JP2003055481A - Curable film and insulant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulant excellent in thermal shock resistance and dielectric properties and a curable film best suited therefor. SOLUTION: There are provided a curable film which comprises a curable resin having in the molecule at least two of at least one crosslinkable functional group selected from the group consisting of an epoxy group, (meth)acryloyl group, alkenylamino group and alkenyloxy group and having a glass transition temperature of 50-150 deg.C and a weight average molecular weight of 10,000-1,000,000 before curing, and has a permittivity of 3.2 or less after curing, and a curable film comprising a composition containing a curable polymer compound having a weight average molecular weight of 10,000-1,000,000, which film has a tensile modulus of 100-250 kgf/mm<2> and a permittivity of 3.5 or less after curing.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable film and an insulator. More specifically, the present invention relates to a curable film and an insulator suitable as an overcoat material or an interlayer insulating material for a circuit board used in various electric devices, electronic parts, semiconductor elements and the like.

[0002]

2. Description of the Related Art As insulating materials, there are defects such as moisture resistance of epoxy resin compositions and polyimide resins, dielectric properties in high frequency range, heat resistance and solvent resistance of polyolefin resins and polyphenylene ether resins. In order to solve the drawbacks such as properties, for example, a copolymer of norbornene-type monomer and ethylene, sulfur cross-linking, organic oxide cross-linking,
Method of electron beam crosslinking or radiation crosslinking (JP-A-62-3
4924), polyphenylene ether substituted with a propargyl group or an allyl group, polyphenylene ether containing a double bond, and unsaturated carboxylic acid or its acid anhydride-modified polyphenylene ether (JP-A-1-69628). Japanese Laid-Open Patent Publication No. 1-69629
Japanese Patent Laid-Open No. 1-113425, Japanese Patent Laid-Open No. 1-141
(13426, JP-A 1-239017, etc.)
Etc. are known.

[0003]

However, the former method has a problem in application to an insulating material such as an overcoat material or an interlayer insulating material because of its high dielectric constant of 3.7 or more.
Further, in the latter example, since an allyl group, an olefinically unsaturated group or an unsaturated carboxylic acid is used as a curing functional group, the curing reactivity is poor, especially in oxygen (in air). , Heat resistance is insufficient. That is, an object of the present invention is to provide an insulator having excellent thermal shock resistance and dielectric properties and a curable film most suitable for the insulator.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to achieve the above object. That is, the first aspect of the present invention is to provide an epoxy group, (meth)
It has at least two crosslinkable functional groups selected from the group consisting of an acryloyl group, an alkenylamino group and an alkenyloxy group in the molecule, has a glass transition temperature before curing of 50 to 150 ° C. and a weight average molecular weight of 10,0
A curable film comprising a curable resin of 0 to 1,000,000 and having a dielectric constant of 3.2 or less after curing (A). Second of the present invention
Comprises a curable resin composition (X) and a thermoplastic resin (Y), and the difference in solubility parameter between (X) and (Y) is 0.5 to 3.0. And (Y) is a curable film comprising a curable resin material having a weight average molecular weight of 5,000 to 1,000,000.

The third aspect of the present invention is the curable resin composition (X).
And a thermoplastic resin (Y), wherein the difference in solubility parameter between (X) and (Y) is 1.0 to 3.0, and the solubility parameter of (X) is 5 .0-1
A curable film comprising a curable resin material of 2.0. A fourth aspect of the present invention is a film comprising a composition containing a curable polymer compound having a weight average molecular weight of 10,000 to 1,000,000, wherein the film has a tensile elastic modulus of 100 to 100 after curing. 250 kgf
/ Mm ² and the dielectric constant after curing is 3.5 or less, which is a curable film. The fifth aspect of the present invention is
The insulator has a tensile elastic modulus of 100 to 250 kgf / mm ² and a thermal expansion coefficient α1 of 30 to 50 ppm.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Regarding the first aspect of the present invention, the curable resin (A) has a crosslinkable functional group selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group and an alkenyloxy group. At least one selected from the above may be used, and a combination of two or more thereof may be used. As the epoxy group, any of the groups represented by formula (1) or (2) can be used.

[Chemical 1]

The (meth) acryloyl group means an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (C
_{H 2 = C (CH 3)} CO-) means. As the alkenylamino group, an alkenylamino group having 2 to 4 carbon atoms or the like is used, and examples thereof include a vinylamino group, a propenylamino group (1-propenylamino group), an allylamino group (2-
And a 1-butenylamino group, a 2-butenylamino group, a 1-methylpropenylamino group, and the like. The alkenyloxy group has 2 to 2 carbon atoms.
4 alkenyloxy group and the like are used, for example, vinyloxy group, propenyloxy group (1-propenyloxy group), allyloxy group (2-propenyloxy group), 1
Examples include -butenyloxy group, 2-butenyloxy group and 1-methylpropenyloxy group. Of these crosslinkable functional groups, an epoxy group, a (meth) acryloyl group, a vinyloxy group, a propenyloxy group and an allyloxy group are preferable, an epoxy group, a (meth) acryloyl group and a propenyloxy group are more preferable, and an epoxy group is particularly preferable. And a (meth) acryloyl group, more preferably an epoxy group, and most preferably an epoxy group represented by the formula (2). The presence of these crosslinkable functional groups makes it easy to obtain an insulator having excellent thermal shock resistance and dielectric constant.

The number of the crosslinkable functional groups may be at least 2, preferably 2 to 5,000, more preferably 3 to 3,000, and particularly preferably 5 to 5.
The number is 1,000, more preferably 7 to 500, and most preferably 10 to 400. When the number of crosslinkable functional groups is within this range, an insulator excellent in thermal shock resistance and dielectric constant can be easily obtained. The glass transition temperature of (A) before curing may be 50 to 150 ° C., preferably 53 to 140 ° C., more preferably 56 to 130 ° C., particularly preferably 59 to 135 ° C., and further particularly preferably 62 to 12
The temperature is 0 ° C, most preferably 65 to 100 ° C. When the glass transition temperature is in this range, an insulator excellent in thermal shock resistance and the like can be easily obtained. The glass transition temperature is TMA-T.
It is measured by g.

The weight average molecular weight of (A) is 10,000.
~ 1,000,000, but 20,000 ~
900,000 is preferable, and more preferably 30,0
00 to 500,000, particularly preferably 40,000 to
200,000, and particularly preferably 50,000 to
150,000, particularly preferably 60,000-12
It is 10,000. When the weight average molecular weight is in this range, an insulator excellent in thermal shock resistance and the like can be easily obtained. The weight average molecular weight is measured by gel permeation chromatography and is abbreviated as Mw hereinafter.
The dielectric constant of (A) after curing may be 3.2 or less, preferably 2.4 to 3.2, and more preferably 2.
5 to 3.1, particularly preferably 2.5 to 3.0, even more preferably 2.6 to 2.9, most preferably 2.6 to
2.8. If the dielectric constant after curing is in this range, the reliability will be further improved when used as an insulator, and when applied to integrated circuits of electronic parts, signal delay is less likely to occur and circuit performance can be easily improved. Tends to become. The curing is carried out by heating at 170 ± 10 ° C. for 90 ± 10 minutes with a normal air type heater. The dielectric constant is JIS
1GHz based on K6911 (1995) 5.14
It is measured by.

(A) has, for example, a method of (co) polymerizing a monomer having a crosslinkable functional group, or a reactive functional group (such as an amino group, a nitrile group, a carboxyl group, a hydroxyl group and an isocyanate group). It can be easily produced by a method of reacting a resin with a monomer having a crosslinkable functional group to convert it into a resin having a crosslinkable functional group. The resin having a reactive functional group can be easily produced by a method of (co) polymerizing a monomer having a reactive functional group. The monomer having a crosslinkable functional group is a monomer having at least two functional groups of at least one selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group and an alkenyloxy group ( a-j, v, w), and the crosslinkable functional group, and at least one functional group selected from the group consisting of a primary amino group, a secondary amino group, a nitrile group, a carboxyl group, a hydroxyl group and an isocyanate group. A monomer (qw) having at least one group and one group can be used. As the monomer having a reactive functional group, in addition to the above monomer (qw), a group consisting of a primary amino group, a secondary amino group, a nitrile group, a carboxyl group, a hydroxyl group and an isocyanate group. A monomer (k-p) having at least two functional groups of at least one selected from the above can be used.

Monomers (a-j,) having at least two functional groups selected from the group consisting of epoxy groups, (meth) acryloyl groups and alkenyloxy groups.
v and w) include a monomer (a) having only an epoxy group, a monomer (b) having only a (meth) acryloyl group, a monomer (c) having only a vinyloxy group, and an allyloxy group only. Having a monomer (d), a monomer having only a 2-propenyloxy group (e), a monomer having an epoxy group and a (meth) acryloyl group (f), a monomer having an epoxy group and a vinyl group Monomer (g), monomer (h) having (meth) acryloyl group and vinyloxy group, monomer (i) having (meth) acryloyl group and allyloxy group, (meth) acryloyl group and propenyloxy A monomer (j) having a group, a monomer (v) having an allylamino group, a monomer (w) having a propenylamino group and the like can be used.

Monomer (kp) having at least two functional groups selected from the group consisting of primary amino group, secondary amino group, nitrile group, carboxyl group, hydroxyl group and isocyanate group. Examples of the monomer include a monomer (k) having a primary amino group, a monomer (m) having a secondary amino group, a monomer (n) having only a carboxyl group, and a monomer having only a hydroxyl group. The monomer (p) having only (o) and an isocyanate group can be used. A single unit having at least one crosslinkable functional group and at least one functional group selected from the group consisting of primary amino group, secondary amino group, nitrile group, carboxyl group, hydroxyl group and isocyanate group. As the monomer (qw), a monomer (q) having a nitrile group and a vinyloxy group, a monomer (r) having a nitrile group and a (meth) acryloyl group, a hydroxyl group and a (meth) acryloyl group. A monomer (s) having, a monomer (t) having a (meth) acryloyl group and an isocyanate group, a monomer (u) having a (meth) acryloyl group and a carboxyl group, and an allylamino group. The monomer (v) and the monomer (w) having a propenylamino group can be used.

As the monomer (a) having only an epoxy group, a polyepoxide having 2 to 7 or more epoxy groups in the molecule can be used, and examples thereof include glycidyl ether type polyepoxide (a1) and glycidyl ester type. Polyepoxide (a2), glycidyl amine type polyepoxide (a3), alicyclic polyepoxide (a4), etc. are used.

Glycidyl ether type polyepoxide (a
As 1), for example, the following (a11) to (a14)
Etc. can be used. (A11) Diglycidyl ether of dihydric phenol (carbon number 6 to 30) 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-
Dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4′-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether,
9,9'-bis (4-hydroxyphenyl) furo orange glycidyl ether and diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin.

(A12) Polyhydric phenol (having 6 to 5 carbon atoms)
0 or more, Mw 110-5,000, trivalent to hexavalent or higher) polyglycidyl ether pyrogallol triglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol tritri Glycidyl ether, tetrakis (4-hydroxyphenyl) ethane tetraglycidyl ether, trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4,4 '-Oxybis (1,4-
Phenylethyl) phenylglycidyl ether and bis (dihydroxynaphthalene) tetraglycidyl ether.

(A13) Dihydric alcohol [C2-C6
Or more alkylene glycol or carbon number 6
To 24 or more alkylene oxide of dihydric phenol (having 2 to 4 carbon atoms) (hereinafter, alkylene oxide having 2 to 4 carbon atoms is abbreviated as AO) 1 to 90 mol adduct] diglycidyl ether ethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (M
w150-4,000) diglycidyl ether, polypropylene glycol (Mw180-5,000) diglycidyl ether, polytetramethylene glycol (Mw
200-5,000) 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 is abbreviated as PO). (1
˜20 mol) diglycidyl ether of adduct and the like.

(A14) Polyhydric alcohol having 3 to 7 valences or more (having 3 to 50 or more carbon atoms, Mw76
Up to 10,000) polyglycidyl ether trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether and poly (polymerization degree 2-5) glycerin polyglycidyl ether.

Glycidyl ester type polyepoxide (a
As 2), for example, the following (a21) to (a22)
Etc. can be used. (A21) Polyglycidyl ester of divalent to hexavalent aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms) diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate and tri Mellitic acid triglycidyl ester, etc. (A22) Aromatic nucleus water additive of polyglycidyl ester (a21) of divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acid (having 6 to 20 or more carbon atoms), diglycidyl dimer acid , Diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and tricarballylic acid triglycidyl ester.

Glycidylamine type polyepoxide (a
As 3), for example, the following (a31) to (a34)
Etc. can be used. (A31) Polyglycidyl aromatic amine having 2 to 10 or more glycidyl groups (C6 to 20 or more carbon atoms of aromatic amine) N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ', N'-tetraglycidyldiaminodiphenylmethane, N, N, N', N'-tetraglycidyldiaminodiphenylsulfone, N, N,
N ', N'-tetraglycidyl diethyldiphenylmethane and N, N, O-triglycidyl aminophenol.

(A32) Polyglycidyl aliphatic or araliphatic amine having 2 to 10 or more glycidyl groups (6 to 20 or more carbon atoms of aliphatic or araliphatic amine) N, N, N ', N'-tetraglycidyl xylylenediamine and N, N, N', N'-tetraglycidyl hexamethylenediamine and the like. (A33) Polyglycidyl alicyclic amine having 2 to 10 or more glycidyl groups (C6 to C20 or more of alicyclic amine) N,
Hydrogenated compounds of N, N ′, N′-tetraglycidyl xylylenediamine and the like. (A34) Polyglycidyl heterocyclic amine having 2 to 10 or more glycidyl groups (heterocyclic amine has 6 to 20 or more carbon atoms) Trisglycidyl melamine, N-glycidyl-4-glycidyloxypyrrolidone, etc. .

As the alicyclic polyepoxide (a4),
For example, having 6 to 50 or more carbon atoms and Mw 98 to
5,000, and alicyclic epoxides having 2 to 4 or more epoxy groups can be used, and examples thereof include 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) Examples include adipate and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine.

The monomer (b) having only a (meth) acryloyl group is a divalent phenol (having 6 to 30 carbon atoms).
Di (meth) acrylate (b1), polyhydric phenol {carbon number 6 to 50 or more, Mw 110 to 5,000
0, trivalent to hexavalent or higher} poly (meth) acrylate (b2), divalent alcohol [alkylene glycol having 2 to 6 or more carbon atoms or dihydric phenol having 6 to 24 carbon atoms or more] AO 1 to 90 mol adduct] di (meth) acrylate (b3) and trivalent to 7
Poly (meth) of a polyhydric alcohol having a valence of 3 or more (having a carbon number of 3 to 50 or more and Mw of 76 to 10,000)
Acrylate (b4) or the like is used.

Examples of the (meth) acrylate (b1) of a dihydric phenol include 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 (eg, tetrachlorobisphenol A di (meth) acrylate), catechin di (meth) acrylate, resorcinol di (meth)
Acrylate, hydroquinone di (meth) acrylate, 1,5-dihydroxynaphthalene di (meth) acrylate, dihydroxybiphenyl di (meth) acrylate, octachloro-4,4′-dihydroxybiphenyl di (meth) acrylate, tetramethylbiphenyl di (meth) ) Acrylate and 9,9′-bis (4-hydroxyphenyl) furo orange (meth) acrylate.

Examples of poly (meth) acrylate (b2) of polyhydric phenol include pyrogallol tri (meth) acrylate, dihydroxynaphthylcresol tri (meth) acrylate, tris (hydroxyphenyl) methane tri (meth) acrylate, dinaphthyltriol. Tri (meth) acrylate, tetrakis (4-hydroxyphenyl) ethanetetra (meth) acrylate, trismethyl-tert-butyl-butylhydroxymethane tri (meth) acrylate, 4,4′-oxybis (1,4-phenylethyl) tetracresol Examples thereof include (meth) acrylate, 4,4′-oxybis (1,4-phenylethyl) phenyl (meth) acrylate and bis (dihydroxynaphthalene) tetra (meth) acrylate.

Examples of the (meth) acrylate (b3) of a dihydric alcohol include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate and 1,6-hexanediol. Di (meth) acrylate, polyethylene glycol (Mw 150 to 4,0
00) di (meth) acrylate, polypropylene glycol (Mw 180 to 5,000) di (meth) acrylate, polytetramethylene glycol (Mw 200 to 5,
000) di (meth) acrylate, neopentyl glycol di (meth) acrylate, and bisphenol A
EO and / or PO (1 to 20 mol) adduct of di (meth) acrylate and the like.

Examples of the poly (meth) acrylate (b4) of a polyhydric alcohol having 3 to 7 valences or more include trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate and pentaerythritol tetra (meth). ) Acrylate, sorbitol hexa (meth) acrylate and poly (degree of polymerization 2-5)
Examples thereof include glycerin poly (meth) acrylate.

Monomer (c) having only vinyloxy group
Is a hydrocarbon compound having 4 to 20 carbon atoms, for example,
Examples thereof include divinyl ether, divinyloxybenzene, divinyloxytoluene, divinyloxyxylene, trivinyloxybenzene and 1,2-divinyloxyethane, and in addition to these, divinyl sulfide, divinyl sulfone, divinyl sulfoxide and the like can also be used. ..

Monomer (d) having only allyloxy groups
As the diallyl ether (d1) of dihydric phenol (having 6 to 30 carbon atoms), polyhydric phenol (having 6 to 50 carbon atoms)
Or more, trivalent to hexavalent or higher Mw 110 to 5,000 or more} polyallyl ether (d2), dihydric alcohol (alkylene glycol having 2 to 6 or more carbon atoms or 6 to 24 carbon atoms or Diallyl ether (d3) of higher dihydric phenol AO1 to 90 mol adduct), polyhydric alcohol having 3 to 7 valences or higher (having 3 to 50 carbon atoms or more, Mw 76 to 10,
000) polyallyl ether (d4), a polyallyl ester (d5) of a divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms), and a divalent to hexavalent thereof. The polyallyl ester (d6) of the above aliphatic or alicyclic polycarboxylic acids (having 6 to 20 or more carbon atoms) can be used.

Diallyl ether of dihydric phenol (d
Examples of 1) include 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-hydroxy) Phenyl) furo orange allyl ether and the like.

Polyallyl ether of polyhydric phenol (d
Examples of 2) include pyrogallol triallyl ether, dihydroxynaphthylcresol triallyl ether, tris (hydroxyphenyl) methane triallyl ether, dinaphthyltriol triallyl ether, tetrakis (4-hydroxyphenyl) ethanetetraallyl ether, trismethyl- tert-butyl-butylhydroxymethane triallyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol allyl ether, 4,4'-oxybis (1,4-phenylethyl) phenyl allyl ether and bis ( Dihydroxynaphthalene) tetraallyl ether and the like.

Diallyl ether of dihydric alcohol (d
Examples of 3) include ethylene glycol diallyl ether, propylene glycol diallyl ether, tetramethylene glycol diallyl ether, 1,6-hexanediol diallyl ether, polyethylene glycol (Mw 150 to 4,000) diallyl ether, polypropylene glycol (Mw 180 to 5). , 000) diallyl ether, polytetramethylene glycol (Mw2
00-5,000) diallyl ether, neopentyl glycol diallyl ether, and diallyl ether of EO and / or PO (1 to 20 mol) adduct of bisphenol A.

Examples of the polyallyl ether (d4) of a polyhydric alcohol having 3 to 7 valences or more include trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, sorbitol hexaallyl ether and Examples thereof include poly (polymerization degree 2 to 5) glycerin polyallyl ether and the like.

Examples of the polyallyl ester (d5) of aromatic polycarboxylic acid include diallyl phthalate, diallyl isophthalate, diallyl terephthalate and triallyl trimellitate. Examples of the polyallyl ester (d6) of the aliphatic or alicyclic polycarboxylic acid include, for example, the aromatic nucleus water additive of (d5), diaryl acid diallyl ester, diallyl oxalate, diallyl malate, diallyl succinate and diallyl. Examples thereof include glutarate, diallyl adipate, diallyl pimelate, and tricarballylic acid triallyl ester.

As the monomer (e) having only a propenyloxy group, a dipropenyl ether (e1) of a divalent phenol (having 6 to 30 carbon atoms), a polyhydric phenol (having 6 to 50 or more carbon atoms, Mw 110-5,000 trivalent to hexavalent or higher} polypropenyl ether (e2), dihydric alcohol (alkylene glycol having 2 to 6 or more carbon atoms or divalent having 6 to 24 or more carbon atoms). Dipropenyl ether (e3) of phenol AO1 to 90 mol adduct), polypropenyl ether of trihydric to heptahydric or higher polyhydric alcohol (having 3 to 50 carbon atoms or more and Mw of 76 to 10,000). (E4) Polypropenyl ester (e5) of divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms), Poly propenyl ester (e6), such as beauty divalent to hexavalent or more aliphatic or cycloaliphatic polycarboxylic acids (number 6 to 20 or more carbon atoms) can be used.

Examples of the dipropenyl ether (e1) of dihydric phenol include bisphenol F dipropenyl ether, bisphenol A dipropenyl ether, bisphenol B dipropenyl ether, bisphenol AD dipropenyl ether, bisphenol S dipropenyl ether and halogenated compounds. Bisphenol A dipropenyl ether, tetrachlorobisphenol A dipropenyl ether, catechin dipropenyl ether, resorcinol dipropenyl ether, hydroquinone dipropenyl ether, 1,5-dihydroxynaphthalene dipropenyl ether, dihydroxybiphenyl dipropenyl ether, octachloro-4,4 '-Dihydroxybiphenyl dipropenyl ether, tetramethyl biphenyl dipropenyl ether Tell and 9,9'-bis (4-
Hydroxyphenyl) furo orange propenyl ether and the like can be mentioned.

Examples of the polypropenyl ether (e2) of polyhydric phenol include pyrogallol tripropenyl ether, dihydroxynaphthylcresol tripropenyl ether, tris (hydroxyphenyl) methane tripropenyl ether, dinaphthyltriol tripropenyl ether, and tetrakis (4). -Hydroxyphenyl) ethane tetrapropenyl ether, trismethyl-
tert-butyl-butylhydroxymethane tripropenyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol propenyl ether, 4,
4′-oxybis (1,4-phenylethyl) phenylpropenyl ether, bis (dihydroxynaphthalene) tetrapropenyl ether and the like can be mentioned.

Examples of the dipropenyl ether (e3) of a dihydric alcohol include 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) dipropenyl ether, polytetramethylene glycol (Mw 200-5,000) dipropenyl ether, neopentyl glycol dipropenyl ether, and EO and / or PO (1-20 mol) adduct of bisphenol A Examples include dipropenyl ether and the like.

Examples of the polypropenyl ether (e4) of a polyhydric alcohol having 3 to 7 valences or more include:
Examples thereof include trimethylolpropane tripropenyl ether, glycerin tripropenyl ether, pentaerythritol tetrapropenyl ether, sorbitol hexapropenyl ether, and poly (polymerization degree 2-5) glycerin polypropenyl ether.

Examples of the polypropenyl ester of aromatic polycarboxylic acid (e5) include phthalic acid dipropenyl ester, isophthalic acid dipropenyl ester, terephthalic acid dipropenyl ester and trimellitic acid tripropenyl ester. Examples of the polypropenyl ester (e6) of an aliphatic or alicyclic polycarboxylic acid include the aromatic nucleus water additive of (d5), dipropenyl ester of dimer acid, dipropenyl oxalate, dipropenyl malate and dipropenyl ester. Examples include succinate, dipropenyl glutarate, dipropenyl adipate, dipropenyl pimelate and tricarballylic acid tripropenyl ester.

Examples of the monomer (f) having an epoxy group and a (meth) acryloyl group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. Examples of the monomer (g) having an epoxy group and a vinyl group include vinylcyclohexene monooxide, glycidyl vinyl ether and butadiene monooxide.

As the monomer (h) having a (meth) acryloyl group and a vinyloxy group as a crosslinkable functional group,
For example, vinyl (meth) acrylate, vinyloxyethyl (meth) acrylate, vinyloxypropyl (meth) acrylate, 3-vinyloxy-2-hydroxypropyl (meth) acrylate, 3-vinyloxy-2
-Chloropropyl (meth) acrylate, vinyloxybutyl (meth) acrylate, vinyloxyhexyl (meth) acrylate and the like can be mentioned. Further, (h) also includes vinyl ether, alkenyl (meth) acrylate and the like.

Examples of vinyl ethers include propenyloxyethyl vinyl ether, propenyloxypropyl vinyl ether, vinyloxyethyl vinyl ether, vinyloxypropyl vinyl ether, allyloxyethyl vinyl ether, allyloxypropyl vinyl ether, hexenyloxyethyl vinyl ether and decenyloxypropyl vinyl ether. Etc. Examples of the alkenyl (meth) acrylate include butenyl (meth) acrylate, butenyloxyethyl (meth) acrylate, octenyloxypropyl (meth) acrylate, 3-butenyloxy-2-hydroxypropyl (meth) acrylate, and 3-hexenyl. Examples thereof include oxy-2-chloropropyl (meth) acrylate, octenyloxy (meth) acrylate and decenyloxyhexyl (meth) acrylate.

As the monomer (i) having a (meth) acryloyl group and an allyl group, for example, allyl (meth) acrylate, allyloxyethyl (meth) acrylate, allyloxypropyl (meth) acrylate, 3-
Examples thereof include allyloxy-2-hydroxypropyl (meth) acrylate, 3-allyloxy-2-chloropropyl (meth) acrylate, allyloxybutyl (meth) acrylate and allyloxyhexyl (meth) acrylate.

Examples of the monomer (j) having a (meth) acryloyl group and a propenyloxy group include propenyl (meth) acrylate, propenyloxyethyl (meth) acrylate, propenyloxypropyl (meth) acrylate and 3- Examples thereof include propenyloxy-2-hydroxypropyl (meth) acrylate, 3-propenyloxy-2-chloropropyl (meth) acrylate, propenyloxybutyl (meth) acrylate, and propenyloxyhexyl (meth) acrylate.

Examples of the monomer (k) having a primary amino group include aliphatic polyamine (having 2 to 18 carbon atoms and 2 to 7 amino groups) (k1), alicyclic polyamine (having 4 to 1 carbon atoms).
5, amino group number 2 to 3) (k2), polyamide polyamine (k3), polyether polyamine (k4) and the like can be used.

Examples of the aliphatic polyamine (k1) include alkylenediamine having 2 to 6 carbon atoms, polyalkylene (having 2 to 6 carbon atoms) polyamine, alkyl (having 1 to 4 carbon atoms) or hydroxyalkyl (having carbon number) of the above polyamine. 2 to
4) Substitutes, alicyclic or heterocyclic-containing aliphatic polyamines (C5-18), aromatic ring-containing aliphatic polyamines (C8-15) and the like are 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 (1 to 3 carbon atoms) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine and methyliminobispropylamine. Examples of the alicyclic or heterocyclic ring-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.

Examples of the alicyclic polyamine (k2) include 1,3-diaminocyclohexane, isophoronediamine, mensendiamine and 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline). As the polyamide polyamine (k3), for example, Mw80 to 2 obtained by condensation of dicarboxylic acid (dimer acid etc.) and excess polyamine (more than 2 mol per mol of acid) (the above alkylenediamine, polyalkylenepolyamine etc.) 1,000 polyamide polyamines and the like are used. Examples of commercially available polyamide polyamine (trade name) include, for example, polymide (Sanyo Kasei),
Examples include tomide (Fuji Kasei), Versamide (Henkel Hakusui), Larkermide (Dainippon Ink), and Sunmide (Sanwa Kagaku).

As the polyether polyamine (k4), for example, polyether polyol (2 to 6 valent, Mw
90 to 2,000) [e.g., a hydride of a cyanoethylated compound such as polyalkylene (C2 to C8) glycol].

As the monomer (m) having a secondary amino group, the primary amino group (-NH ₂ group) of (k) is -NH.
Those substituted with —R (R is an alkyl group having 1 to 4 carbon atoms) can be used, and examples thereof include di (methylamino) ethylene, di (ethylamino) hexane and 1,3-di (methylamino) cyclohexane. Can be mentioned.

Monomer (n) having only carboxyl group
Are divalent to hexavalent or higher aromatic polycarboxylic acids (having 6 to 20 or more carbon atoms) (n1) and divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acids ( (C2-6 or more) (n2) etc. can be used. As the aromatic polycarboxylic acid (n1), for example,
Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, hymic acid and trimellitic acid. Examples of the aliphatic or alicyclic polycarboxylic acid (n2) include (n1) aromatic nucleus water additive, dimer acid, oxalic acid, maleic acid,
Examples thereof include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, tricarballylic acid and dodecenylsuccinic acid.

As the monomer (o) having only a hydroxyl group, a dihydric phenol (o1) having 6 to 30 carbon atoms, a polyhydric phenol (having 6 to 50 carbon atoms or more, Mw 110
Up to 5,000 trivalent to hexavalent or higher) (o2), 2
Polyhydric alcohols (alkylene glycols having 2 to 6 or more carbon atoms or AO 1 to 90 mol adducts of dihydric phenols having 6 to 24 or more carbon atoms) (o3) and polyhydric compounds having 3 to 7 valences or more Alcohol (carbon number 3
~ 50 or more, Mw 76-10,000) (o
4) etc. can be used.

Examples of the dihydric phenol (o1) include bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A (eg, tetrachlorobisphenol A, etc.), catechin, resorcinol, hydroquinone, 1 , 5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4'-dihydroxybiphenyl, tetramethylbiphenyl and 9,9'-bis (4-hydroxyphenyl) fluorene.

As the polyphenol (o2), for example, 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, bis (dihydroxynaphthalene) and the like can be mentioned.

Examples of the dihydric alcohol (o3) include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol (Mw 150 to 4,000), polypropylene glycol (Mw 180 to 5,000). ,
Polytetramethylene glycol (Mw200-5,00
0), neopentyl glycol, and EO and / or PO (1 to 20 mol) adducts of bisphenol A.

Examples of the polyhydric alcohol (o4) include trimethylolpropane, ditrimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, and poly (polymerization degree 2 to 5) glycerin.

As the monomer (p) having only an isocyanate group, an aromatic polyisocyanate (p1) having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same applies hereinafter) and 2 to 2 carbon atoms are included. 18 aliphatic polyisocyanates (p2), alicyclic polyisocyanates having 4 to 15 carbon atoms (p3), araliphatic polyisocyanates having 8 to 15 carbon atoms (p4), and modified products of the above polyisocyanates (urethane groups, Carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group-containing modified product) (p5) and the like can be used.

Examples of the aromatic polyisocyanate (p1) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, and 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 its 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] phosgene: polyaryl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate and the like can be mentioned.

Examples of the aliphatic polyisocyanate (p2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,
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- Diisocyanato hexanoate etc. are mentioned.

Examples of the alicyclic polyisocyanate (p3) include isophorone diisocyanate (IPD).
I), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-di Carboxylate and 2,5-
Alternatively, 2,6-norbornane diisocyanate and the like can be mentioned. Examples of the araliphatic polyisocyanate (p4) include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

Modified product of the above polyisocyanate (p5)
For example, modified MDI (urethane modified MDI,
Carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, and other modified polyisocyanates, and mixtures of two or more thereof [eg, modified MD
I in combination with urethane-modified TDI (isocyanate-containing prepolymer)]. The urethane-modified polyisocyanate [excess polyisocyanate (TDI, MD
I etc.) and a free isocyanate (reactive functional group) -containing resin (prepolymer) obtained by reacting a polyol]
As the polyol used for the production of
Zero polyols can be used. For example, glycols (ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, etc.), triols (trimethylolpropane, glycerin, etc.), high-functional polyols (pentaerythritol, sorbitol, etc.) and their AOs (EO and / or PO 1 to 20 mol). ) Examples include adducts.

Examples of the monomer (q) having a nitrile group and a vinyloxy group include cyanobutene and cyanovinyloxybenzene. Examples of the monomer (r) having a nitrile group and a (meth) acryloyl group include (meth) acrylonitrile and cyanoethyl (meth) acrylate.

Examples of the monomer (s) having a hydroxyl group and a (meth) acryloyl group include polyalkylene (having 2 to 2 carbon atoms).
8) Mono (meth) acrylate (Mw300 to 3,000) having a glycol chain can be used, and examples thereof include polyethylene glycol (Mw300) mono (meth) acrylate, polypropylene glycol (Mw500) mono (meth) acrylate, and ethylene glycol mono. (Meth) acrylate, propylene glycol mono (meth)
Acrylate, glycerin mono (meth) acrylate,
Examples include trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and polyglycerin (degree of polymerization same as above) mono (meth) acrylate.

Examples of the monomer (t) having a (meth) acryloyl group and an isocyanate group include 2- (meth) acryloylethyl isocyanate and (meth) acryloylpropyl isocyanate.
Examples of the monomer (u) having a (meth) acryloyl group and a carboxyl group include (meth) acrylic acid, maleic acid and maleic anhydride. As the monomer (v) having an allylamino group, at least a part of the primary amino group (—NH ₂ group) of (k) is —NH—R.
(R is an allyl group) can be used, for example, di (allylamino) ethylene, di (allylamino)
Propylene, 4,7,10-triazatrideca-1,1
2-diene, 4,7,10,13-tetraazahexadeca-1,15-diene, di (allylamino) hexane,
Examples thereof include N, N-diallylxylylenediamine, N, N-di (allylamino) cyclohexane and N, N-diallylisophoronediamine.

Monomer (w) having propenylamino group
As may be used those replaced with at least a portion -NH-R a (k) of the primary amino group (-NH ₂ group) (R is propenyl), for example, di (propenylamino) ethylene, Di (propenylamino) propylene,
4,7,10-triazatrideca-2,11-diene,
4,7,10,13-tetraazahexadeca-2,14
-Diene, di (propenylamino) hexane, N, N-
Examples include dipropenyl xylylenediamine, N, N-di (propenylamino) cyclohexane, N, N-dipropenylisophoronediamine and the like.

Among these monomers having a crosslinkable functional group, (a)-(f), (n), (o), (q)-(s)
And (u) are preferable, and (a)-is more preferable.
(F), (n), (o), (s) and (u), particularly preferably (a), (b) and (f), even more preferably (a), (b) and (f). , And most preferably (a) and (f). These monomers are each alone,
Two or more kinds can be used in combination and / or with other copolymerizable monomers.

Other copolymerizable monomers include the following (a)
a) to (ww) can be used. Examples of the monomer (aa) copolymerizable with the monomer (a) having only an epoxy group include hydrocarbon oxides (aa1) having 4 to 24 carbon atoms and monoglycidyl ethers of hydrocarbons (3 to 21 carbon atoms). (Aa2), an aliphatic carboxylic acid having 1 to 18 carbon atoms (aa
3), an aromatic carboxylic acid having 7 to 18 carbon atoms (aa4),
Alcohol having 1 to 18 carbon atoms (aa5), 6 to 1 carbon atoms
Phenol having 8 carbons (aa6), aliphatic amine having 1-18 carbon atoms (aa7), aromatic amine having 6-18 carbon atoms (aa8) and the like are used.

Examples of the hydrocarbon oxide (aa1) include EO, PO, butene oxide, α-olefin oxide having 5 to 18 carbon atoms (eg pentane oxide,
Decene oxide and octadecene oxide) and styrene oxide. Hydrocarbons (4 to 2 carbon atoms
Examples of the monoglycidyl ether (aa2) of 1) include methyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and octadecyl glycidyl ether.

Examples of the aliphatic carboxylic acid (aa3) include acetic acid, butanoic acid, 2-ethylhexanoic acid, undecanoic acid and octadecanoic acid. Examples of the aromatic carboxylic acid (aa4) include benzoic acid, p-methylbenzoic acid and naphthalenecarboxylic acid. Examples of the alcohol (aa5) include methanol, isopropanol, butanol, 2-ethylhexanol, tetradecyl alcohol, octadecyl alcohol and benzyl alcohol. Examples of the phenol (aa6) include phenol, o-,
Examples thereof include m- or p-cresol and p-ethylphenol.

Examples of the aliphatic amine (aa7) include methylamine, dimethylamine, methylbutylamine, undecylamine, decalylamine and octadecylamine. Examples of the aromatic amine (aa8) include aniline, p-methylaniline, p-undecylaniline, m-methoxyaniline and naphthylamine.

Examples of the monomer (bb) copolymerizable with the monomer (b) having only a (meth) acryloyl group include an olefin (bb1) having 4 to 20 carbon atoms and a polymerizable non-polymerizable monomer having 8 to 18 carbon atoms. An aromatic compound (bb2) having a saturated double bond,
(Meth) acrylic acid alkyl ester having 5 to 22 carbon atoms (bb3), polymerizable fatty acid ester having 4 to 20 carbon atoms (bb4), and vinyl ether having 4 to 20 carbon atoms (bb)
5) etc. are used. As the olefin (bb1),
For example, 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, 5-ethylidene-2-norbornene and the like can be mentioned.

As the aromatic compound (bb2) having a polymerizable unsaturated double bond, for example, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene,
m-methylstyrene, p-decylstyrene, o-bromostyrene, m-bromostyrene, p-iodostyrene,
p-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,6-dichlorostyrene, 2,6-difluorostyrene, 2,3,4, 5,6
-Pentafluorostyrene, divinylbenzene and the like.

(Meth) acrylic acid alkyl ester (b
Examples of b3) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, undecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl. (Meth) acrylate, 3-methylcyclohexyl (meth) acrylate, cyclopentenyl (meth)
Acrylate and cyclohexenyl (meth) acrylate etc. are mentioned.

Examples of the polymerizable fatty acid ester (bb4) include vinyl acetate, vinyl propanoate, vinyl octadecanoate, allyl acetate, allyl butanoate, propenyl acetate and propenyl hexanoate. Examples of the vinyl ether (bb5) include ethyl vinyl ether, octyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, isobornyl vinyl ether, adamantyl vinyl ether, 3-
Examples thereof include methylcyclohexyl vinyl ether, cyclopentenyl vinyl ether and cyclohexenyl vinyl ether.

Monomer (c) having only vinyloxy group
A monomer (cc) capable of being copolymerized with, a monomer (dd) having only an allyloxy group, and a monomer (e) having only a propenyloxy group. As the monomer (ee), (bb) or the like is used. Examples of the monomer (ff) copolymerizable with the monomer (f) having an epoxy group and a (meth) acryloyl group include:
(Aa) and (bb) are used. As the monomer (gg) copolymerizable with the monomer (g) having an epoxy group and a vinyl group, (aa), (bb) and the like are used. As the monomer (hh) copolymerizable with the monomer (h) having a (meth) acryloyl group and a vinyloxy group, (bb) and the like are used. As the monomer (ii) copolymerizable with the monomer (i) having a (meth) acryloyl group and an allyloxy group, (bb) and the like are used.

A monomer (j) copolymerizable with the monomer (j) having a (meth) acryloyl group and a propenyloxy group.
(bb) or the like is used as j). As the monomer (kk) copolymerizable with the monomer (k) having a primary amino group, (aa1) to (aa4) are used.

The monomer (mm) copolymerizable with the monomer (m) having a secondary amino group includes (aa1) to (a)
a4) or the like is used. Examples of the monomer (nn) copolymerizable with the monomer (n) having only a carboxyl group include (a)
a1), (aa2) and (aa5) to (aa8) are used. As the monomer (oo) copolymerizable with the monomer (o) having only a hydroxyl group, (aa1) to (aa4) are used.

The monomer (pp) copolymerizable with the monomer (p) having only an isocyanate group is (a)
a) or the like is used. As the monomer (qq) copolymerizable with the monomer (q) having a nitrile group and a vinyloxy group, (bb) and the like are used. Nitrile group and (meth)
As the monomer (rr) copolymerizable with the monomer (r) having an acryloyl group, (bb) and the like are used. Monomer (s) having hydroxyl group and (meth) acryloyl group
Examples of the monomer (ss) that can be copolymerized with (aa1) to
(Aa4) and (bb) are used.

A monomer (t) copolymerizable with the monomer (t) having a (meth) acryloyl group and an isocyanate group.
As t), (aa) and (bb) are used.
Examples of the monomer (uu) copolymerizable with the monomer (u) having a (meth) acryloyl group and a carboxyl group include
(Aa1), (aa2), (aa5) to (aa8) and (bb) are used. Examples of the monomer (vv) copolymerizable with the monomer (v) having an allylamino group include (a
a1) to (aa4) and (bb) are used. Examples of the monomer (ww) that can be copolymerized with the monomer (w) having a propenylamino group include (aa1) to (aa4) and (bb).

Among these other copolymerizable monomers, heat resistance,
From the viewpoint of electrical characteristics and resin strength, (aa) and (b
b) is preferable, more preferably (bb), particularly preferably (bb1), (bb2) and (bb3), even more preferably (bb1) and (bb2), most preferably styrene, ethylene, propylene, 6- Methyl-
1,4: 5,8-Dimethano-1,4,4a, 5,6
7,8,8a-octahydronaphthalene, norbornene, dicyclopentadiene and 5-ethylidene-2-norbornene. These other copolymerizable monomers may be used alone or in combination of two or more.

When using another copolymerizable monomer,
The content of the other copolymerizable monomer is not particularly limited, but from the viewpoint of heat resistance and resin strength, it is preferably 20 to 80% by weight, more preferably 35, based on the weight of all the monomers used. ˜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 an ordinary method can be applied. A method in which a group-containing monomer and, if necessary, this and another copolymerization monomer are added dropwise and then aged for an appropriate time can be applied. The reaction temperature is usually 0 to 180 ° C,
It is preferably 60 to 150 ° C. Also, the aging time is
It is usually 0 to 50 hours, preferably 4 to 15 hours. When two or more kinds of monomers are used, the polymerization method may be block type or random type.

A solvent can be used for the polymerization, and the solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the monomer and the resin to be produced. For example, an aromatic solvent (for example, Toluene and xylene etc.), ketone solvent (eg acetone, methyl ethyl ketone and methyl isobutyl ketone etc.), ether solvent (eg diethyl ether, dioxane and tetrahydrofuran etc.) and chlorine solvent (eg chloroform, carbon tetrachloride and dichloromethane etc.) Etc. are used. When a solvent is used, the amount of the solvent used is 20 to 20 based on the total weight of the monomers.
100% by weight is preferable, and more preferably 25-80.
%, Particularly preferably 30 to 65% by weight.

A reaction initiator (C) can be used, and there is no particular limitation on (C), and those used in ordinary reactions can be used. Depending on the type of the crosslinkable functional group, a radical reaction can be used. Initiation catalyst (C1), cationic polymerization initiation catalyst (C2), esterification catalyst (C3), amidation catalyst (C
4), an epoxy ring-opening catalyst (C5), an isocyanate reaction catalyst (C6) and the like are used. As the radical reaction initiation catalyst (C1), a thermal radical reaction initiation catalyst (C11)
Also, a photoradical reaction initiation catalyst (C12) and the like can be used. The thermal radical reaction initiation catalyst (C11) preferably has a 10-hour half-life temperature of 80 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint of storage stability. 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-butylperoxide, 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 can be mentioned.

Examples of the azo compound include 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 benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoylphore. Examples thereof include mate and isopropyl thioxanthone.

Further, a sensitizer can be used together with these photoradical reaction initiation catalysts (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 and 2-nitrofluorene, etc.), aromatic hydrocarbons (eg, anthracene and chrysene, etc.), sulfur compounds (eg, diphenyldisulfide, etc.) And nitrogen compounds (for example, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene, etc.) and the like.

As the cationic polymerization catalyst (C2), there are a thermal cationic polymerization catalyst (C21) and a photo cationic polymerization catalyst (C
22) etc. can be used. Thermal cationic polymerization catalyst (C21)
Examples of usable catalysts include onium salt catalysts (eg, triarylsulfonium salts and diaryl iodonium salts), and examples thereof include San-Aid SI series (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.).

As the photocationic polymerization 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, diallyl iodonium hexafluoroantimonate and the like can be mentioned.

These can be easily obtained from the market, for example, SP-150, SP-170 (trade name of Asahi Denka Co., Ltd.), Irgacure 261 (trade name of Ciba Geigy Co., Ltd.), UVR-6974, UVR-6990 (trade name of Union Carbide Co., Ltd.), CI-2855 (trade name of Nippon Soda Co., Ltd.), CD-1012 (trade name of Sartomer Co., Ltd.) and the like can be mentioned.

Examples of the esterification catalyst (C3) and the amidation catalyst (C4) include acid catalysts (hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroborane, etc.), alkalis (eg, Examples include sodium hydroxide, potassium hydroxide, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU, registered trademark of San-Apro Co., Ltd.), and metal complexes (eg, tetrapropyl titanium). To be

As the epoxy ring-opening catalyst (C5), for example, an imidazole catalyst (2-methylimidazole, 2-methylimidazole
Ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole and 1-cyanoethyl-2-methylimidazole), tertiary amines (benzyl Methylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine, DBU, etc., and onium salt (Sanshin SI series, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) Etc.

As the isocyanate reaction catalyst (C6), an organometallic compound (eg, trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannas octoate, dibutyltin maleate, Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, bismuth octoate, bismuth naphthenate, cobalt naphthenate and phenylmercuric propionate, etc., and tertiary amines (for example, DB
U, N-methylmorpholine, N-ethylmorpholine, methyldibutylamine, triethylamine, and their carbonates and organic acid salts having 1 to 8 carbon atoms (formate salts, etc.)
Etc. These reaction initiators (C) can be used either 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, particularly preferably 0.05 to 1.0% by weight.

Further, in order to leave at least two crosslinkable functional groups in the resin (A), a polymerization inhibitor can be used, and the polymerization inhibitor is not particularly limited and is used in ordinary reactions. Are used, 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 0.1 to 5.0% by weight, more preferably 0.1 to 2.0% by weight, based on the total weight of the monomers. , Particularly preferably 0.5 to 1.0.

The method for reacting a resin having a crosslinkable functional group with a monomer having a crosslinkable functional group to convert the crosslinkable functional group is not particularly limited, and a usual method can be applied.
For example, a method of producing a resin having a reactive functional group using a monomer (qw) and reacting the monomer (kp) for conversion, or a crosslinkable functional group produced by the method In a resin having at least two, a monomer (a-j) or a monomer (q
The method of reacting -w) can be applied. The reaction temperature, aging time, solvent, reaction initiator (C) and polymerization inhibitor are the same as in the method. 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 subjected to an esterification reaction of (meth) acrylic acid, Hydroxyl groups can be converted to (meth) acryloyl groups.

Further, the monomer (a-j, v, w) having a crosslinkable functional group can be introduced into the resin having an unsaturated double bond by a graft reaction. For example, 20-40 mol parts of propylene, 60-80 mol parts of 5-ethylidene-2-norbornene, a solvent and a transition metal compound (for example, a titanium compound) / aluminum compound-based catalyst are used for addition copolymerization and copolymerization. After the polymer is obtained, the unsaturated double bond is converted into an epoxy group by grafting glycidyl (meth) acrylate, vinylcyclohexene monooxide, 3,4-epoxycyclohexylmethyl (meth) acrylate or the like on this polymer. be able to.

In addition to the curable resin (A), the curable film of the present invention is selected from the group consisting of epoxy groups, (meth) acryloyl groups and alkenyloxy groups from the viewpoint of thermal shock resistance and dielectric properties. It is preferable to contain the low molecular weight compound (B) having at least two crosslinkable functional groups in the molecule. Low molecular weight compound (B)
The Mw of is preferably 170 to 3,000, more preferably 200 to 1,500, and particularly preferably 500 to
1,200, most preferably 600 to 1,000. It is preferable that Mw is in this range from the viewpoint of thermal shock resistance and handleability. The crosslinking functional group of (B) includes (A)
And the preferred ones are also the same. The number of crosslinkable functional groups of (B) is at least 2, preferably 2 to 5,000, and more preferably 3 to 3,000.
The number is particularly preferably 5 to 1,000, more preferably 7 to 500, and most preferably 10 to 200. As (B), for example, monomer (aj), monomer (qw), (aa1), (aa2), (bb3).
And (bb4) and the like can be used. In addition to these, the following monoepoxide (x), polyepoxide (y), and curing agent (z) can be used.

The monoepoxide (x) is a glycidyl ester (x of a monocarboxylic acid (having 3 to 30 carbon atoms)).
1) and the cyclohexene monooxide group-containing compound (x2) are used. Examples of the glycidyl ester of monocarboxylic acid (x1) include glycidyl (meth) acrylate, epihalohydrin (eg, epichlorohydrin, epibromohydrin, etc.), and hydroxyl group-containing oxide (eg, glycidol, etc.).

Examples of the cyclohexene monooxide group-containing compound (x2) include, for example, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxymethylcyclohexanecarboxylate and 3,4-epoxy-6-methylcyclohexylmethyl-3. ', 4'-epoxy-
6'-methylcyclohexanecarboxylate and the like can be mentioned.

Examples of the polyepoxide (y) include vinylcyclohexene dioxide and bis (3,4-epoxy-6).
-Methylcyclohexylmethyl) adipate, phenol or cresol novolac resin (Mw 400-
3,000) glycidyl ether, limonenephenol novolac resin (Mw 400 to 3,000) glycidyl ether, polyphenol (Mw 400 to 3,000) obtained by condensation reaction of phenol and glyoxal, glutaraldehyde or formaldehyde.
0) polyglycidyl ether, polyglycidyl ether of polyphenol having Mw of 400 to 3,000 obtained by condensation reaction of resorcin and acetone, (co) polymer of glycidyl (meth) acrylate (polymerization degree is, for example, 2 to 10), epoxy Examples include epoxidized polybutadiene (Mw 170 to 3000) having an equivalent weight of 130 to 1,000, epoxidized soybean oil (Mw 170 to 3,000), and the like.

As the curing agent (z), a monomer (n) having only a carboxyl group, an aliphatic carboxylic acid (aa3)
Alternatively, an acid anhydride of an aromatic carboxylic acid (aa4) and the like can be mentioned. Among these low molecular weight compounds (B), (a),
(B), (c), (d), (e), (m), (n),
(F), (g), (h), (r), (s), (i),
(J), (m), (aa3) and (aa4) are preferable, and more preferably (a), (b), (n),
(F), (g) and (s), particularly preferably (a),
(B), (n) and (f). When using a monoepoxide (x), a polyepoxide (y), a curing agent (z), etc., the amount of these is not particularly limited, but in terms of heat resistance and resin strength, the amount of all the monomers used is Based on this, 20 to 80% by weight is preferable, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight. The weight ratio (A: B) of (A) and (B) is from 10 to 10.
95: 5 to 90 is preferable, and 20 to 9 is more preferable.
0:10 to 80, particularly preferably 30 to 80:20 to 7
It is 0.

The curable film 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 phenol-based antioxidant, a phosphorus-based antioxidant, a flame retardant, a phenol-based thermal deterioration inhibitor, a benzophenone-based ultraviolet stabilizer and an antistatic agent. When (D) is used, the content of (D) is (A)
The total weight of (B) and (B) is the weight of (A) only when (B) is not used. The same applies below. }On the basis of,
0.001 to 3.0% by weight is preferable, 0.01 to 2.0% by weight is more preferable, and 0.05 to 2.0% is particularly preferable.
It is 1.0% by weight.

As the other resin (E), those used for ordinary insulators can be used. Examples thereof include ABS resin, polystyrene, polycarbonate, polyamide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, Mention may be made of polyimides, polysulfones, polyether sulfones and polyarylates. Mw of other resins is
It is preferably 10,000 to 500,000, more preferably 20,000 to 100,000, and particularly preferably 40,000 to 60,000. When (E) is used, the content of (E) is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, particularly preferably 1 to 10% by weight based on the total weight of (A) and (B). Preferably 2 to 8% by weight,
Most preferably, it is 3 to 5% 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. Elongation of rubber (JIS K6301 (1995) 3. Tensile test)
Is preferably 500 to 2,000%, more preferably 700 to 1,500%, particularly preferably 800 to 1,
It is 000%. When (F) is used, the content of (F) is 1 to 40 based on the total weight of (A) and (B).
Wt% is preferred, more preferably 5-30 wt%,
It is particularly preferably 8 to 25% by weight.

As the filler (G), those used for ordinary insulators can be used, and examples thereof include silica, alumina, calcium carbonate, barium sulfate, titanium oxide and talc. When (G) is used, the content of (G) is 1 to 1 based on the total weight of (A) and (B).
It is preferably 50% by weight, more preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight.

The thickness of the curable film of the present invention can be appropriately determined according to the purpose of use, but is preferably 1 to 100 μm, more preferably 5 to 70 μm, particularly preferably 15 to 60 μm, and most preferably 20 to It is 50 μm.

The curable film of the present invention is prepared by uniformly mixing (A) with (B) to (G) and / or a solvent, if necessary, by a usual method, and then using a usual molding method such as curtain. It can be produced by a method such as coating on a support or substrate using a coater, knife coater, spray gun, roll coater, spin coater, dispenser, bar coater, screen printing machine, etc., or by dipping or injection molding. it can. Among these molding apparatuses, a curtain coater, a knife coater, a method using a spray gun or a roll coater is preferable, and a method using a curtain coater or a knife coater is more preferable,
A method using a knife coater is particularly preferable.

When forming the film, the viscosity can be adjusted by using a solvent or the like, if necessary. As a solvent,
There is no particular limitation as long as the curable resin composition containing (A) can be dissolved, emulsified or dispersed, but for example, a solvent that can be used in the production of the curable resin (A) is used. When a solvent is used, the solvent may be left as it is without being removed during the polymerization of (A). The same or different solvent as used in may be added,
You may mix (B) and a solvent and may mix it with (A). When a solvent is used, the content of the solvent is not particularly limited as long as it can be adjusted to a viscosity that facilitates film formation, but it is 5-9 based on the total weight of (A) (weight not including solvent) and (B).
It is preferably 0% by weight, more preferably 10 to 80% by weight, particularly preferably 30 to 70% by weight.

As the support, those usually used for film formation can be used, and for example, PET (polyethylene terephthalate), polyethylene, polypropylene and modified products thereof can be used. As the base material, various printed wiring boards having conductive (copper, gold, silver, aluminum, etc.) circuits can be used. For example, a resin for manufacturing a substrate (epoxy resin, bismaleimide triazine resin (B
T) and polyamide resin, etc.) impregnated into a non-woven fabric (glass fiber non-woven fabric, aramid fiber non-woven fabric, etc.), etc., or cured by adding glass fiber to the resin for manufacturing the substrate, with a copper circuit bonded (For example, a BT substrate, a glass epoxy substrate, a paper phenol substrate, a paper epoxy substrate, etc.) can be used.

When a support is used, the film on the support can be transferred to a substrate or the like for use, and when a substrate or the like is used, it can be cured as it is. After applying the composition, it is preferable to heat the composition for the purpose of drying the solvent and the like. The heating conditions include, for example, temperature: 10 to 150 ° C.
(Preferably 20 to 120 ° C.), time: 1 to 60 minutes (preferably 2 to 40 minutes). The curable film of the present invention is easily softened by heating (such as hot pressing), and has good penetration into a minute portion (uneven portion, etc.) such as a substrate,
Excellent workability.

(2) Regarding the second and third aspects of the present invention, the difference in the solubility parameter (hereinafter abbreviated as SP) value between the curable resin composition (X) and the thermoplastic resin (Y) is:
0.5 to 3.0, preferably 0.6 to 2.5,
It is more preferably 0.7 to 2.0, and particularly preferably 0.
It is 8 to 1.8, particularly preferably 0.9 to 1.5, and most preferably 1.0 to 1.2. When the solubility parameter is within this range, it is easy to obtain an insulator having excellent thermal shock resistance. The SP value of the curable resin composition (X) is 5.0.
To 12.0 are preferable, and 6.0 to 1 is more preferable.
1.5, particularly preferably 7.0-11.0, even more preferably 8.0-10.5, most preferably 9.0.
It is 10.0.

The SP value is expressed by the following equation.

## EQU1 ## SP value (δ) = (ΔH / V) ^1/2 However, in the formula, ΔH represents the heat of vaporization (cal) and V represents the molar volume (cm ³ ). Further, ΔH and V are “PO
LYMER ENGINEERING ANDFEBR
UARY, 1974, Vol. 14, No. 2, ROB
ERT F. FEDORS. (Pages 151 to 153) ”, the total (V) of the molar evaporation heat (Δe _i ) of the atomic groups (ΔH _i ) and the molar volume (Δv _i ) can be used. Mw of (Y) is 3,000 to 1,000,000.
, Preferably 5,000 to 800,000, more preferably 10,000 to 600,000, particularly preferably 50,000 to 400,000, most preferably 60,000 to 100,000.

The dielectric constant of (X) after curing is preferably 3.5 or less, more preferably 2 to 3.5, particularly preferably 2.2 to 3.4, and particularly preferably 2.4 to 3. ．
3, most preferably 2.7-3.2. If the dielectric constant after curing is in this range, the reliability will be further improved when used as an insulator, and when applied to integrated circuits of electronic parts, signal delay is less likely to occur and circuit performance can be easily improved. Tends to become. The curing conditions and the method of measuring the dielectric constant are the same as for the curable resin (A). From the viewpoint of thermal shock resistance and electric insulation, the boiling water absorption after curing of (X) is
It is preferably 3% or less, more preferably 3.00 to 0.
001, particularly preferably 2.5 to 0.005, most preferably 2 to 0.001%. The curing conditions are the same as the case of the dielectric constant after curing. In addition, the boiling water absorption rate is JIS
It is measured in accordance with the K7209 (2000) 6.3B method.

The dielectric constant after curing of the curable resin material is 2.
4 to 3.2 is preferable, and 2.5 to 3.
2, particularly preferably 2.5 to 3.0, even more preferably 2.6 to 2.9, and most preferably 2.6 to 2.8. If the dielectric constant after curing is in this range, the reliability will be further improved when used as an insulator, and when applied to integrated circuits of electronic parts, signal delay is less likely to occur and circuit performance can be easily improved. Tends to become. The curing conditions and the method of measuring the dielectric constant are the same as for the curable resin (A).

As the curable resin composition (X), resins which can be cured by heat or the like can be widely used, but the following three are preferable from the viewpoint of thermal shock resistance and the like. (1) The curable resin composition (X containing the curable resin (A) and the low molecular weight compound (B) described above.
1). (2) α-olefin (Ha) and cyclic olefin (H
It is a copolymer having b) as a constitutional unit and having a carbon-carbon double bond (H) and a cross-linking agent (I) having a carbon-carbon double bond as essential components. Curable resin composition (X2).

(3) A monomer (f) having an epoxy group and a (meth) acryloyl group, a monomer (g) having an epoxy group and a vinyl group, and a (meth) acryloyl group and a vinyloxy group. Monomer (h), monomer (i) having (meth) acryloyl group and allyloxy group, monomer (j) having (meth) acryloyl group and propenyloxy group, monomer having allylamino group (V) and at least one monomer (fgw) selected from the group consisting of a monomer (w) having a propenylamino group, and a monomer (345) represented by formula (3) to (5). ), And optionally, an aromatic compound (bb2) having a polymerizable unsaturated double bond having 8 to 18 carbon atoms, a (meth) acrylic acid alkyl ester having 5 to 22 carbon atoms (bb3), and 4 to 20 carbon atoms.
Of the vinyl ether (bb5) of at least one monomer (bb235) and a copolymer (J) having a Mw of 2,000 to 1.0.
The curable resin composition (X3) which is 0,000.

[0117]

[Chemical 2] In formula (3), n represents an integer of 1 to 10.

[0118]

[Chemical 3] In the formula (4), R ¹ is a hydrogen atom or a methyl group. m represents an integer of 0 to 6, and n represents an integer of 1 to 10.

[0119]

[Chemical 4] In the formula (5), R ³ is a hydrogen atom or a fluorine atom. R ⁴
Is a hydrogen atom, a chlorine atom or a fluorine atom. R ⁵ is a hydrogen atom, a fluorine atom or a trifluoromethyl group.

First, the curable resin composition (X1) will be further described. (X1) may contain other additives (D), other resins (E), rubbers (F), fillers (G), and the like. When (D) is used, the content of (D) is based on the total weight of (A) and (B),
0.001 to 3.0% by weight is preferable, 0.01 to 2.0% by weight is more preferable, and 0.05 to 2.0% is particularly preferable.
It is 1.0% by weight. When (E) is used, the content of (E) is 0.1% based on the total weight of (A) and (B).
1 to 20% by weight is preferable, and 1 to 10 is more preferable.
% By weight, particularly preferably 2-8% by weight, most preferably 3-5% by weight. When (F) is used, the content of (F) is 1-based on the total weight of (A) and (B).
It is preferably 40% by weight, more preferably 5 to 30% by weight, particularly preferably 8 to 25% by weight. When (G) is used, the content of (G) is preferably from 1 to 50% by weight, more preferably from 5 to 40% by weight, particularly preferably from the total weight of (A) and (B). It is 8 to 30% by weight.

Further, (X1) may contain a solvent. As the solvent, the same solvent as that used in the polymerization of (A) can be used. The solvent may not be removed during the polymerization of (A) and may be left as it is (X1).
After removing the solvent during the polymerization of (X1), the same or different solvent as that used for the polymerization of (A) may be added during the production of (X1), and the solvent may be mixed with (B) and (A). May be mixed with. When using a solvent, the content of the solvent is (A)
Based on the total weight of (weight not including solvent) and (B), it is preferably 5 to 90% by weight, more preferably 10
˜80 wt%, particularly preferably 30-70 wt%.

(X1) can be easily produced by uniformly mixing (A) and (B) with (D) to (G) and / or a solvent, if necessary, 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 optionally mixing (D) to (G) and / or a solvent. (2) A method in which (A) is mixed with (D) to (G) and / or a solvent, if necessary, and then (B) is mixed. (3) (A) and (B) and, if necessary, (D) to (G)
And / or a method of simultaneously mixing the solvents.

As a method of adjusting the dielectric constant of (X1) after curing, there is a method of adjusting it according to the kind of the monomer used as the starting material for (A). For example, ethylene, propylene,
When the content ratio of butadiene, isoprene, (meth) acrylic acid ester having 4 or more carbon atoms and styrene is increased, the dielectric constant tends to be low, and the content of (meth) acrylic acid and acrylonitrile is decreased. The higher the ratio, the higher the dielectric constant. For example, as a composition having a dielectric constant of 2 to 3.5, styrene / glycidyl (meth) acrylate = 10 to 55/90 to 45 parts by mass, bisphenol A diglycidyl ether and 4-methylcyclohexane-1,2-dicarboxylic acid. Stoichiometric ratio (equivalent ratio) mixture with acid anhydride, styrene / glycidyl (meth) acrylate = 10-55 / 90-45 parts by mass, mixture of bisphenol A diglycidyl ether and tris (hydroxyphenyl) methane, styrene / Glycidyl (meth) acrylate = 10-55 / 90-45 parts by mass, a mixture of bisphenol A diglycidyl ether and phenol novolac resin (2-8 nuclide), styrene / glycidyl (meth) acrylate = 10-55 / 90- 45
Mixture of parts by mass and bisphenol A diglycidyl ether, styrene / glycidyl (meth) acrylate = 1
Examples include a mixture of 0 to 55/90 to 45 parts by mass and phenolbonolac polyglycidyl ether.

Next, the curable resin composition (X2) will be described. The carbon number of the α-olefin (Ha) is 2 to 20.
Is more preferable, 3 to 18 is more preferable, and 3 to 12 is particularly preferable. Examples of (Ha) include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-. Octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. The number of carbon-carbon double bonds contained in the cyclic olefin (Hb) is preferably at least 2, more preferably 2 to 5, and particularly preferably 2 to 3.
Examples of (Hb) include a cyclic olefin represented by formula (6) (Hb1), a cyclic olefin represented by formula (7) (Hb2), and a cyclic olefin represented by formula (8) (Hb).
b3) and mixtures thereof are used.

[0125]

[Chemical 5]

In the formula (6), R ^{7 to} R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 (preferably 1 to 2) carbon atoms. As the alkyl group, for example, a methyl group,
Examples thereof include an ethyl group, an isopropyl group, a butyl group and a t-butyl group. From the viewpoint of heat resistance, R ^{7 to} R ¹⁷ are preferably a hydrogen atom, a methyl group and an ethyl group. In addition, n represents an integer of 0 to 5, and mechanical strength (tensile strength,
From the viewpoint of (e.g. tensile elongation), an integer of 0 to 2 is preferable.
Examples of (Hb1) include dicyclopentadiene (when n is 0 in formula (6) and all of R ^{7 to} R ¹⁷ are hydrogen atoms), tricyclopentadiene (formula (6)).
Where n is 1 and all of R ^{7 to} R ¹⁷ are hydrogen atoms) and tetracyclopentadiene (in formula (6), n is 2 and all of R ^{7 to} R ¹⁷ are hydrogen atoms). ) And the like.

[0127]

[Chemical 6]

In the formula (7), R ^{18 to} R ²¹ are R in the formula (6).
^{7 to} R ¹⁷ are the same and the preferable range is also the same.
Examples of (Hb2) include norbornadiene and 3
-Methyl norbornadiene and the like.

[0129]

[Chemical 7]

In the formula (8), R ^{22 to} R ²⁹ are the same as those in the formula (6).
^{7 to} R ¹⁷ are the same and the preferable range is also the same. R
³⁰ and R ³¹ are each independently a hydrogen atom or 1 to 4 carbon atoms.
It represents a (preferably 1 to 2) hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, a butyl group, a t-butyl group, an ethylidene group and a vinylidene group. From the viewpoint of heat resistance, R ³⁰ and R ³¹ are preferably a methyl group, an ethyl group, an ethylidene group and a vinylidene group.

Further, m represents an integer of 0 to 5, and 0 to 2 is preferable from the viewpoint of mechanical strength (tensile strength, tensile elongation, etc.). Examples of (Hb3) include 5-ethylidene-
2-norbornene, 5-vinylidene-2-norbornene and 2-ethylidene-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene etc. are mentioned. Of these (Hb), (Hb
3) is preferable, and more preferably 5-ethylidene-2.
-Norbornene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, particularly preferably 5-ethylidene-2.
-Norbornene.

The weight ratio of α-olefin (Ha) / cyclic olefin (Hb) is preferably 99/1 to 10/90, more preferably 90/10 to 20/80, particularly preferably 30/70 to 60 /. 40. Within this range, the thermal shock resistance of the resin after curing tends to be further improved.

The number of carbon-carbon double bonds contained in the copolymer (H) is preferably 2 to 3,000, more preferably 3 to 1,000, and particularly preferably 5 to 500.
Most preferably, it is 10 to 200. Copolymer (H)
Has a Mw of preferably 3,000 to 1,000,000, and more preferably 50,000 to 400,000.
0, particularly preferably 70,000 to 200,000, most preferably 80,000 to 100,000.
(H) can be easily obtained by copolymerizing (Ha) and (Hb), and the polymerization method is (X1)
The same method as the polymerization method of (A) used for the above is used.

The number of carbon-carbon double bonds contained in the cross-linking agent (I) is preferably 1-6, more preferably 1-5.
The number is particularly preferably 1 to 3. (I)
(Meth) acrylate, unsaturated hydrocarbon, alkenyl ether and the like can be used.

Examples of the (meth) acrylate include (meth)
A monomer (b) having only an acryloyl group, a monomer (f) having an epoxy group and a (meth) acryloyl group,
Monomer (h) having (meth) acryloyl group and vinyloxy group, monomer (i) having (meth) acryloyl group and allyloxy group, monomer having (meth) acryloyl group and propenyloxy group Body (j), a monomer (s) having a hydroxyl group and a (meth) acryloyl group, a monomer (t) having a (meth) acryloyl group and an isocyanate group, a (meth) acryloyl group and a carboxyl group The monomer (u), the (meth) acrylic acid alkyl ester (bb3), the phenoxy group-containing (meth) acrylate and the like are used. Examples of the phenoxy group-containing (meth) acrylate include phenoxyethyl (meth)
Acrylate and phenol EO 2 mol addition product (meth)
Acrylates and (meth) acrylates of 2 moles of phenol EO and 2 moles of PO are included.

As the unsaturated hydrocarbon, an aromatic compound (bb2) having a polymerizable unsaturated double bond, an α-olefin (Ha), an aliphatic non-conjugated polyene having 5 to 10 carbon atoms,
A cyclic olefin having 5 to 10 carbon atoms, an oligomer of a cyclic olefin, and the like are used. Examples of the aliphatic non-conjugated polyene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-
1,5-heptadiene, 7-methyl-1,6-octadiene, 1,3,5-octatriene, 1,4,9-decatriene and the like can be mentioned.

Examples of the cyclic olefin include cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclohexadiene,
Cyclooctadiene, dicyclopentadiene, methyltetrahydroindene, norbornadiene, 2-propenyl-2,5-norbornadiene, norbornene, dicyclopentadiene, dimethanocyclopentadienonaphthalene, cyclopentadiene 3-4mer, 2-norbornene , 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene,
5-ethylidene-2-norbornene, 5-vinylidene-
2-norbornene, 5-phenyl-2-norbornene,
5-phenyl-5-methyl-2-norbornene, 6-ethyl-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 2,3-
Cyclopentadienonaphthalene, 2-ethylidene-1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a-octahydronaphthalene and 1,4: 5,1
0: 6,9-trimethano-1,2,3,4,4a, 5
5a, 6,9,9a, 10,10a-dodecahydro-
2,3-cyclopentadienoanthracene and the like can be mentioned.

Examples of the cyclic olefin oligomer include cyclopentadiene trimer and tetramer, dicyclopentadiene oligomer (2 to 30 mer) and 5-ethylidene-2-norbornene oligomer (2 to 30 mer).
Etc. can be mentioned.

The alkenyl ether has 4 to 4 carbon atoms.
A vinyl ether having 10 carbon atoms, a propenyl ether having 5 to 12 carbon atoms, an allyl ether having 5 to 12 carbon atoms and the like are used. Examples of vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether and butylene glycol divinyl ether.

Examples of propenyl ethers include ethylene glycol dipropenyl ether, diethylene glycol dipropenyl ether, triethylene glycol dipropenyl ether, tetraethylene glycol dipropenyl ether, propylene glycol dipropenyl ether, dipropylene glycol dipropenyl ether and butylene glycol. Examples include dipropenyl ether and the like.

As the allyl ether, for example, ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether,
Examples thereof include propylene glycol diallyl ether, dipropylene glycol diallyl ether and butylene glycol diallyl ether.

From the standpoint of reactivity and dielectric constant, (I) is preferably one containing no polar group in the molecule from the viewpoint of dielectric constant, and from the viewpoint of reactivity and dielectric constant, α-olefin, cyclic olefin, oligomer of cyclic olefin, vinyl ether, propenyl ether. And allyl ethers are preferable, cycloolefins, oligomers of cyclic olefins, vinyl ethers, propenyl ethers and allyl ethers are more preferable, and propenyl ethers are particularly preferable. The boiling point of (I) is preferably at least 250 ° C, more preferably 250 to 350 ° C, and particularly preferably 280 to 300 ° C.
Is.

These cross-linking agents (I) can be used alone or in combination of two or more kinds. Incidentally, since the copolymer (H) itself also has at least one carbon-carbon double bond, a part of this may act as a cross-linking agent, and (H) may react with each other. It is preferable to use the agent (I) from the viewpoint of physical properties such as heat resistance.

The weight ratio of copolymer (H) / crosslinking agent (I) is preferably 99/1 to 20/80, more preferably 90/10 to 40/60, and particularly preferably 85/15.
~ 50/50. Within this range, crosslinking tends to proceed sufficiently and the cured resin tends to have better thermal shock resistance.

(X2) may contain other additives (D), other resins (E), rubbers (F), fillers (G) and the like. When (D) is used, the content of (D) is 0.0 based on the total weight of (H) and (I).
It is preferably from 0.1 to 3.0% by weight, more preferably from 0.
01 to 2.0% by weight, particularly preferably 0.05 to 1.0
% By weight.

When (E) is used, the content of (E) is 1 to 45, based on the total weight of (H) and (I).
Wt% is preferred, more preferably 5-40 wt%,
It is particularly preferably 10 to 30% by weight.

When (F) is used, the content of (F) is from 1 to 40 based on the total weight of (H) and (I).
Wt% is preferred, more preferably 5-30 wt%,
It is particularly preferably 8 to 25% by weight.

When (G) is used, the content of (G) is from 1 to 50 based on the total weight of (H) and (I).
Wt% is preferred, more preferably 5-40 wt%,
It is particularly preferably 8 to 30% by weight.

Further, (X2) may contain a solvent. As the solvent, the same solvent as that used in the polymerization of (A) can be used. When using a solvent,
The content of the solvent is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, particularly preferably 30 to 10% by weight based on the total weight of (H) (weight not including solvent) and (I). It is 70% by weight.

(X2) can be easily produced by uniformly mixing (H) and (I) with (D) to (G) and / or a solvent, if necessary, by a usual method. It can be manufactured by the following methods (1) to (3). (1) A method of blending (H) and (I) and then optionally mixing (D) to (G) and / or a solvent. (2) A method of mixing (H) with (D) to (G) and / or a solvent, if necessary, and then mixing (I). (3) (H) and (I) and, if necessary, (D) to (G)
And / or a method of simultaneously mixing the solvents.

As a method of adjusting the dielectric constant of (X2) after curing, a method of adjusting it depending on the kind of the cross-linking agent (I), for example, increasing the content of α-olefin, cyclic olefin and cyclic olefin oligomer, etc. Then, the dielectric constant tends to decrease, and when the contents of (meth) acrylate and alkenyl ether are increased, the dielectric constant tends to increase. The composition having a dielectric constant of 2 to 3.5 includes, for example, a mixture of a 1-hexene / 5-ethylidene-2-norbornene copolymer and ethylene glycol diallyl ether, 1-hexene / 5-ethylidene-2-norbornene. Mixtures of copolymers with ethylene glycol dimethacrylate, 1-hexene / dicyclopentadiene copolymers with ethylene glycol diallyl ether, 1-hexene / dicyclopentadiene copolymers with ethylene glycol dimethacrylate, etc. Is mentioned.

Next, the curable resin composition (X3) will be described. Monomers (345) represented by formulas (3) to (5)
Will be described in order. In the formula (3), n is 2
The integer of -6 is preferable and the integer of 2-4 is more preferable. Examples of the monomer represented by the formula (3) include:
Examples thereof include perfluoromethyl perfluorovinyl ether, perfluoroethyl perfluorovinyl ether, perfluoropropyl perfluorovinyl ether, perfluoroisobutyl perfluorovinyl ether, perfluorohexyl perfluorovinyl ether and perfluorodecyl perfluorovinyl ether.
Among these, from the viewpoint of heat resistance, perfluoromethyl perfluorovinyl ether, perfluoroethyl perfluorovinyl ether, perfluoropropyl perfluorovinyl ether, perfluoroisobutyl perfluorovinyl ether and perfluorohexyl perfluorovinyl ether are preferable, and more preferable. Perfluoromethyl perfluorovinyl ether, perfluoroethyl perfluorovinyl ether, perfluoropropyl perfluorovinyl ether and perfluoroisobutyl perfluorovinyl ether.

In the formula (4), m is preferably an integer of 0-4, more preferably an integer of 0-2. n
Is preferably an integer of 2 to 6, more preferably 2 to 4
Is an integer. Examples of the monomer represented by the formula (4) include perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, and perfluorohexyl. (Meta)
Acrylate, tridecafluorohexylethyl (meth) acrylate, perfluorodecyl (meth) acrylate, perfluoropropylmethyl (meth) acrylate, perfluoroisobutylethyl (meth) acrylate, perfluoromethylbutyl (meth) acrylate and perfluoroethylhexyl (Meth) acrylate etc. are mentioned. Among these, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, perfluorohexyl (meth) acrylate, perfluoropropylmethyl (meth) acrylate, from the viewpoint of dielectric constant. , Perfluoroisobutylethyl (meth) acrylate, perfluoromethylbutyl (meth)
Acrylate and perfluoroethylhexyl (meth)
Acrylate is preferable, and perfluoroethyl (meth) acrylate is more preferable.

In the formula (5), R ³ and R ⁴ are preferably fluorine atoms, and R ⁵ is preferably a fluorine atom or a trifluoromethyl group. Examples of the monomer represented by the formula (5) include vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, dichlorodifluoroethylene,
Examples thereof include tetrafluoroethylene and hexafluoropropylene. Among these, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene are preferable from the viewpoint of dielectric constant, and tetrafluoroethylene and hexafluoropropylene are more preferable.

In (X3), (f) and (g) are preferable among the monomers (fgw). In (X3),
Among the monomers (bb235), (bb2) is preferable,
From the viewpoint of dielectric constant and heat resistance, more preferably styrene, o-methylstyrene, p-methylstyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,6-difluorostyrene and 2,3,3.
It is 4,5,6-pentafluorostyrene.

(X3) is at least one monomer selected from the monomers (fgw), the monomer (345), and optionally at least one monomer selected from the monomers (bb235). It consists of a copolymer (J) with the body. That is,
(X3) is one kind of monomer selected from the monomer (fgw), any one kind of the monomer (345), and at least one kind of monomer selected from the (bb235) if necessary. It may be a binary copolymer composed of a monomer (fg
w), at least one monomer selected from w) and any two or more monomers (345), and if necessary (bb2
It may be a multi-component copolymer or the like composed of a combination with at least one monomer selected from the group consisting of 35). These binary copolymers, multicomponent copolymers and the like are collectively abbreviated as a copolymer (J).

From the viewpoint of dielectric constant, heat resistance and processability, a multi-component copolymer is preferable, and (f) and //
Alternatively, a polymer having (g) as an essential constituent monomer, particularly preferably a polymer having (f) and / or (g) and the monomer (4) as essential constituent monomers, and more particularly Preferably, (f) and / or (g), the monomer (4), and optionally a polymer comprising (bb2), (bb3) and / or (bb5), (f) and / or (g), Monomers (3) and (4), and optionally a polymer comprising (bb2), (bb3) and / or (bb5), and (f) and / or (g), monomers (4) and (5), and optionally a polymer comprising (bb2), (bb3) and / or (bb5), most preferably (f) and / or (g),
A polymer composed of the monomer (4) and (bb2),
A polymer comprising (f) and / or (g), monomers (3) and (4), and (bb2), and (f) and / or (g), monomers (4) and (5) ), And (bb2)
Is a polymer consisting of

The weight ratio of monomer (fgw) / monomer (345) is preferably 5/95 to 95/5, more preferably 20/80 to 70/30, particularly preferably 30/7.
It is 0 to 60/40. In the case of a multi-component copolymer, it is preferable that the weight ratio of the monomer (345) is larger from the viewpoint of the dielectric constant, and when the monomer (bb235) is used, the monomer (f
The weight ratio of gw) / monomer (bb235) is 10/90.
To 95/5 are preferable, and more preferably 30/70 to
90/10, particularly preferably 40/60 to 80/20. The bonding form of these copolymers (J) may be block, random, or a combination thereof.
The total number of epoxy groups and alkenyl ether groups contained in the copolymer (J) is preferably 2 to 3,000, more preferably 3 to 1,000, and particularly preferably 5 to 50.
It is 0, most preferably 10 to 200. The Mw of (J) is preferably 2,000 to 1,000,000,
It is more preferably 3,000 to 700,000, and particularly preferably 50,000 to 400,000.

(J) is a monomer (fgw) or a monomer (3
45) and optionally a monomer (bb235) can be easily obtained, and the same polymerization method as (A) used in (X1) can be used.

(X3) may contain other additives (D), other resins (E), rubbers (F), fillers (G) and the like. When (D) is used, the content of (D) is 0.001 to 1 based on the weight of the copolymer (J).
3.0% by weight is preferable, and more preferably 0.01 to
2.0% by weight, particularly preferably 0.05 to 1.0% by weight
Is.

When (E) is used, the content of (E) is 1 to 45% by weight based on the weight of the copolymer (J).
Is more preferable, 5 to 40% by weight is more preferable, and 10 to 30% by weight is particularly preferable.

When (F) is used, the content of (F) is from 1 to 40% by weight based on the weight of the copolymer (J).
Is more preferable, 5 to 30% by weight is more preferable, and 8 to 25% by weight is particularly preferable.

When (G) is used, the content of (G) is from 1 to 50% by weight based on the weight of the copolymer (J).
Is more preferable, 5 to 40% by weight is more preferable, and 8 to 30% by weight is particularly preferable.

Further, (X3) may contain a solvent. As the solvent, the same solvent as that used in the polymerization of (A) can be used. When using a solvent,
The content of the solvent is 5 based on the weight of the copolymer (J).
Is preferably 90 to 90% by weight, more preferably 10 to 80%.
%, Particularly preferably 30 to 70% by weight.

(X3) can be easily produced by uniformly mixing the copolymer (J) and, if necessary, (D) to (G) and / or a solvent, for example, It can be manufactured by the following methods (1) to (3). (1) A method in which (D) to (G) and / or a solvent are sequentially compounded and mixed with the copolymer (J) as needed. (2) A method of blending the copolymer (J) and a solvent, and then optionally mixing (D) to (G). (3) A method of simultaneously mixing the copolymer (J) and, if necessary, (D) to (G) and / or a solvent.

As a method of adjusting the dielectric constant of (X3) after curing, there is a method of adjusting the type of the monomer (ggw), the monomer (345) and the monomer (bb235).
For example, if the contents of (f), (g) and (bb2) are increased, the dielectric constant tends to increase. Dielectric constant is 2-3.
The composition of 5 is, for example, a styrene / propenoxyethyl methacrylate copolymer (weight ratio: 45 to 90).
/ 55 to 10), a styrene / propenoxyethyl methacrylate / 2-ethylhexyl acrylate copolymer (weight ratio: 44 to 80/55 to 10/1 to 10) and the like.

Next, the thermoplastic resin (Y) will be described. The dielectric constant of the thermoplastic resin (Y) is preferably 3.0 or less, more preferably 1.9 to 2.8, particularly preferably 2.0 to 2.6, and most preferably 2.0 to 2.
5, most preferably 2.1 to 2.3. When the dielectric constant is in this range, reliability is further improved when used as an insulator, and when applied to an integrated circuit of electronic parts, etc., signal delay is less likely to occur and circuit performance tends to be easier. is there. The curing conditions and the method of measuring the dielectric constant are the same as for the curable resin (A).

The carbon-carbon double bond or carbon-in (Y)
The content of nitrogen bond is 1 for (Y) from the viewpoint of adhesion and the like.
5 × 10 ^{−5 to} 3.5 × 10 ⁻² mol / g is preferable, and in the case of carbon-carbon double bond, 1.0 × 10 ^{−4 to} 3.
5 × 10 ⁻² mol / g is more preferable, and in the case of carbon-nitrogen bond, 1 × 10 ^{−4 to} 3.5 × 10 ⁻² mol / g is more preferable. Particularly from the viewpoint of the dielectric constant, 1.0 × 10 ^{−3 to} 2.5 × 10 ⁻² mol / g is preferable in the case of a carbon-carbon double bond, and 5 × 10 ⁻⁴ to 2. 5 x 10 ^-2
Mol / g is preferred.

When the content of the carbon-carbon double bond or the carbon-nitrogen bond is less than this range, the thermoplastic resin on the surface of the insulating layer is less likely to be eluted by the oxidizing agent, and fine irregularities are less likely to be formed, resulting in no electrolysis. Adhesion to plating tends to be poor. On the other hand, if it exceeds this range, the dielectric constant of the curable resin material tends to deteriorate. The carbon-carbon double bond or the carbon-nitrogen bond may be present in either the main chain skeleton or side chain skeleton of the resin as long as it is present in (Y), but it is present in the main chain skeleton of the resin. It is preferable.

As (Y), a thermoplastic resin (Y1) having a carbon-carbon double bond and a thermoplastic resin (Y2) having a carbon-nitrogen bond can be used. Examples of the thermoplastic resin (Y1) having a carbon-carbon double bond include (b
1), (b3), (c), (d1), (d3), (e
A (co) polymer having 1) and / or (e3) as essential constituent monomers is used. In the case of a copolymer,
These copolymers may be random type or block type.

For (Y1), other than the essential constituent monomers, other copolymerizable monomers can be used. Other copolymerizable monomers include (b2), (b4), (d2),
(D4), (d5), (d6), (e2), (e4),
(E5), (e6), (f), (g), (h),
(I), (j), (q), (r), (s), (t),
(U), (v), (w), (bb), etc. are mentioned.

When other copolymerizable monomers are used, the content of the other copolymerizable monomers is not particularly limited, but from the viewpoint of heat resistance and resin strength, the content of the total amount of the used monomers is not limited. On the basis of,
20-80% by weight is preferable, and 35-35 is more preferable.
70% by weight, particularly preferably 50-60% by weight.
(Y1) can be easily obtained by the same method as the polymerization method of (A) used for (X1).

Examples of (Y1) include polybutadiene, polyisoprene, styrene-butadiene copolymer,
Styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, norbornene ring-opening polymer, and the like,
It can be easily obtained as the following commercial products.

Commercially available products (trade name) include, for example, JSR BR series (manufactured by JSR Corporation) as polybutadiene and JSR IR series (JSR) as polyisoprene.
SR company), JS as a styrene-butadiene copolymer
Examples include R TR series (manufactured by JSR), JSR SIS series (manufactured by JSR) as a styrene-isoprene copolymer, and Nosolex series (manufactured by JSR) as a ring-opening polymer of norbornene.

Thermoplastic resin having carbon-nitrogen bond (Y
As 2), polyamide, polyurethane, polyurea, polyimide, polyamino acid, and a reaction product of a bifunctional epoxy with a monofunctional primary amine are used. As the polyamide, a diamine having 2 to 18 carbon atoms and 6 to 20 carbon atoms
Alternatively, those obtained from the reaction with more dicarboxylic acids are used. Examples of the diamine include the diamines in (k) and (m). Examples of the dicarboxylic acid include the dicarboxylic acid in (n). In the reaction for obtaining a polyamide, other than diamine and dicarboxylic acid, other than diamine in (k) and (m), (aa7), (aa) for the purpose of adjusting the molecular weight and the like.
Other than dicarboxylic acid in 8) and (n), (aa3) and (aa4), etc. can also be used.

The polyurethane has 2 to 100 carbon atoms.
Or the thing obtained from the reaction of more dihydric phenol or dihydric alcohol and diisocyanate having 6 to 20 carbon atoms is used. Examples of the dihydric phenol include (o1), and examples of the dihydric alcohol include:
For example, (o3) and the like can be mentioned. Examples of the diisocyanate include the diisocyanate in (p). In the reaction for obtaining polyurethane, a compound other than diisocyanate in (o2), (o4) and (p) may be used for the purpose of adjusting the molecular weight and the like.

As the polyurea, those obtained by reacting a diamine having 2 to 18 carbon atoms with a diisocyanate having 6 to 20 carbon atoms are used. Examples of the diamine include the diamines in (k) and (m). Examples of the diisocyanate include the diisocyanate in (p). For the reaction to obtain polyurea,
Other than diamine in (k) and (m), and other than diisocyanate in (aa7), (aa8) and (p) can be used for the purpose of adjusting the molecular weight.

As the polyimide, those obtained by reacting a diamine having 2 to 18 carbon atoms with a polycarboxylic acid having 6 to 20 carbon atoms or more are used. Examples of the diamine include the diamines in (k) and (m). Examples of the polycarboxylic acid include (n). In the reaction for obtaining a polyimide, for the purpose of adjusting the molecular weight and the like, other than diamine in (k) and (m), (aa7), (aa8), (aa3) and (aa)
4) etc. can also be used.

As the polyamino acid, a condensate of aminocarboxylic acid having 2 to 12 carbon atoms and a ring-opening polymer of lactam having 6 to 12 carbon atoms can be used. Examples of the aminocarboxylic acid include amino acids (glycine, alanine, valine, leucine, isoleucine and phenylalanine), ω-aminocaproic acid, ω-aminoenanthic acid,
ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-
Amino dodecanoic acid and the like can be mentioned. As a lactam,
Examples thereof include caprolactam, enantolactam, laurolactam and undecanolactam. In the reaction to obtain polyamino acid, for the purpose of adjusting the molecular weight,
(K), (m), (aa7), (aa8), (n),
(Aa3) and (aa4) can also be used.

As the bifunctional epoxy, for example, (a1
1), (a13) and divalent glycidyl ester in (a2), divalent glycidyl amine in (a3) and (a)
The divalent epoxide in 4) and the like can be mentioned. Examples of monofunctional primary amines include primary amines in (aa7) and (aa8). In the reaction between the bifunctional epoxy and the monofunctional primary amine, (a), (k), (m), (n), other than the above, for the purpose of adjusting the molecular weight and the like.
(P) and (p) can also be used. (Y2)
Can be easily obtained by the same method as the polymerization method of (A) used for (X1).

Of these (Y), from the viewpoint of the dielectric constant, (Y1) and a reaction product of a bifunctional epoxy with a monofunctional primary amine are preferable, and polybutadiene, polyisoprene, and styrene-butadiene copolymerization are more preferable. Coalescing,
It is a styrene-isoprene copolymer, a ring-opening polymer of norbornene, and a reaction product of a bifunctional epoxy with a monofunctional primary amine.

(Y) can contain other additives (D), other resins (E), rubbers (F), fillers (G) and the like. When (D) is used, the content of (D) is preferably 0.001 to 3.0% by weight, more preferably 0.01 to 2.0% by weight, based on the weight of (Y). It is particularly preferably 0.05 to 1.0% by weight.

When (E) is used, the content of (E) is preferably 1 to 45% by weight, more preferably 5 to 40% by weight, particularly preferably 10% by weight, based on the weight of (Y). It is 30% by weight.

When (F) is used, the content of (F) is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, particularly preferably 8 to 10% by weight, based on the weight of (Y). It is 25% by weight.

When (G) is used, the content of (G) is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 8 to 10% by weight, based on the weight of (Y). It is 30% by weight.

Further, (Y) may contain a solvent. As the solvent, the same solvent as that used in the polymerization of (A) can be used. When a solvent is used, the content of the solvent is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 30 to 70% by weight, based on the weight of (Y).

(Y) can be easily produced by uniformly mixing (D) to (G) and / or a solvent, if necessary, by a usual method. As a method of adjusting the dielectric constant of (Y), in the case of (Y1), a method of adjusting the used amount of the manufacturing raw material of (Y1), for example, when the content of butadiene or the like is increased, the dielectric constant tends to be low. However, if the amount of styrene or the like is increased, the dielectric constant tends to increase. Further, in the case of (Y2), a method of adjusting the amount of use of the raw material for manufacturing (Y2), for example, using a diamine having a relatively large number of carbon atoms, a dicarboxylic acid, a monoalkylamine, etc., tends to lower the dielectric constant. If a diamine, dicarboxylic acid, monoalkylamine, or the like having a relatively small carbon number is used, the dielectric constant tends to increase. The dielectric constant of the curable resin material is 2 to 3.5
Examples of the composition that may be mentioned include styrene / butadiene copolymers, styrene / butadiene / acrylonitrile copolymers, bisphenol A / monododecylamine copolymers, and the like.

The weight ratio of (X) / (Y) is 40 to 98/2 to 60 as a weight ratio containing no solvent (calculated as pure content).
Is preferable, and more preferably 65 from the viewpoint of resin strength.
To 96/4 to 35, and particularly preferably 7 from the viewpoint of heat resistance.
0-90 / 10-30, most preferably 80-85 / 1
5 to 20. The curable resin material can optionally contain a curing catalyst (C). (C) may be added just before using the curable resin material, or may be added at the time of producing the curable resin material. When using (C),
Content of (C) ((A), (X1), (X2) and (X
It does not include those used in the adjustment of 3). ) Is (X)
And 0.001 to 10% by weight based on the weight of (Y)
Is more preferable, 0.01 to 8.0% by weight is more preferable, 0.05 to 5.0% by weight is particularly preferable, and 0.1 to 2.0% by weight is most preferable.

For the curable resin material, other additives (D),
Other resin (E), rubber (F), filler (G), etc. can be contained. When using (D), (D)
Content of 0., based on the weight of (X) and (Y).
001 to 3.0 wt% is preferable, 0.01 to 2.0 wt% is more preferable, and 0.05 to 2.0 wt% is particularly preferable.
It is 1.0% by weight.

When (E) is used, the content of (E) is 1 to 45 based on the total weight of (X) and (Y).
Wt% is preferred, more preferably 5-40 wt%,
It is particularly preferably 10 to 30% by weight.

When (F) is used, the content of (F) is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, especially preferably 5 to 30% by weight, based on the weight of (X) and (Y). It is preferably 8 to 25% by weight.

When (G) is used, the content of (G) is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 5 to 40% by weight, based on the weight of (X) and (Y). It is preferably 8 to 30% by weight.

Further, the curable resin material may contain a solvent. As the solvent, the same solvent as that used in the polymerization of (A) can be used. When a solvent is used, the content of the solvent is preferably 5 to 90% by weight, more preferably 1 based on the weight of (X) and (Y).
It is from 0 to 80% by weight, particularly preferably from 30 to 70% by weight.

The curable resin material may be composed of (X) and (Y), but it is preferable that (Y) is uniformly present in (X), and (Y) is (X). It is preferable that they are uniformly dispersed in When (Y) is dispersed in (X), the dispersion average particle size of (Y) is not particularly limited, but is preferably 0.001 to 50 μm, and more preferably from the viewpoint of resin strength. 0.005
To 20 μm, particularly preferably 0.01 to 10 μm, and particularly preferably 0.05 to 5 μ from the viewpoint of adhesion.
m, most preferably 0.1 to 2 μm. The dispersion average particle diameter is obtained by performing a curing treatment on a curable resin material at 180 ° C. for 3 hours, observing the cross section with a scanning electron microscope, and calculating the arithmetic average of the particle diameters of at least 10 (Y) particles. To be

The curable resin material only needs to be a uniform mixture of (X) and (Y) and, if necessary, (C) to (G) and / or a solvent, and can be easily produced by a usual method. Yes, for example, the following method can be applied. (1) (X) and (Y) and, if necessary, (C) to (G)
A method of uniformly dissolving and in a solvent and then removing the solvent by an appropriate method. (2) A method of dissolving (Y) and optionally (C) to (G) in a solvent, polymerizing (X) in this solution, and removing the solvent by an appropriate method. (3) (A), (B) and (Y) and (C) if necessary
After uniformly dissolving (G) to (G) in a solvent, the solvent is removed by an appropriate method. (4) (H), (I) and (Y) and (C) if necessary
After uniformly dissolving (G) to (G) in a solvent, the solvent is removed by an appropriate method. The solvent is not particularly limited as long as it can dissolve both resins, for example,
The thing etc. which are used at the time of manufacture of (A) can be used. Although no special operation is required for dissolution, polymerization and solvent removal, stirring at 1,000 to 20,000 rpm is preferably added.

The thickness of the curable film of the present invention can be appropriately determined according to the purpose of use, but is preferably 1 to 100 μm, more preferably 5 to 70 μm, particularly preferably 15 to 60 μm, most preferably 20 to It is 50 μm. The curable film of the present invention can be produced in the same manner as in the first aspect of the present invention, and the preferable range is also the same.

(3) Fourth aspect of the present invention Tensile elastic modulus after curing of the curable film of the present invention is 10
0 to 250 Kgf / mm ²It may be 110-2
40 Kgf / mm²Is preferable, and more preferably 12
0-230Kgf / mm²And particularly preferably 130 to 2
20 kgf / mm²And more preferably 140 to 2
10 Kgf / mm², Most preferably 150-200K
gf / mm²Is. If the tensile modulus is in this range
It is easy to obtain an insulator with excellent thermal shock resistance. Also pull
Elastic modulus is based on JIS K7113 (1995)
Measured. The dielectric constant after curing of the curable film is 3.
5 or less, but 1.9 to 3.5 is preferable,
Furthermore, preferably 2.0 to 3.4, particularly preferably 2.0.
~ 3.3, most preferably 2.1-3.3, most preferably
It is preferably 2.1 to 3.2. The curable fill
The curing conditions for the film are the same as the curing conditions for the dielectric constant. Starting
The composition of the light-curable film is a curable polymer.
It contains a compound.

The Mw of the curable polymer compound is 10,000.
~ 1,000,000, but 20,000 ~
It is preferably 500,000, more preferably 30,
00 to 100,000, particularly preferably 40,000 to
500,000, and particularly preferably 50,000 to
200,000, particularly preferably 60,000 to 10
It is 10,000. When Mw is in this range, an insulator having excellent thermal shock resistance and the like is easily obtained.

As the curable polymer compound, curable resins (A), (X1), (X2) and (X3) can be used. As the composition constituting the curable film of the present invention, the above curable resin materials and the like can be used, and particularly (X1)
A curable resin material containing is preferable. The thickness of the curable film of the present invention can be appropriately determined according to the purpose of use, but is preferably 1 to 100 μm, more preferably 5
˜70 μm, particularly preferably 15 to 60 μm, most preferably 20 to 50 μm. The curable film of the present invention can be produced in the same manner as in the first aspect of the present invention, and the preferable range is also the same.

(4) Fifth aspect of the present invention The tensile modulus of elasticity of the insulator of the present invention is 100 to 250 Kgf.
/ Mm ² is sufficient, but 110-240 Kgf / mm ²
Is preferred, and more preferably 120-230 Kgf /
mm ² , particularly preferably 130 to 220 Kgf / mm ² ,
More particularly preferably 140 to 210 Kgf / mm ² ,
Most preferably, it is 150 to 200 Kgf / mm ² .
When the tensile modulus is within this range, the thermal shock resistance is excellent. The tensile modulus is JIS K7113 (1995)
It is measured according to. The thermal expansion coefficient (α1) of the insulator of the present invention may be 30 to 50 ppm,
49 ppm is preferred, and more preferably 32-48 p
pm, particularly preferably 35 to 47 ppm, even more preferably 38 to 46 ppm, most preferably 40 to 45
It is ppm. When the coefficient of thermal expansion is within this range, the thermal shock resistance is excellent. The coefficient of thermal expansion is determined by the tensile load method of TMA (differential expansion method). That is, the thickness is 40 μm
The cured film of No. 2 is cut into 20 mm × 2 mm, a load of 5 g is applied, the temperature is raised from room temperature (about 25 ° C.) to 250 ° C. at a speed of 10 ° C./min, and the rate of change in sample length of 30 to 100 ° C. is obtained. The dielectric constant of the insulator of the present invention is 3.5.
The following are preferred, more preferably 1.9 to 3.5, particularly preferably 2.0 to 3.4, even more preferably 2.0 to 3.3, more preferably 2.1 to 3.3, most preferably It is preferably 2.1 to 3.2. The insulator of the present invention is
A curable film (first of the present invention) containing the above curable resin (A), a curable film (second and third of the present invention) composed of a curable resin material, or a curable film (of the present invention). It can be easily produced by thermosetting the fourth) and the like. The conditions for heat curing are 80 to 250 ° C. (preferably 120 to 200 ° C., more preferably 150 to 20).
At 0 ° C., for 0.1 to 15 hours (preferably 0.2 to 5 hours, more preferably 0.5 to 2.0 hours).

The boiling water absorption of the insulator of the present invention is 3.00.
To 0.001%, preferably 2.50 to 0.00
5%, more preferably 2.00 to 0.01%, particularly preferably
It is preferably 1.0 to 0.05%. Boiled water absorption is J
In conformity with IS K7209 (2000) 6.3B method
To be measured. The volume resistance of the insulator of the present invention is 10^Ten~ 1
0¹⁹Ω / cm, preferably 10 ¹²~ 5 x 10¹⁸Ω
/ Cm, more preferably 10¹⁴-10¹⁸Ω / cm, special
Preferably 10¹⁶~ 5 x 10¹⁷Ω / cm, conventional
The insulating material used is epoxy resin or polyimid.
It has superior electrical insulation compared to resin. The volume
Resistance is measured according to JIS K6011 (1995).
Is determined.

The insulator of the present invention has good adhesion to copper formed by oxidant treatment and electroless copper plating, and has a peel strength (JIS C6481 (1995) 5.7).
Indicates 0.8 kgf / cm or more. On the other hand, the heat resistance of the insulator of the present invention is equivalent to that of the conventional insulator, and even if the insulator is contacted with solder at 300 ° C. for 1 minute, no abnormalities such as pattern sagging, swelling and swelling are observed, and Very good chemical resistance to solvents. Further, the insulator of the present invention is also excellent in 10% sulfuric acid resistance, 10% hydrochloric acid resistance, 10% nitric acid resistance and 10% sodium hydroxide resistance measured by the method defined in JIS K6911 (1995) 5.32. . Therefore, the insulator of the present invention has great advantages for speeding up and increasing the density of electronic circuits.

A curable film containing the curable resin (A) of the present invention (the first of the present invention), a curable film made of a curable resin material (the second and third of the present invention), and a curable film. As a method of using (Fourth of the present invention) as an insulator, for example, when using it as an interlayer insulating material, after applying a curable resin (A) or a curable resin material to a substrate,
Alternatively, the curable film of the present invention (the first to the first of the present invention
After laminating 4), heat pressing, if necessary, processing such as punching (roughening, conductive circuit formation, etc.), further laminating the base material, repeating this operation, and finally by heat curing Examples include a method of forming multiple layers. Also,
When the curable resin (A), the curable resin material and the curable film are used as a part of the substrate material of the multilayer substrate, after the curable resin (A) and the curable resin material are applied to the base material, or After laminating the curable film of the present invention (Nos. 1 to 4 of the present invention) on a material, hot pressing, if necessary, processing such as punching, repeating this operation, and finally by heat curing Examples include a method of forming multiple layers. It is also possible to directly use the printed wiring board without using the base material.

When used as an interlayer insulating material for a multilayer circuit board of an electronic circuit, one interlayer insulating layer may consist of one layer or multiple layers, and the film thickness (after curing) thereof is 1 to 100.
μm is preferable, and more preferably 15 to 50 μm. The conditions for hot pressing are as follows: temperature 25 to 180 ° C. (preferably 50 to 150 ° C.), pressure 0.01 MPa to 10
MPa (preferably 0.1 to 1 MPa), time 1 to 12
00 seconds (preferably 10 to 300 seconds) and the like are preferable. The holes (via holes, through holes, etc.) for connecting the layers of the multilayer substrate can be formed by an ordinary method, and for example, a method using a laser (carbon dioxide gas, YAG, excimer, etc.), a drill, etc. can be used. The roughening can be carried out by an ordinary method, and for example, the method described in JP-B-6-49852 can be used. The conductive circuit can be formed by a usual method, and for example, a sputtering method and an electroless method can be used.

A curable film containing the curable resin (A) (the first of the present invention), a curable film containing a curable resin material (the second and the third of the present invention), a curable film (the present invention). The fourth) and the insulator (fifth of the present invention) can be widely used as insulators, and are suitable as, for example, an overcoat material, an interlayer insulating material, a printed circuit board, and the like, and particularly, an overcoat material and an interlayer insulating material. Is suitable as It is optimal as an overcoat material or an interlayer insulating material for electronic elements (semiconductor elements, light emitting diodes, various memories, etc.), hybrid ICs, MCMs, electric wiring circuit boards, display parts and the like.

[0206]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means “part by weight” and “%” means “% by weight”. Synthesis Example 1 5 Methyl ethyl ketone was placed in a reaction vessel purged with nitrogen.
Glycidyl methacrylate 200, which was prepared by charging 0 parts of the solution, heated to 80 ° C., and uniformly dissolved in another nitrogen-substituted container.
Parts, styrene 200 parts, methyl ethyl ketone 200 parts,
Styrene / butadiene / styrene block copolymer (Y
1) 170 parts of trade name TR2250 (styrene / butadiene weight ratio = 52/48, Mw = 90,000, carbon-carbon bond concentration 8.9 × 10 ⁻³ mol / g) manufactured by JSR, and azobisisobutyro A mixture of 1.5 parts of nitrile was added dropwise into the reaction vessel over 4 hours.

After completion of the dropping, the mixture was aged at 100 ° C. for 4 hours to obtain a styrene / glycidyl methacrylate copolymer (styrene / glycidyl methacrylate weight ratio = 50/50) in which the styrene / butadiene / styrene block copolymer (Y1) was dispersed. A curable resin material () containing the curable resin (A) was obtained. The Mw of (A) is 220,
000, the number average molecular weight by GPC (hereinafter abbreviated as Mn) is 90,000, the epoxy equivalent is 246,
Based on Mn and the epoxy equivalent, the number of crosslinkable functional groups (epoxy groups) in (A) was 365. () Is dissolved in methyl ethyl ketone so that the solid content becomes 40%,
A curable resin material solution (S) was obtained.

Synthesis Example 2 A styrene / butadiene / styrene block was prepared in the same manner as in Synthesis Example 1 except that 232 parts of glycidyl methacrylate and 168 parts of styrene were used instead of 200 parts of glycidyl methacrylate and 200 parts of styrene used in Synthesis Example 1. A curable resin material () comprising a styrene / glycidyl methacrylate copolymer in which the copolymer was dispersed (styrene / glycidyl methacrylate weight ratio = 42/58, curable resin (A)) was obtained. Mw of (A) is 21
50,000, Mn is 88,000, epoxy equivalent is 18
It was 0, and the number of crosslinkable functional groups (epoxy groups) of (A) was 489 based on Mn and epoxy equivalent. ()
Was dissolved in methyl ethyl ketone so that the solid content was 40% to obtain a curable resin solution (S).

Synthesis Example 3 The following polymerization experiment was carried out 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.
Temperature, and then a hexane solution of diethylaluminum chloride (catalyst concentration of hexane solution 0.2 mmol / m
1) 5 parts by weight of vanadium oxytrichloride in hexane (catalyst concentration of hexane solution 0.02 mmol / ml) 5
By weight, 50 parts of 5-ethylidene-2-norbornene and 50 parts of 1-hexene were charged and polymerized at 30 ° C. for 120 minutes to obtain a copolymer solution. This copolymer solution was added dropwise to 3000 parts of isopropanol with stirring to form a precipitate, and the precipitate was dried in a vacuum dryer at 100 ° C for 10 ° C.
The solvent was distilled off under reduced pressure of mmHg to give a copolymer (H
) 70 parts were obtained. Mw of (H) is 98,000,
Mn was 25,000, the equivalent of the double bond analyzed by NMR was 204, and Mn and the equivalent of the double bond were (H
The number of crosslinkable functional groups (double bonds) in () was 114. (H) was dissolved in toluene so that the solid content was 40% to obtain a copolymer solution (HS).

Synthesis Example 4 100 parts of the copolymer solution (HS) obtained in Synthesis Example 3, 20 parts of glycidyl methacrylate and 2,5-dimethyl-
After dry blending 7.0 parts of 2,5-di (t-butylperoxy) hexane (trade name: Perhexa 25B, manufactured by NOF CORPORATION) at room temperature, the screw was twin-screwed at a cylinder temperature of 260 ° C. and a screw rotation speed of 230 rpm. It was extruded by an extruder to obtain a curable resin (A). Mw of (A) is 11
7,000, Mn 29,000, epoxy equivalent 85
The number of crosslinkable functional groups (epoxy groups) in (A) was 138 based on Mn and epoxy equivalent. (A)
Was dissolved in toluene so that the solid content was 40% to obtain a curable resin solution (AS).

Synthesis Example 5 6-Methyl-1,4: 5,8-dimethano-1,4,4
100 parts of a cyclic olefin resin (Mw 28,000) produced by ring-opening polymerization of a, 5,6,7,8,8a-octahydronaphthalene (MTD) by a known method, 20 parts of glycidyl methacrylate and 2,5 -Dimethyl-2,
After dry blending 7.0 parts of 5-di (t-butylperoxy) hexane (manufactured by NOF Corporation, trade name: Perhexa 25B) at room temperature, a cylinder temperature of 260 ° C. and a screw rotation speed of 230 rpm were applied to 2 It was extruded by a shaft extruder to obtain a curable resin (A). (A) has Mw of 33,000, Mn of 8,400, and epoxy equivalent of 84.
It was 0, and the number of crosslinkable functional groups (epoxy groups) of (A) was 10 from Mn and epoxy equivalent. (A) was dissolved in toluene so that the solid content was 40% to obtain a curable resin solution (AS).

Synthesis Example 6 Methyl ethyl ketone was added to a reaction vessel purged with nitrogen.
200 parts of hydroxyethyl methacrylate, 200 parts of styrene, and 20 parts of methyl ethyl ketone which were charged with 0 part, heated to 80 ° C. and uniformly dissolved in another nitrogen-substituted container.
A mixture of 0 parts and 1.5 parts of azobisisobutyronitrile was added dropwise to the reaction vessel over 4 hours. After completion of dropping, the mixture was aged at 100 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a hydroxyl group-containing resin. To 100 parts of a methyl ethyl ketone solution of a hydroxyl group-containing resin, 30 parts of acrylic acid was added, and while adding a solvent (methyl ethyl ketone), under reduced pressure, 1
The esterification reaction was carried out at 00 ° C for 4 hours, and the curable resin (A
) Of methyl ethyl ketone was obtained. (A) Mw
Is 160,000, Mn is 45,000, the equivalent of acryloyl groups analyzed by NMR is 610, and the number of crosslinkable functional groups (acryloyl groups) of (A) is 74 from Mn and acryloyl group equivalents. . (A) was adjusted by adding methyl ethyl ketone to a solid content of 40% to obtain a curable resin solution (AS).

Synthetic Example 7 Methyl ethyl ketone was added to a reaction vessel purged with nitrogen.
0 part was charged and the temperature was raised to 80 ° C., and 120 parts of propenyloxyethyl methacrylate, 280 parts of styrene, 200 parts of methyl ethyl ketone and 200 parts of styrene / butadiene / styrene block copolymer (Y1) which were uniformly dissolved in another nitrogen-substituted container. ) (Trade name TR2250 manufactured by JSR Corporation (styrene / butadiene weight ratio = 52/48, Mw = 90,
000, carbon-carbon bond concentration 8.9 × 10 ⁻³ mol /
g)) 170 parts and a mixture consisting of 1.5 parts of azobisisobutyronitrile were dropped into the reaction vessel over 4 hours.
After completion of dropping, aging at 100 ° C. for 4 hours to give styrene /
The butadiene / styrene block copolymer is a styrene / propenyloxyethyl methacrylate copolymer (styrene / propenoxyethyl methacrylate weight ratio = 70 /
30, a solution of the curable resin material () dispersed in the curable resin (A) was obtained. The curable resin material () has Mw of 230,000, Mn of 90,000, and a propenyl ether group equivalent analyzed by NMR of 570. From the Mn and the propenyl ether group equivalent, a crosslinkable functional group (propenyl ether) of () is obtained. The number of groups was 158.
() Was dissolved in methyl ethyl ketone so that the solid content was 40% to obtain a curable resin material solution (S).

Synthesis Example 8 100 parts of toluene, 100 parts of Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd .; bisphenol A type epoxy resin) and 50 parts of dodecylamine were added to a reaction vessel replaced with nitrogen, and the mixture was stirred. The reaction was carried out at 25 ° C for 4 hours to obtain a thermoplastic resin (Y2). The Mw of (Y2) is 7
5,000 and Mn were 37,000. (Y2
The nitrogen-carbon bond concentration of) is 1.9 × 10 ⁻³ mol / g.
there were. Then, the solid content of (Y2) is dissolved in toluene so that the solid content of the thermoplastic resin solution (Y2) becomes 40%.
S) was obtained.

Synthesis Example 9 Methyl ethyl ketone was charged in a reaction vessel purged with nitrogen.
Glycidyl methacrylate 2 was charged with 0 parts and heated to 80 ° C. and uniformly dissolved in another nitrogen-substituted container.
00 parts, 200 parts of styrene, tridecafluorohexyl-ethyl acrylate _{(C 6 F 13 C 2 H} 4 -OCOCH = C
H ₂ ) 200 parts, methyl ethyl ketone 200 parts, styrene / butadiene / styrene block copolymer (Y1)
(JSR Corporation trade name TR2250 (styrene / butadiene weight ratio = 52/48, Mw = 90,000, carbon-carbon bond concentration 8.9 × 10 ⁻³ mol / g)) 170 parts and azobisisobutyronitrile A mixture of 1.5 parts was dropped into the reaction vessel over 4 hours. 100 after dropping
Aged at 4 ° C. for 4 hours to give styrene / butadiene / styrene block copolymer (Y1) dispersed styrene /
Glycidyl methacrylate / tridecafluorohexyl ethyl acrylate copolymer (monomer weight ratio = 50/5
A curable resin material () containing 0/50 and the curable resin (A) was obtained. (A) has Mw of 120,000 and GP
The number average molecular weight by C (hereinafter abbreviated as Mn) is 6
10,000, the epoxy equivalent is 325, and the crosslinkable functional group (epoxy group) of (A) from Mn and the epoxy equivalent.
Was 185. () Was dissolved in methyl ethyl ketone so that the solid content was 40% to obtain a curable resin material solution (AS).

Example 1 (Example consisting of X1 and Y1) To 175 parts of the thermosetting resin material solution (S), 30 parts of resorcinol diglycidyl ether (B) and 2-ethyl-4-methylimidazole (C). Was added and stirred to obtain a solution of the curable resin material () of the present invention. This solution was applied to a PET film (257 mm x 3) with a thickness of 50 μm.
64 mm) with a knife coater (manufactured by Yasui Seiki; knife coater SNC-300) and coated at 60 ° C. for 3 hours.
It was dried for 0 minutes, the solvent was removed, and a curable film (F) was prepared on a PET film. Curable film (
The thickness of F) was 47 ± 2 μm. Curable film (F) is BT substrate (Mitsubishi Gas Chemical Industry Co., Ltd., CC
L-HL830, 100 mm x 100 mm, each half of the front and back sides of the copper foil removed by etching) and hot pressed at 120 ° C for 5 minutes at 0.4 kg / cm ² , and then the PET film was peeled off. Then, it was heated and cured at 180 ° C. for 3 hours to obtain an insulator (Z).

The insulator (Z) was cut with a diamond cutter, and the cross section was observed with a scanning electron microscope (Y1
(Styrene / butadiene block copolymer)) The average particle size of the particles was calculated to be 0.4 μm. Using this insulator (Z), after continuing at -55 ° C for 30 seconds, 1
A temperature pattern of increasing the temperature to 125 ° C. in 0 seconds, continuing 125 ° C. for 30 seconds and decreasing the temperature to −55 ° C. in 10 seconds was defined as one cycle, and a thermal cycle test was repeated. But crack,
No blister or peeling defect was observed. Further, in the same manner as the method described in the example of Japanese Examined Patent Publication No. 6-49852, after the insulating (Z) hardened surface is roughened and subjected to copper plating treatment, peeling strength (JIS C6481 (1995)
When the (year) 5.7) was measured, it was 0.8 kg / cm. In addition, the above curable film (F) is heated to 170 ° C.
Then, heat cure it for 90 minutes, and then use JIS K6911 (1
995) 5.14, the cured dielectric constant at 1 GHz was 2.9, the dielectric loss tangent was 0.009, and the volume resistance was 5.1 × 10 ¹⁶ Ω / cm. Also,(
Tensile elastic modulus after curing (F) (JIS K7113 (19
1995)) was 16000 kgf / mm ² . Further, the thermal expansion coefficient (TMA tensile load method) of (F) after curing was 45 ppm / ° C. In addition, SP of styrene / butadiene / styrene block copolymer (Y1)
The value is 9.1, and the SP value of the curable resin composition (X1) comprising the styrene / glycidyl methacrylate copolymer (curable resin (A)) and resorcinol diglycidyl ether (B) is 11.0. Met. Therefore,
The difference in SP value between (Y1) and (X1) was 1.9.

Example 2 (Example consisting of X1 and Y1) In Example 1, the thermosetting resin material solution (S) 17 was used.
Instead of 5 parts, thermosetting resin material solution (S) 175
A solution of a curable resin material (), a curable film (F) and an insulator (Z) were obtained in the same manner as in Example 1 except that the parts were used. The curable film (F) had a thickness of 47 ± 2 μm. Insulator (Z) (Y1 (styrene / butadiene / calculated in the same manner as in Example 1
Styrene block copolymer)) The average particle size of the particles is
It was 0.4 μm. When a thermal cycle test was conducted in the same manner as in Example 1, no defects such as cracking, swelling or peeling were observed even after 1000 cycles. The peel strength was measured in the same manner as in Example 1 and found to be 0.8 kg / cm. Also, the dielectric constant after curing of (F) measured in the same manner as in Example 1 was 2.9, the dielectric loss tangent was 0.009, and the volume resistance was 3.5 × 10 ¹⁶ Ω / c.
It was m. Further, the tensile modulus of elasticity of (F) after curing is 1
It was 7400 kgf / mm ² . The coefficient of thermal expansion of (F) after curing was 46 ppm / ° C. In addition,
The difference in SP value between (Y1) and (X1) was 1.9 as in Example 1.

Example 3 (Example consisting of X2 and Y1) To 175 parts of the copolymer solution (HS), 30 parts of ethylene glycol diallyl ether (I), 2 parts of p-menthane hydroperoxide (C) and styrene. / Butadiene / styrene block copolymer (Y1) (T manufactured by JSR Corporation
R2250) 15 parts was added and stirred to obtain a solution of curable resin material (). Using the solution of the curable resin material () in the same manner as in Example 1, the curable film (
F) was prepared, and using this, an insulator (Z) was obtained in the same manner as in Example 1. The curable film (F) had a thickness of 47 ± 2 μm. The average particle size of the (Y1 (styrene / butadiene / styrene block copolymer)) particles of the insulator (Z) calculated in the same manner as in Example 1 was 0.3 μm. In the thermal cycle test evaluated using this insulator (Z) in the same manner as in Example 1, no swelling or peeling defects were observed. The peel strength was measured in the same manner as in Example 1 and found to be 0.8 kg / cm. Further, (F) measured in the same manner as in Example 1 has a cured dielectric constant of 2.4, a dielectric loss tangent of 0.006, and a volume resistance of 4.1 × 10 ¹⁷ Ω / c.
m, the tensile elastic modulus was 18400 kgf / mm ² , and the thermal expansion coefficient was 47 ppm / ° C. The styrene / butadiene / styrene block copolymer (Y1) had an SP value of 9.1, and was a curable resin composition (X2) composed of a copolymer solution (HS) and ethylene glycol diallyl ether (I). SP value of was 9.9. Therefore, the difference in SP value between (Y1) and (X2) was 0.8.

Example 4 (Example consisting of X1 and Y2) To 175 parts of a curable resin solution (AS), 30 parts of resorcinol diglycidyl ether (B), 2-ethyl-
6 parts of 4-methylimidazole (C5) and 15 parts of the thermoplastic resin solution (Y2S) were added and stirred to obtain a solution of the curable resin material (). The curable film () was used in the same manner as in Example 1 using the solution of the curable resin material ().
F) was adjusted, and using this, an insulator (Z) was obtained in the same manner as in Example 1. The curable film (F) had a thickness of 47 ± 2 μm. The average particle diameter of (Y2) of the insulator (Z) calculated in the same manner as in Example 1 is
It was 0.8 μm. In the thermal cycle test evaluated using this insulator (Z) in the same manner as in Example 1, no swelling or peeling defects were observed. In addition, Example 1
When the peeling strength was measured in the same manner as
It was 0.8 kg / cm. Further, the dielectric constant after curing of (F) measured in the same manner as in Example 1 is 2.5, the dielectric loss tangent is 0.006, and the volume resistance is 4.3 × 10 ¹⁷ Ω / cm.
The tensile elastic modulus was 18,800 kgf / mm ² , and the thermal expansion coefficient was 47 ppm / ° C. The curable resin (Y2
SP value of 1) is 13.5, and the curable resin (A)
And the SP value of the curable resin composition (X1) comprising resorcinol diglycidyl ether (B) is 11.2
Met. Therefore, the difference in SP value between (Y2) and (X1) was 2.3.

Example 5 (Example consisting of X1 and Y2) Except that 175 parts of the curable resin solution (AS) of Example 4 was used, 175 parts of the curable resin solution (AS) was used.
A solution of the curable resin material () was obtained in the same manner as in Example 4. A curable film (F) was prepared in the same manner as in Example 1 using a solution of the curable resin material (), and using this, an insulator (Z) was obtained in the same manner as in Example 1.
The curable film (F) had a thickness of 47 ± 2 μm. Insulator (Z) calculated in the same manner as in Example 1
The average particle diameter of (Y2) was 0.8 μm. In the thermal cycle test evaluated using this insulator (Z) in the same manner as in Example 1, no swelling or peeling defects were observed. The peel strength was measured in the same manner as in Example 1 and found to be 0.8 kg / cm. Moreover, the dielectric constant after curing of (F) measured in the same manner as in Example 1 was 2.5, the dielectric loss tangent was 0.006, the volume resistance was 2.9 × 10 ¹⁷ Ω / cm, and the tensile elastic modulus was 16800.
kgf / mm ² and coefficient of thermal expansion were 46 ppm. The SP value of the curable resin (Y2) was 13.5, and the curable resin composition (X1 containing the curable resin (A) and the resorcinol diglycidyl ether (B) was used.
SP value of 10) was 10.2. Therefore, (Y2)
The difference in SP value between (X1) and (X1) was 3.5.

Example 6 (Example consisting of X1 and Y2) To 175 parts of a curable resin solution (AS), 30 parts of ethylene glycol dimethacrylate (B), 2 parts of p-menthane hydroperoxide (C) and heat were added. 15 parts of the plastic resin solution (Y2S) was added and stirred to obtain a solution of the curable resin material (). A curable film (F) was prepared using the solution of the curable resin material () in the same manner as in Example 1, and using this, an insulator (Z) was obtained in the same manner as in Example 1. The curable film (F) had a thickness of 47 ± 2 μm. The average particle diameter of (Y2) of the insulator (Z) calculated in the same manner as in Example 1 is 0.5.
was μm. Example 1 using this insulator (Z)
In the thermal cycle test evaluated in the same manner as,
No peeling defect was observed. The peel strength was measured in the same manner as in Example 1 and found to be 0.8 k.
It was g / cm. Further, the dielectric constant after curing of (F) measured in the same manner as in Example 1 was 2.9, and the dielectric loss tangent was 0.
009, volume resistance 4.6 × 10 ¹⁶ Ω / cm, tensile modulus 18200 kgf / mm ² , thermal expansion coefficient 47 pp.
It was m. The SP value of the curable resin (Y2) is
It was 13.5, and the SP value of the curable resin composition (X1) comprising the curable resin (A) and ethylene glycol dimethacrylate (B) was 10.4. Therefore, the difference in SP value between (Y2) and (X1) was 3.1.

Example 7 (Example consisting of X1 and Y1) 175 parts of the curable resin material solution (S) and a cationic photopolymerization initiator (“UVR-699” manufactured by Union Carbide Co., Ltd.)
0 ") 5.0 parts by weight was stirred to obtain a solution of the curable resin material (10). A curable film (10F) was prepared in the same manner as in Example 1 using the solution of the curable resin material (10). Irradiate the curable film (10F) with ultraviolet rays at 150 ° C for 1 minute (using a high pressure mercury lamp of 80W / cm, distance of 10cm, irradiation intensity of 160mW / cm ² )
Heat treatment at 150 ° C for 3 hours, and
Z) was obtained. The thickness of the curable film (10F) is 4
It was 7 ± 2 μm. The average particle diameter of (Y1) of the insulator (10Z) calculated in the same manner as in Example 1 is 0.4 μm.
Met. In the thermal cycle test evaluated using this insulator (10Z) in the same manner as in Example 1, no swelling or peeling defects were observed. The peel strength was measured in the same manner as in Example 1 and found to be 0.8 kg /
It was cm. Also, the dielectric constant after curing of (10F) measured in the same manner as in Example 1 is 2.9, and the dielectric loss tangent is 0.0.
09, volume resistance 6.7 × 10 ¹⁶ Ω / cm, tensile modulus 22000 kgf / mm ² , thermal expansion coefficient 45 ppm
Met. Also, irradiate (10F) with UV light at 150 ° C for 1 minute (using a high pressure mercury lamp of 80W / cm, distance 1
The dielectric constant was 2.9 after curing under heating conditions of 0 cm and irradiation intensity of 160 mW / cm ² for 3 hours. In addition, S of the curable resin (Y1)
The P value was 9.1, and the SP value of the curable resin composition (X1) composed of the curable resin (A) was 10.2. Therefore, the difference in SP value between (Y1) and (X1) was 1.1.

Example 8 (Example consisting of X3 and Y1) To 175 parts of the thermosetting resin material solution (S), 30 parts of resorcinol diglycidyl ether (B) and 2-ethyl-4-methylimidazole (C). Was added and stirred to obtain a solution of the curable resin material (11) of the present invention. This solution was applied to a PET film (257 mm x 3) with a thickness of 50 μm.
64 mm) with a knife coater (manufactured by Yasui Seiki; knife coater SNC-300) and coated at 60 ° C. for 3 hours.
It was dried for 0 minutes, the solvent was removed, and a curable film (11F) was prepared on a PET film. Curable film (11
The thickness of F) was 47 ± 2 μm. A curable film (11F) is attached to a BT substrate (Mitsubishi Gas Chemical Industry Co., Ltd., CC
L-HL830, 100 mm x 100 mm, each half of the front and back sides of the copper foil removed by etching) and hot pressed at 120 ° C for 5 minutes under the condition of 0.4 kg / cm ² , and then the PET film is peeled off. Then, it was heated and cured at 180 ° C. for 3 hours to obtain an insulator (11Z). Example 1
The average particle diameter of (Y1) of the insulator (11Z) calculated in the same manner as in was 0.5 μm. This insulator (11Z)
In a thermal cycle test evaluated in the same manner as in Example 1 using No. 1, no swelling or peeling defect was observed. The peel strength was measured in the same manner as in Example 1 and found to be 0.8 kg / cm. In addition, Example 1
The dielectric constant after curing of (11F) measured in the same manner as in 2.
7, dielectric loss tangent is 0.007, volume resistance is 5.7 × 10 ¹⁶
Ω / cm, the tensile elastic modulus was 19000 kgf / mm ² , and the thermal expansion coefficient was 43 ppm. The curable resin (Y
The SP value of 1) is 9.1, and the curable resin (A)
The SP value of the curable resin composition (X1) consisting of
Met. Therefore, the difference in SP value between (Y1) and (X1) was 0.6.

Comparative Example 1 Epicoat 828 (trade name of Yuka Shell Epoxy Co., Ltd .; bisphenol A type epoxy resin) was added to 8 parts per 100 parts.
5 parts of 4-methylcyclohexane-1,2-dicarboxylic acid were added and mixed by stirring, and a BT substrate (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.) was used using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300). , CCL-830, 100
mm × 100 mm, half of the copper foil on each of the front and back sides was removed by etching) and then applied at a thickness of 62 ± 2 μm, followed by heat curing at 180 ° C. for 3 hours to obtain a comparative insulator (1). . A thermal cycle test was conducted using this comparative insulator (1) in the same manner as in Example 1, but cracks occurred at a rate of 1 piece / cm ^{2 in} 500 cycles. Further, the peel strength after roughening and copper plating treatment was measured in the same manner as in Example 1 and found to be 0.2 kg / cm.
Met. The dielectric constant of the comparative insulator (1) measured in the same manner as in Example 1 was 3.6, and the dielectric loss tangent was 0.02.
0, the volume resistance was 4.8 × 10 ¹⁶ Ω / cm, the tensile elastic modulus was 38000 kgf / mm ² , and the thermal expansion coefficient was 60 ppm.

Comparative Example 2 Cresol Novolac Epoxy Resin 10 with Mw 1040
0 parts to 95 parts of 4-methylcyclohexane-1,2-
Dicarboxylic acid was added and mixed by stirring, and a BT substrate (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., CCL-83) using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300).
0, 100 mm x 100 mm, half of the copper foil on both sides, removed by etching) 62 ± 2 on top
After being applied in a thickness of μm, it was heated and cured at 180 ° C. for 3 hours to obtain a comparative insulator (2). Using this comparative insulator (2), a thermal cycle test was conducted in the same manner as in Example 1, but cracks occurred at a rate of 1 piece / cm ^{2 in} 700 cycles. The peel strength after roughening and copper plating was measured in the same manner as in Example 1.
It was 2 kg / cm. Moreover, the dielectric constant of the comparative insulator (2) measured in the same manner as in Example 1 was 3.5, the dielectric loss tangent was 0.020, the volume resistance was 5.3 × 10 ¹⁶ Ω / cm, and the tensile elastic modulus was 35,000 kgf / mm ² , coefficient of thermal expansion is 7
It was 0 ppm / ° C.

[0227]

INDUSTRIAL APPLICABILITY The curable resin, curable resin material and curable film of the present invention can produce an insulator having excellent thermal shock resistance and dielectric properties. Furthermore, by using the curable resin, curable resin material and curable film of the present invention, it is excellent in adhesiveness, heat resistance, solvent resistance, low water absorption, electrical insulation, chemical resistance and processability. Insulators can be formed. Therefore, it is most suitable as an overcoat material or an interlayer insulating material used for a circuit board used for various electric devices, electronic parts or semiconductor elements. The curable resin, curable resin material and curable film of the present invention are not limited to use in the technical field of circuit boards and the like,
It is an excellent material that can be used in various fields, and particularly can be used for forming a thin film.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/28 H05K 3/28 F 5F033 3/46 T 3/46 H01L 21/90 S (72) Inventor Masahito Inoue Kyoto 1-11, Hitotsubashi-Honcho, Higashiyama-ku, Yokohama F-term inside Sanyo Chemical Industries Co., Ltd. (reference) 4F071 AA04 AA15 AA20 AA22 AA39 AA42 AA80 AA81 AA86 AF15Y AF23 AF39 AF40Y AF45 AH12 AH13 BC01 4W002 BC09W BC11W BD12W BD13W BD14W BE04W BF01W BF04W BF05W BG01W BG04W BG05W BG07W BG08W BG09W BH02W BJ00W BK00W BK00X BQ00W CD01W CD02W CD02X CD04W CD04X CD05W CD06X CD07W CD08W CD10W CD11W CD12W CD13W CD16X CD18X CD19W CD19X CK01W CK01Y CK02W CK05Y CL02Y CL03Y CM04Y EA016 ED026 EH076 EL026 EL036 ER006 FD010 FD14W FD14X FD146 GH00 GQ01 HA05 4J036 AA01 AA05 AK04 AK06 EA01 EA03 JA05 5E314 AA25 AA32 BB02 BB11 BB12 BB13 CC15 FF01 GG09 5E346 AA12 BB01 CC02 CC09 DD02 RR21 SS16H22

Claims (11)

[Claims] 1. An epoxy group, a (meth) acryloyl group,
It has at least two crosslinkable functional groups selected from the group consisting of alkenylamino groups and alkenyloxy groups in the molecule, and has a glass transition temperature of 50 to 50 before curing.
150 ° C, weight average molecular weight 10,000 to 1,000
A curable film comprising a curable resin (A) of 10,000 and having a dielectric constant after curing of the (A) of 3.2 or less. 2. The curable film according to claim 1, wherein the crosslinkable functional group is an epoxy group. 3. (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 film according to claim 1 or 2. 4. A weight average of at least two crosslinkable functional groups selected from the group consisting of epoxy groups, (meth) acryloyl groups, alkenylamino groups and alkenyloxy groups in the molecule. Molecular weight is 1
A low molecular weight compound (B) of 70 to 3,000 is contained, and the dielectric constant after curing is 3.5 or less.
The curable film according to any one of 3 above. 5. A curable resin composition (X) and a thermoplastic resin (Y) are contained, and the solubility parameter difference between (X) and (Y) is 0.5 to 3.0. A curable film comprising a curable resin material having a weight average molecular weight of (Y) of 5,000 to 1,000,000. 6. A curable resin composition (X) and a thermoplastic resin (Y) are contained, and the difference in solubility parameter between (X) and (Y) is 1.0 to 3.0. And the curable film which consists of a curable resin material whose solubility parameter of this (X) is 5.0-12.0. 7. The curable resin composition (X) contains a curable resin (A) and / or (B).
The curable film described. Curable resin (A): having at least two cross-linkable functional groups selected from the group consisting of epoxy group, (meth) acryloyl group, alkenylamino group and alkenyloxy group in the molecule, before curing. Curable resin having a glass transition temperature of 50 to 150 ° C. and a weight average molecular weight of 10,000 to 1,000,000 Curable resin (B): epoxy group, (meth) acryloyl group, alkenylamino group and alkenyloxy group A low molecular weight compound having at least two crosslinkable functional groups selected from the group consisting of 8. A weight average molecular weight of 10,000 to 1,0.
A film comprising a composition containing a curable high molecular compound of 0,000, having a tensile elastic modulus after curing of 100 to 250 kgf / mm ² and a dielectric constant after curing of 3.5 or less. A curable film characterized by being present. 9. The tensile modulus of elasticity is 100 to 250 kgf / m.
m ² and a thermal expansion coefficient α1 of 30 to 50 ppm. 10. A tensile elastic modulus of 150 to 200 kgf /
a mm ^2, an insulator of claim 12, wherein the thermal expansion coefficient α1 is 35～45Ppm. 11. An insulator obtained by curing the curable film according to claim 1.