weight used thereof is not particularly limited. 20 to 80% by weight, more preferably 30 to 70% by weight, based on the weight of the body,
Particularly preferably, it is 40 to 60% by weight. The weight ratio (A: B) of (A) and (B) used is 10-95: 5-
90 is preferred, and more preferably 20 to 90:10.
80, particularly preferably 30-80: 20-70.

In the curable resin composition of the present invention, a reaction initiator (C) can be used. (C) may be added immediately before use of the curable resin composition of the present invention, or may be added during the production of the curable resin composition. When (C) is used, the amount of (C) used (excluding the amount used during preparation of (A)) is from 0.001 to 10 based on the total weight of (A) and (B). % By weight, more preferably 0.01 to 8% by weight, particularly preferably 0.05 to 8% by weight.
It is 5% by weight, most preferably 0.1 to 2% by weight.

The curable resin composition of the present invention may contain other additives (D), other resins (E), rubbers (F), fillers (G) and the like. Other additives (D)
Examples thereof include a phenolic antioxidant, a phosphorus antioxidant, a flame retardant, a phenolic thermal deterioration inhibitor, a benzophenone ultraviolet stabilizer, and an antistatic agent. When using (D), the amount of (D) used is (A)
0.001 to 3.0 based on the total weight of
% By weight, more preferably 0.01 to 2.0% by weight.
%, Particularly preferably 0.05 to 1.0% by weight.

As the other resin (E), for example, ABS
Resin, polystyrene, polycarbonate, polyamide,
Examples thereof include polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyimide, polysulfone, polyether sulfone, and polyarylate. When (E) is used, the amount of (E) used is preferably 1 to 45% by weight, more preferably 5 to 40% by weight, and particularly preferably based on the total weight of (A) and (B). Is 10-30
% By weight.

Examples of the rubber (F) include isoprene rubber, butadiene rubber, styrene-butadiene rubber, styrene / isoprene rubber, nitrile rubber, chloroprene rubber, and ethylene-propylene rubber.
When (F) is used, the amount of (F) used is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably based on the total weight of (A) and (B). Is 8 to 25% by weight.

Examples of the filler (G) include silica, alumina, calcium carbonate, barium sulfate, and titanium oxide. When (G) is used, (G)
Is used based on the total weight of (A) and (B),
It is preferably 1 to 50% by weight, more preferably 5 to 40% by weight.
%, Particularly preferably 8 to 30% by weight.

Further, the curable resin composition of the present invention can contain a solvent. As the solvent, the same solvents as those usable in the polymerization of (A) can be used.
The curable resin composition of the present invention may be used as it is without removing the solvent during the polymerization of (A), and after the solvent is removed during the polymerization of (A), the production of the curable resin composition of the present invention At the same time, the same or different solvent as used in the polymerization of (A) may be added, or (B) and the solvent may be mixed and mixed with (A). When a solvent is used, the amount of the solvent used is (A)
The amount is preferably 5 to 90% by weight, more preferably 10 to 90% by weight, based on the total weight of (the weight not including the solvent) and (B).
It is preferably from 80 to 80% by weight, particularly preferably from 30 to 70% by weight.

The curable resin composition of the present invention can be easily produced by uniformly mixing (A) and (B) and, if necessary, (C) to (G) by a usual method. It can be manufactured by the following methods (1) to (3). (1) A method of blending (A) and (B) and then mixing (C) to (G) and / or a solvent as necessary. (2) A method in which (A) is mixed with (C) to (G) and / or a solvent as required, and then (B) is mixed. (3) (A) and (B) and if necessary (C) to (G)
And / or a method of simultaneously mixing with a solvent

The dielectric constant after curing of the curable resin composition of the present invention (based on JIS K6911 (1995) 5.14) is 3.5 or less at 1 GHz, preferably 2 to 3.5. is there. When the dielectric constant exceeds 3.5, when applied to an integrated circuit of an electronic component, signal delay tends to occur, and it tends to be difficult to improve the performance of the circuit. When the dielectric constant is 2 or more, bubbles do not have to be dispersed in the curable resin composition, and the resin strength does not decrease.

As a method of adjusting the dielectric constant,
(A) a method of adjusting according to the kind of a monomer as a raw material for production, for example, the proportion of ethylene, propylene, butadiene, isoprene, (meth) acrylate having 4 or more carbon atoms and styrene to all monomers such as styrene When the amount of (meth) acrylic acid and acrylonitrile and the like are increased, the dielectric constant tends to increase. For example, as the composition having a dielectric constant of 2 to 3.5, styrene / glycidyl (meth) acrylate = 10 to 55/90 to 45 parts by mass and the amount of 4-methylcyclohexane-1,2-dicarboxylic anhydride And stoichiometric (equivalent) mixtures. In addition, the boiling water absorption (JIS K7209) of the curable resin composition of the present invention after curing.
(2000) 6.3B method)
001% is preferred, and more preferably 2.50-0.
005%, particularly preferably 2.00 to 0.01%.

The form of the curable resin composition of the present invention may be, for example, either a liquid form (including a solution form) or a film form (including a plate form and a sheet form), and the film thickness is 1 to 100 μm. Preferably, more preferably 5
To 50 μm, particularly preferably 15 to 50 μm. To form a film, the liquid curable resin composition of the present invention can be formed by a usual molding method, for example, a curtain coater,
A method of applying to a support or a substrate using a knife coater, a spray gun, a roll coater, a spin coater, a dispenser, a bar coater, a screen printer, or the like, or a film by a dipping method, an injection molding method, or the like. it can. Even in the case of a film, it is softened by heating (hot press or the like), has good penetration into minute parts (such as irregularities) of the substrate, and is excellent in workability. When a support is used, the film on the support can be transferred to a substrate or the like and used. When a substrate or the like is used, it can be used as it is. After coating, it is preferable to heat for the purpose of drying the solvent and the like. The heating conditions include, for example, temperature: 1
0 to 150 ° C (preferably 20 to 120 ° C), time: 1
６０60 minutes (preferably 2-40 minutes).

As the support, for example, PET (polyethylene terephthalate), polyethylene, polypropylene and modified products thereof can be used. As a substrate,
Various printed wiring boards having a conductive (copper, gold, silver, aluminum, etc.) circuit and the like can be used.
T) and polyamide resin) impregnated into a non-woven fabric (glass fiber non-woven fabric, aramid fiber non-woven fabric, etc.), etc. (For example, a BT substrate, a glass epoxy substrate, a paper phenol substrate, a paper epoxy substrate, etc.) can be used.

The curable resin composition of the present invention can be used as an insulator by heating and curing, and is suitable as an overcoat material, an interlayer insulating material, a printed circuit board, and the like. It is suitable as an interlayer insulating material. It is most suitable as an overcoat material or an interlayer insulating material for electronic devices (semiconductor devices, light emitting diodes, various memories, etc.), hybrid ICs, MCMs, electric wiring circuit boards, display components, and the like. The conditions for the heat curing include 80 to 250 ° C. (preferably 120 to 200 ° C.) and 0.1 to 15 hours (preferably 0.2 to 12 hours).

As a method of using the composition of the present invention as an insulator, for example, when the composition is used as an interlayer insulating material,
After applying the liquid composition of the present invention to the substrate or after laminating the film-like composition of the present invention, hot pressing,
If necessary, drilling or the like (roughening, formation of a conductive circuit, etc.) is performed, a base material is laminated, this operation is repeated, and finally, heat curing is performed to form a multilayer. Further, when the composition of the present invention is used as a part of the substrate material of a multilayer substrate, the liquid composition of the present invention is applied to a substrate, or after the film-like composition of the present invention is laminated, There is a method in which hot pressing is performed, processing such as perforation is performed as necessary, and this operation is repeated. In addition, it can also be used as a printed wiring board as it is without using a base material.

When used as an interlayer insulating material for a multilayer circuit board of an electronic circuit or the like, one interlayer insulating layer may be composed of one layer or multiple layers, and the thickness is preferably 1 to 100 μm, more preferably 15 to 50 μm. It is. The condition of the hot pressing is a temperature of 25 to 180 ° C. (preferably 5 to 180 ° C.).
0 to 150 ° C.), a pressure of 0.01 MPa to 10 MPa (preferably 0.1 to 1 MPa), and a time of 1 to 1200 seconds (preferably 10 to 300 seconds). Holes (via holes, through holes, etc.) for conducting between layers of a multilayer substrate
Can be prepared by an ordinary method, for example, a method using a laser (carbon dioxide, YAG, excimer, or the like), a drill, or the like can be used. Roughening can be performed by a usual method, for example, a method described in Japanese Patent Publication No. 6-49852 can be used. The conductive circuit can be formed by an ordinary method, for example, a sputtering method, an electroless method, or the like can be used.

The insulator obtained from the curable resin composition of the present invention has a volume resistivity (JIS K6011 (1995)).
10 ¹⁵ Ω / cm to 10 ¹⁷ Ω / cm, which is excellent in electrical insulation as compared with conventionally used insulating materials such as epoxy resin and polyimide resin. Further, it has good adhesion to copper formed by oxidizing agent treatment and electroless copper plating, and has a peel strength (JIS C6481 (1995)
Year) 5.7) shows 0.8 kgf / cm or more. On the other hand, the heat resistance is equivalent to that of the
No abnormalities such as sagging, collapse, and blistering of the pattern are observed even when the solder is brought into contact with the solder for one minute, and the crack resistance to various solvents is very good. The insulating material according to the present invention is JIS K 6911 (199).
5 years) Excellent in 10% sulfuric acid resistance, 10% hydrochloric acid resistance, 10% nitric acid resistance and 10% sodium hydroxide resistance measured by the method specified in 5.32. Therefore, the curable resin composition of the present invention has a great merit for speeding up and increasing the density of an electronic circuit.

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Hereinafter, parts represent parts by mass, and% represents mass%. Synthesis Example 1 5 methyl ethyl ketone in a reaction vessel purged with nitrogen
Glycidyl methacrylate 200 which was charged with 0 parts, heated to 80 ° C., and uniformly dissolved in another nitrogen-purged container.
, 200 parts of styrene, 200 parts of methyl ethyl ketone and 1.5 parts of azobisisobutyronitrile were dropped into the reaction vessel over 4 hours. After dropping, 1
After aging at 00 ° C. for 4 hours, a solution of the resin (A1) with styrene / glycidyl methacrylate = 50 parts / 50 parts was obtained. (A1) has a Mw of 160,000, a number average molecular weight by GPC (hereinafter abbreviated as Mn) of 53,000, an epoxy equivalent of 284, and a crosslinkable functional group (A1) based on the Mn and the epoxy equivalent. The number of (epoxy groups) was 187. (A1) was prepared using methyl ethyl ketone so as to have a solid content of 40% to obtain a resin solution (A11).

Synthesis Example 2 The following polymerization experiments were performed in a glove box purged with nitrogen. 100 parts of toluene was charged into a four-necked flask equipped with a stirrer and a temperature controller, and stirred at 30 ° C.
Then, 5 parts by weight of a hexane solution of diethyl aluminum chloride (catalyst concentration 0.2 mmol / ml) and a hexane solution of vanadium oxytrichloride (catalyst concentration 0.0
2 mmol / ml) 5 parts by weight, 50 parts of 5-ethylidene-2-norbornene and 50 parts of 1-hexene were charged, and
Polymerization was carried out at 0 ° C. for 120 minutes. This copolymer solution was added to 3000
The mixture was added dropwise to a portion of isopropanol with stirring to form a precipitate.
The solvent was distilled off under reduced pressure of 0 mmHg, and the resin (A2)
70 parts were obtained. Mw of (A2) was 98,000.

(A2) 100 parts, 20 parts of glycidyl methacrylate, and 7.0 of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: Perhexa 25B, manufactured by NOF Corporation) The part was dry-blended at room temperature and then extruded with a twin-screw extruder at a cylinder temperature of 260 ° C. and a screw rotation speed of 230 rpm to obtain a resin (A3). Mw of (A3) is 117,000, M
n is 29,000, epoxy equivalent is 850, and Mn is
The number of crosslinkable functional groups (epoxy groups) in (A3) was 138 from the above and the epoxy equivalent. (A3) having a solid content of 40
% And dissolved in toluene to give a resin solution (A3
3) was obtained.

Synthesis Example 3 6-methyl-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-Octahydronaphthalene (MTD) by ring-opening polymerization by a known method, 100 parts of a cyclic olefin resin (Mw 28,000), 20 parts of glycidyl methacrylate and 2,5 -Dimethyl-2,
After dry blending 7.0 parts of 5-di (t-butylperoxy) hexane (trade name: Perhexa 25B, manufactured by NOF Corporation) at a room temperature of 260 ° C. and a screw rotation speed of 230 rpm, 2 parts were mixed. The resin was extruded with a screw extruder to obtain a resin (A4). Mw of (A4) is 33,
000, Mn was 8,400, and the epoxy equivalent was 840. From the Mn and the epoxy equivalent, the number of crosslinkable functional groups (epoxy groups) in (A4) was 10. (A4) was dissolved in toluene so that the solid content was 40%, and the resin solution (A
44) was obtained.

Synthesis Example 4 Methyl ethyl ketone was placed in a reaction vessel purged with nitrogen.
0 parts, heated to 80 ° C., and dissolved uniformly in another nitrogen-purged container in 200 parts of hydroxyethyl methacrylate, 200 parts of styrene, and 20 parts of methyl ethyl ketone.
A mixture consisting of 0 parts and 1.5 parts of azobisisobutyronitrile was dropped into the reaction vessel over 4 hours. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 4 hours to obtain a solution of the resin (A5) in methyl ethyl ketone. 30 parts of acrylic acid is added to 100 parts of a methyl ethyl ketone solution of the resin (A5), and while adding a solvent (methyl ethyl ketone), 10 parts of
Esterification was performed at 0 ° C. for 4 hours to obtain a solution of the resin (A6) in methyl ethyl ketone. Mw of (A6) is 160,
000, Mn was 45,000, and the equivalent of the acryloyl group analyzed by NMR was 610. From the Mn and the acryloyl group equivalent, the number of crosslinkable functional groups (acryloyl groups) in (A6) was 74. (A6) was adjusted by adding methyl ethyl ketone so that the solid content became 40%, to obtain a resin solution (A66).

Synthesis Example 5 30 parts of methacrylic acid was added to 100 parts of a solution of the resin (A5) obtained in Synthesis Example 4 in methyl ethyl ketone, and the mixture was reacted at 100 ° C. for 4 hours under reduced pressure while adding methyl ethyl ketone. Was obtained in methyl ethyl ketone.
(A7) has Mw of 160,000 and Mn of 45,000.
0, the equivalent of the methacryloyl group analyzed by NMR was 6
25, and based on Mn and the methacryloyl group equivalent, (A
The number of the crosslinkable functional groups (methacryloyl groups) in 7) was 72. (A7) was adjusted by adding methyl ethyl ketone so that the solid content became 40%, to obtain a resin solution (A77).

Example 1 To 175 parts of the resin solution (A11), 30 parts of resorcinol diglycidyl ether and 6 parts of 2-ethyl-4-methylimidazole were added and mixed with stirring. This was coated on a PET film having a thickness of 50 μm (257 mm × 364 mm) by a knife coater (manufactured by Yasui Seiki; knife coater SNC-3).
00) and dried at 60 ° C. for 30 minutes to remove the solvent, thereby preparing a curable resin composition of the present invention on a PET film. When the thickness of the curable resin composition was measured, it was 47 ± 2 μm.

The curable resin composition was coated on a BT substrate (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., CCL-830, 100 mm × 10 mm).
0 mm, each half of which is removed by etching).
After hot pressing under the condition of 4 kgf, the PET film was peeled off and cured by heating at 180 ° C. for 3 hours to obtain a sample for evaluation. Using a sample for evaluation, after performing −55 ° C. for 30 minutes, 125 ° C. was continued for 30 minutes (the temperature rising rate and the temperature decreasing rate are both 100 ° C./min), and a thermal cycle test in which this was repeated was performed. No cracking, blistering or peeling failure was observed even after 1000 cycles. Also, JIS K6911 (1995) 5.14.
The dielectric constant after curing of the curable resin composition at 1 GHz measured in accordance with JIS was 2.9.

Example 2 To 175 parts of the resin solution (A33), 30 parts of resorcinol diglycidyl ether and 6 parts of 2-ethyl-4-methylimidazole were added and mixed with stirring. This was coated on a PET film (257 mm × 364 mm) having a thickness of 50 μm by a knife coater (manufactured by Yasui Seiki; knife coater SNC-30).
0), dried at 60 ° C. for 30 minutes, and the solvent was removed to prepare the curable resin composition of the present invention on a PET film. When the thickness of the curable resin composition was measured, it was 47 ± 2 μm.

An evaluation sample was obtained in the same manner as in Example 1 using the curable resin composition. A thermal cycle test was performed using the evaluation sample in the same manner as in Example 1. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles. The cured dielectric constant of the curable resin composition measured in the same manner as in Example 1 was 2.5.

Example 3 To 175 parts of the resin solution (A44), 30 parts of resorcinol diglycidyl ether and 6 parts of 2-ethyl-4-methylimidazole were added and mixed with stirring. This was coated on a 50 μm-thick PET film (257 mm × 364 mm) by a knife coater (manufactured by Yasui Seiki; knife coater SNC-3).
00) and dried at 60 ° C. for 30 minutes to remove the solvent, thereby preparing the curable resin composition of the present invention on a PET film. When the thickness of the curable resin composition was measured, it was 47 ± 2 μm.

An evaluation sample was obtained in the same manner as in Example 1 using the curable resin composition. A thermal cycle test was performed using the evaluation sample in the same manner as in Example 1. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles. The cured dielectric constant of the curable resin composition measured in the same manner as in Example 1 was 2.7.

Example 4 To 175 parts of the resin solution (A66), 30 parts of ethylene glycol diacrylate and 5 parts of dicumyl peroxide were added and mixed by stirring. This was applied on a PET film (257 mm × 364 mm) having a thickness of 50 μm using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300), dried at 60 ° C. for 30 minutes, and the solvent was removed.
The curable resin composition of the present invention was prepared on an ET film. When the thickness of the curable resin composition was measured, 47 ±
It was 2 μm.

An evaluation sample was obtained in the same manner as in Example 1 using the curable resin composition. A thermal cycle test was performed using the evaluation sample in the same manner as in Example 1. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles. The cured dielectric constant of the curable resin composition measured in the same manner as in Example 1 was 2.9.

Example 5 To 175 parts of the resin solution (A77), 30 parts of ethylene glycol diacrylate and 5 parts of dicumyl peroxide were added and mixed with stirring. This was applied on a PET film (257 mm × 364 mm) having a thickness of 50 μm using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300), dried at 60 ° C. for 30 minutes, and the solvent was removed.
The curable resin composition of the present invention was prepared on an ET film. When the thickness of the curable resin composition was measured, 47 ±
It was 2 μm.

An evaluation sample was obtained in the same manner as in Example 1 using the curable resin composition. Using this evaluation sample, a thermal cycle test was conducted in the same manner as in Example 1. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles. The cured dielectric constant of the curable resin composition measured in the same manner as in Example 1 was 2.9.

Comparative Example 1 85 parts per 100 parts of Epicoat 828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd .; bisphenol A type epoxy resin)
Of 4-methylcyclohexane-1,2-dicarboxylic acid was added and mixed by stirring, and a knife coater (manufactured by Yasui Seiki;
BT substrate (Mitsubishi Gas Chemical Industry Co., Ltd., CCL-830, 100 mm) using knife coater SNC-300
A sample having a thickness of 62 ± 2 μm was applied on a sheet having a thickness of 100 mm and half of the copper foil on both the front and rear sides removed by etching, and then heated and cured at 180 ° C. for 3 hours to obtain a sample for comparative evaluation. Using the sample for comparative evaluation, a heat cycle test was performed in the same manner as in Example 1.
Cracks occurred at a rate of 1 piece / cm ^{2 in} the cycle. The dielectric constant measured in the same manner as in Example 1 was 3.6.

Comparative Example 2 Cresol novolak epoxy resin 10 having Mw of 1040
To 0 parts, 95 parts of 4-methylcyclohexane-1,2-dicarboxylic acid was added and mixed by stirring, and B was added using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300).
T substrate (CCL-830, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.)
100 ± 100 mm, half of copper foil on both sides are removed by etching) 62 ± 2 μm
, And cured by heating at 180 ° C. for 3 hours to obtain a sample for comparative evaluation. Using this sample for comparative evaluation, a thermal cycle test was performed in the same manner as in Example 1, but cracks occurred at a rate of 1 piece / cm ^{2 in} 700 cycles. The dielectric constant measured in the same manner as in Example 1 was 3.5.

[0137]

The curable resin composition of the present invention can produce an insulator having extremely excellent thermal shock resistance and dielectric properties. Furthermore, the curable resin composition of the present invention has adhesiveness, heat resistance,
An insulator having excellent solvent resistance, low water absorption, electrical insulation, chemical resistance, workability, and the like can be formed. Therefore, it is particularly suitable for an overcoat material or an interlayer insulating material used for a circuit board used for various electric devices, electronic components or semiconductor elements. The curable resin composition of the present invention is not limited to the technical field such as a circuit board, but can be used in various fields, and is a very useful material that can be used particularly for forming a thin film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/44 H01B 3/44 A

Claims (4)

[Claims] 1. A resin (A) having at least two crosslinkable functional groups in a molecule, and a low molecular compound (B) having at least two crosslinkable functional groups of the same type in the molecule.
And the weight average molecular weight of (A) is 3,000.
Ｂ1,000,000, the weight average molecular weight of (B) is 170１７０3,000, and the dielectric constant after curing is 3.5.
A curable resin composition characterized by the following. 2. The curable resin composition according to claim 1, wherein the crosslinkable functional group is an epoxy group derived from a glycidyl group or a cyclohexenyl monooxide group, or a (meth) acryloyl group. 3. A method according to claim 1, wherein (A) is styrene, ethylene, propylene, 6-methyl-1,4: 5,8-dimethano-1,
At least one monomer selected from the group consisting of 4,4a, 5,6,7,8,8a-octahydronaphthalene, norbornene, dicyclopentadiene and 5-ethylidene-2-norbornene is an essential constituent monomer The curable resin composition according to claim 1, wherein 4. An insulator obtained by curing the curable resin composition according to claim 1.