JP2004162074A - Curable film and insulator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulator having excellent thermal shock resistance and dielectric characteristics and a curable film optimal for the same. <P>SOLUTION: This curable film comprises a curable resin which has, per molecule, at least two functional cross-linking groups comprising at least one kind of group selected from among an epoxy, a (meth)acryloyl, an alkenylamino and an alkenyloxy group, has a glass transition temperature of 50-150°C and a weight average molecular weight of 10,000-1,000,000, and, when cured, gives a cured film with a dielectric constant of 3.2 or less; otherwise, the curable film comprises a composition containing a curable polymer compound with a weight average molecular weight of 10,000-1,000,000 and, when cured, gives a cured film with a tensile modulus of 100-250 kgf/mm<SP>2</SP>and a dielectric constant of 3.5 or less. <P>COPYRIGHT: (C)2004,JPO

Description

  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 for various electric devices, electronic components, semiconductor devices, and the like.

As insulating materials, defects such as moisture resistance and dielectric properties in the high-frequency region of epoxy resin-based compositions and polyimide-based resins, and defects such as heat resistance and solvent resistance of polyolefin-based resins and polyphenylene ether-based resins, etc. In order to solve the problem, for example, a method of crosslinking a copolymer of norbornene-type monomer and ethylene with sulfur, organic oxide, electron beam or radiation (JP-A-62-34924), a propargyl group or an allyl group Examples of using a polyphenylene ether substituted with a group, a polyphenylene ether containing a double bond, and a polyphenylene ether modified with an unsaturated carboxylic acid or an acid anhydride thereof (for example, Patent Documents 1 to 5) are known.
JP-A-1-69628 JP-A-1-69629 JP-A-1-113425 JP-A-1-113426 JP-A 1-239017, etc.

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

The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention.
That is, a first aspect of the present invention is that a polymer having at least two kinds of crosslinkable functional groups selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group and an alkenyloxy group in a molecule is provided. It contains a curable resin having a previous glass transition temperature of 50 to 150 ° C and a weight average molecular weight of 10,000 to 1,000,000, and has a dielectric constant of 3.2 or less after curing of (A). It is a curable film characterized by the following.
A second aspect 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 And a curable resin material comprising a curable resin material having a weight average molecular weight of 5,000 to 1,000,000.

A third aspect 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 1.0 to 3. 0 is a curable film comprising a curable resin material having a solubility parameter (X) of 5.0 to 12.0.
A fourth aspect of the present invention is a film comprising a composition containing a curable polymer having a weight-average molecular weight of 10,000 to 1,000,000, and having a tensile modulus of 100 to 100 after curing of the film. a curable film, characterized in that 250 kgf / mm ² a and dielectric constant after curing is 3.5 or less.
A fifth aspect of the present invention is an insulator characterized by having a tensile modulus of 100 to 250 kgf / mm ² and a thermal expansion coefficient α1 of 30 to 50 ppm.

The curable resin, the curable resin material, and the curable film of the present invention can produce an insulator having extremely excellent thermal shock resistance and dielectric properties.
Furthermore, by using the curable resin, the curable resin material and the curable film of the present invention, the adhesiveness, heat resistance, solvent resistance, low water absorption, electric insulation, chemical resistance, workability, etc. are excellent. Can be formed.

(1) Regarding the First of the Present Invention The crosslinkable functional group of the curable resin (A) is at least one selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group and an alkenyloxy group. Or a combination of two or more of these.
As the epoxy group, any of the groups represented by the formulas (1) and (2) can be used.

The (meth) acryloyl group means an acryloyl group (CH ₂ ＣＨCHCO—) or a methacryloyl group (CH ₂ ＣC (CH ₃ ) CO—).
Examples of the alkenylamino group include an alkenylamino group having 2 to 4 carbon atoms, such as a vinylamino group, a propenylamino group (1-propenylamino group), an allylamino group (2-propenyloxy group), and 1-butenylamino. Group, 2-butenylamino group and 1-methylpropenylamino group.
Examples of the alkenyloxy group include an alkenyloxy group having 2 to 4 carbon atoms, such as a vinyloxy group, a propenyloxy group (1-propenyloxy group), an allyloxy group (2-propenyloxy group), and a 1-butenyloxy group. , 2-butenyloxy group and 1-methylpropenyloxy group.
Among these crosslinkable functional groups, an epoxy group, a (meth) acryloyl group, a vinyloxy group, a propenyloxy group and an allyloxy group are preferred, more preferably an epoxy group, a (meth) acryloyl group and a propenyloxy group, particularly preferably epoxy And an (meth) acryloyl group, more preferably an epoxy group, and most preferably an epoxy group represented by the formula (2).
Having 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 two, but is preferably 2 to 5,000, more preferably 3 to 3,000, particularly preferably 5 to 1,000, and more particularly It is preferably from 7 to 500, most preferably from 10 to 400. When the number of crosslinkable functional groups is within this range, an insulator excellent in thermal shock resistance, dielectric constant, and the like is easily obtained.
The glass transition temperature before curing of (A) may be 50 to 150 ° C, preferably 53 to 140 ° C, more preferably 56 to 130 ° C, particularly preferably 59 to 135 ° C, and still more preferably 62 to 130 ° C. 120C, most preferably 65-100C. 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 measured by TMA-Tg.

The weight average molecular weight of (A) may be 10,000 to 1,000,000, preferably 20,000 to 900,000, more preferably 30,000 to 500,000, and particularly preferably 40,000 to 500,000. 000 to 200,000, more preferably 50,000 to 150,000, particularly preferably 60,000 to 120,000. 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 hereinafter abbreviated as Mw.
The dielectric constant of (A) after curing may be 3.2 or less, but is preferably 2.4 to 3.2, more preferably 2.5 to 3.1, and particularly preferably 2.5 to 3. 2.0, more preferably 2.6 to 2.9, and most preferably 2.6 to 2.8. When the dielectric constant after curing is in this range, the reliability is further improved when used as an insulator, and when applied to an integrated circuit of electronic components, signal delay hardly occurs and the performance of the circuit is easily improved. Tends to be.
The hardening is performed by heating and hardening at 170 ± 10 ° C. for 90 ± 10 minutes with a forward air heater.
The dielectric constant is measured at 1 GHz according to JIS K6911 (1995) 5.14.

(A) includes, for example, (i) a method of (co) polymerizing a monomer having a crosslinkable functional group, or (ii) a reactive functional group (such as an amino group, a nitrile group, a carboxyl group, a hydroxyl group, and an isocyanate group). ) Is reacted 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.
Examples of the monomer having a crosslinkable functional group include a monomer having at least two functional groups selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group, and an alkenyloxy group ( aj, 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. And a monomer (qw) having at least one group each.
As the monomer having a reactive functional group, in addition to the 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 Monomers (kp) having at least two functional groups selected from at least one selected from the group consisting of (kp) and the like can be used.

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

Examples of the monomer (kp) having at least two functional groups of at least one kind 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 include: Monomer having primary amino group (k), monomer having secondary amino group (m), monomer having only carboxyl group (n), monomer having only hydroxyl group (o) And a monomer (p) having only an isocyanate group can be used.
A simple compound having at least one 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. The monomer (qw) includes 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. (S), 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 a molecule and the like can be used. For example, a glycidyl ether type polyepoxide (a1), a glycidyl ester type polyepoxide (a2) ), Glycidylamine type polyepoxide (a3) and alicyclic polyepoxide (a4).

As the glycidyl ether type polyepoxide (a1), for example, the following (a11) to (a14) can be used.
(A11) Diglycidyl ether of dihydric phenol (C6-30) 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-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4 ' Dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9, 9'-bis (4-hydroxyphenyl) furorange glycidyl ether and diglycidyl ether obtained by reacting 2 mol of bisphenol A with 3 mol of epichlorohydrin.

(A12) Polyglycidyl ether pyrogallol triglycidyl ether, polyhydroxynaphthyl cresol triglycidyl ether, polyhydric phenol (C6 to 50 or more, Mw 110 to 5,000, trivalent to hexavalent or more) Phenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, trismethyl-tert-butyl-butylhydroxymethanetriglycidyl ether, 4,4′-oxybis (1,4- Phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) phenylglycidyl ether and bis (dihydroxynaphthalene) tetraglycidyl Ether and the like.

(A13) a dihydric alcohol [alkylene glycol having 2 to 6 or more carbon atoms or alkylene oxide (2 to 4 carbon atoms) of a dihydric phenol having 6 to 24 or more carbon atoms (hereinafter, having 2 to 4 carbon atoms) Alkylene oxide is abbreviated as AO.) 1-90 mol adduct] diglycidyl ether ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene Glycol (Mw 150-4,000) diglycidyl ether, polypropylene glycol (Mw 180-5,000) diglycidyl ether, polytetramethylene glycol (Mw 200-5,000) diglycidyl ether, neopen Diglycidyl of butyl glycol diglycidyl ether and an adduct of bisphenol A with ethylene oxide (hereinafter, ethylene oxide is abbreviated as EO) and / or propylene oxide (hereinafter, propylene oxide is abbreviated as PO) (1 to 20 mol). Ether and the like.

(A14) Polyglycidyl ether of trihydric to heptavalent or higher polyhydric alcohol (having 3 to 50 or more carbon atoms and Mw of 76 to 10,000), trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol Tetraglycidyl ether, sorbitol hexaglycidyl ether and poly (polymerization degree 2-5) glycerin polyglycidyl ether;

As the glycidyl ester type polyepoxide (a2), for example, the following (a21) to (a22) can be used.
(A21) Polyglycidyl ester of a divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms) diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate and triglyceride Triglycidyl melitate and the like.
(A22) Additive of aromatic nucleus of polyglycidyl ester of divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acid (C6 to 20 or more) (a21), diglycidyl dimer acid , Diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimerate and triglycidyl tricarballylate.

As the glycidylamine-type polyepoxide (a3), for example, the following (a31) to (a34) can be used.
(A31) polyglycidyl aromatic amine having 2 to 10 or more glycidyl groups (aromatic amine having 6 to 20 or more carbon atoms)
N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyldiaminodiphenylsulfone, N, N , N ', N'-tetraglycidyldiethyldiphenylmethane and N, N, O-triglycidylaminophenol.

(A32) a polyglycidyl aliphatic or araliphatic amine having 2 to 10 or more glycidyl groups (aliphatic or araliphatic amine having 6 to 20 or more carbon atoms)
N, N, N ', N'-tetraglycidylxylylenediamine and N, N, N', N'-tetraglycidylhexamethylenediamine and the like.
(A33) a polyglycidyl alicyclic amine having 2 to 10 or more glycidyl groups (the alicyclic amine has 6 to 20 or more carbon atoms)
Hydrogenated compounds of N, N, N ', N'-tetraglycidylxylylenediamine;
(A34) Polyglycidyl heterocyclic amine having 2 to 10 or more glycidyl groups (heterocyclic amine having 6 to 20 or more carbon atoms)
Tris glycidyl melamine and N-glycidyl-4-glycidyloxypyrrolidone and the like.

  Examples of the alicyclic polyepoxide (a4) include alicyclic epoxides having 6 to 50 or more carbon atoms, Mw of 98 to 5,000, and 2 to 4 or more epoxy groups. Vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, 3,4 epoxy-6-methylcyclohexylmethyl 3 ', 4'- Epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine and the like.

  As the monomer (b) having only a (meth) acryloyl group, di (meth) acrylate (b1) of dihydric phenol (C6 to C30), polyhydric phenol {C6 to C50 or more, Mw 110 to 5,000, trivalent to hexavalent or higher poly (meth) acrylate (b2), dihydric alcohol [alkylene glycol having 2 to 6 or more carbon atoms or 6 to 24 or more carbon atoms] Di (meth) acrylate (b3) and a polyhydric alcohol having 3 to 7 or more valences (3 to 50 or more carbon atoms, Mw 76 to 10,000) Poly (meth) acrylate (b4) is used.

  Examples of the dihydric phenol (meth) acrylate (b1) include bisphenol F di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol B di (meth) acrylate, bisphenol AD di (meth) acrylate, and bisphenol S Di (meth) acrylate, halogenated bisphenol A di (meth) acrylate (for example, tetrachlorobisphenol A di (meth) acrylate, etc.), catechin di (meth) acrylate, resorcinol di (meth) acrylate, hydroquinone di (meth) acrylate, 1,5-dihydroxynaphthalenedi (meth) acrylate, dihydroxybiphenyldi (meth) acrylate, octachloro-4,4'-dihydroxybiphenyldi (meth) acrylate, tetramethyl Biphenyl di (meth) acrylate and 9,9'-bis (4-hydroxyphenyl) furo Orange (meth) acrylate.

  Examples of the polyhydric phenol poly (meth) acrylate (b2) include pyrogallol tri (meth) acrylate, dihydroxynaphthyl cresol tri (meth) acrylate, tris (hydroxyphenyl) methane tri (meth) acrylate, and dinaphthyl triol tri (meth) ) Acrylate, tetrakis (4-hydroxyphenyl) ethanetetra (meth) acrylate, trismethyl-tert-butyl-butylhydroxymethanetri (meth) acrylate, 4,4′-oxybis (1,4-phenylethyl) tetracresol (meth) Acrylate, 4,4′-oxybis (1,4-phenylethyl) phenyl (meth) acrylate, bis (dihydroxynaphthalene) tetra (meth) acrylate, and the like can be given.

  Examples of the dihydric alcohol (meth) acrylate (b3) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. ) Acrylate, polyethylene glycol (Mw 150 to 4,000) 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 di (meth) acrylate of an EO and / or PO (1 to 20 mol) adduct of bisphenol A, and the like.

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

  Examples of the monomer (c) having only a vinyloxy group include hydrocarbon compounds having 4 to 20 carbon atoms, such as divinyl ether, divinyloxybenzene, divinyloxytoluene, divinyloxyxylene, trivinyloxybenzene, and 1,2- Examples thereof include divinyloxyethane and the like. In addition, divinyl sulfide, divinyl sulfone, divinyl sulfoxide, and the like can also be used.

  Examples of the monomer (d) having only an allyloxy group include diallyl ether (d1) of dihydric phenol (C6 to C30), polyhydric phenol @ C6 to C50 or more, and Mw of 110 to 5,000. Trivalent to hexavalent or higher polyallyl ether (d2), dihydric alcohol (alkylene glycol having 2 to 6 or more carbon atoms or AO 1 to 90 of dihydric phenol having 6 to 24 or more carbon atoms) Mole adduct) diallyl ether (d3), polyallyl ether (d4) of polyhydric alcohol of 3 to 7 or more (C3 to 50 or more, Mw 76 to 10,000) (d4), divalent A polyallyl ester (d5) of an aromatic polycarboxylic acid having 6 to 6 or more (C6 to 20 or more), and a divalent to hexavalent or more aliphatic or Polyallyl esters of cycloaliphatic polycarboxylic acids (6-20 or more carbon atoms) (d6) or the like can be used.

  Examples of diallyl ether (d1) of dihydric phenol 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, and tetrachlorobisphenol A Diallyl ether, catechin diallyl ether, resorcinol diallyl ether, hydroquinone diallyl ether, 1,5-dihydroxynaphthalene diallyl ether, dihydroxybiphenyl diallyl ether, octachloro-4,4'-dihydroxybiphenyl diallyl ether, tetramethylbiphenyl diallyl ether and 9,9 '-Bis (4-hydroxyphenyl) fluoro orange allyl Le, and the like.

  Examples of the polyallyl ether of polyhydric phenol (d2) include pyrogallol triallyl ether, dihydroxynaphthyl cresol triallyl ether, tris (hydroxyphenyl) methane triallyl ether, dinaphthyltriol triallyl ether, and tetrakis (4-hydroxyphenyl) ) Ethane tetraallyl ether, trismethyl-tert-butyl-butylhydroxymethanetriallyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol allyl ether, 4,4′-oxybis (1,4-phenyl Ethyl) phenylallyl ether and bis (dihydroxynaphthalene) tetraallyl ether.

  Examples of the diallyl ether (d3) of a dihydric alcohol include ethylene glycol diallyl ether, propylene glycol diallyl ether, tetramethylene glycol diallyl ether, 1,6-hexanediol diallyl ether, and polyethylene glycol (Mw 150 to 4,000) diallyl ether. , Polypropylene glycol (Mw 180-5,000) diallyl ether, polytetramethylene glycol (Mw 200-5,000) diallyl ether, neopentyl glycol diallyl ether, and adduct of bisphenol A with EO and / or PO (1-20 mol) Diallyl ether and the like.

  Examples of the polyallyl ether (d4) of a trihydric to heptavalent or higher polyhydric alcohol include trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, sorbitol hexaallyl ether, and poly (polymerization Degree 2 to 5) glycerin polyallyl ether and the like.

Examples of the polyallyl ester (d5) of an aromatic polycarboxylic acid include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and triallyl trimellitate.
Examples of the aliphatic or alicyclic polycarboxylic acid polyallyl ester (d6) include (d5) an aromatic nucleus water additive, diallyl dimer acid, diallyl oxalate, diallyl maleate, diallyl succinate, diallyl Glutarate, diallyl adipate, diallyl pimerate and triallyl tricarballyl ester are exemplified.

  Examples of the monomer (e) having only a propenyloxy group include dipropenyl ether (e1) of dihydric phenol (C6 to C30), polyhydric phenol @ C6 to C50 or more, and Mw of 110 to 5 3,000 trivalent to hexavalent or higher polypropenyl ether (e2), dihydric alcohol (alkylene glycol having 2 to 6 or more carbon atoms or AO1 of dihydric phenol having 6 to 24 or more carbon atoms) ~ 90 mol adduct) dipropenyl ether (e3), polypropenyl ether of trihydric to heptavalent or higher polyhydric alcohol (3 to 50 or more carbon atoms, Mw 76 to 10,000) (e4) A polypropenyl ester (e5) of a divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms); Or more aliphatic or cycloaliphatic polycarboxylic acid (6-20 or more carbon atoms) poly propenyl ester (e6) or the like can be used for.

  Examples of 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 bisphenol A diphenyl. Propenyl ether, tetrachlorobisphenol A dipropenyl ether, catechin dipropenyl ether, resorcinol dipropenyl ether, hydroquinone dipropenyl ether, 1,5-dihydroxynaphthalenedipropenyl ether, dihydroxybiphenyldipropenyl ether, octachloro-4,4'-dihydroxy Biphenyl dipropenyl ether, tetramethyl biphenyl dipropenyl ether and 9 9'-bis (4-hydroxyphenyl) furo Orange propenyl ether and the like.

  Examples of the polypropenyl ether (e2) of polyhydric phenol include pyrogallol tripropenyl ether, dihydroxynaphthyl cresol tripropenyl ether, tris (hydroxyphenyl) methane tripropenyl ether, dinaphthyl triol tripropenyl ether, and tetrakis (4-hydroxyphenyl). ) Ethane tetrapropenyl ether, trismethyl-tert-butyl-butylhydroxymethanetripropenyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresolpropenyl ether, 4,4′-oxybis (1,4-phenyl Ethyl) phenylpropenyl ether and bis (dihydroxynaphthalene) tetrapropenyl ether.

  Examples of 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, and polyethylene glycol (Mw 150 to 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 the EO and / or bisphenol A And dipropenyl ether of PO (1 to 20 mol) adduct.

  Examples of the polypropenyl ether (e4) of a trihydric to heptavalent or higher polyhydric alcohol include, for example, trimethylolpropane tripropenyl ether, glycerin tripropenyl ether, pentaerythritol tetrapropenyl ether, sorbitol hexapropenyl ether and poly (polymerization Degree 2 to 5) glycerin polypropenyl ether and the like.

Examples of the polypropenyl ester of an aromatic polycarboxylic acid (e5) include dipropenyl phthalate, dipropenyl isophthalate, dipropenyl terephthalate, and tripropenyl trimellitate.
Examples of the aliphatic or alicyclic polycarboxylic acid polypropenyl ester (e6) include (d5) an aromatic nucleus water additive, dimer acid dipropenyl ester, dipropenyl oxalate, dipropenyl malate, and dipropenyls. Succinate, dipropenyl glutarate, dipropenyl adipate, dipropenyl pimerate and tripropenyl 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 vinyl cyclohexene monooxide, glycidyl vinyl ether, and butadiene monooxide.

  Examples of the monomer (h) having a (meth) acryloyl group and a vinyloxy group as a crosslinkable functional group include vinyl (meth) acrylate, vinyloxyethyl (meth) acrylate, vinyloxypropyl (meth) acrylate and 3 -Vinyloxy-2-hydroxypropyl (meth) acrylate, 3-vinyloxy-2-chloropropyl (meth) acrylate, vinyloxybutyl (meth) acrylate and vinyloxyhexyl (meth) acrylate. In addition, (h) also includes vinyl ether and alkenyl (meth) acrylate.

Examples of the vinyl ether 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. Can be
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 Oxy-2-chloropropyl (meth) acrylate, octenyloxy (meth) acrylate, decenyloxyhexyl (meth) acrylate and the like can be mentioned.

  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-allyloxy-2- Examples thereof include 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, for example, propenyl (meth) acrylate, propenyloxyethyl (meth) acrylate, propenyloxypropyl (meth) acrylate, 3-propenyloxy- Examples include 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 polyamines (C2-18, amino groups 2-7) (k1), alicyclic polyamines (C4-15, amino groups 2). 3) (k2), polyamide polyamine (k3), polyether polyamine (k4) and the like can be used.

Examples of the aliphatic polyamine (k1) include an alkylenediamine having 2 to 6 carbon atoms, a polyalkylene (2 to 6 carbon atoms) polyamine, an alkyl (1 to 4 carbon atoms) or a hydroxyalkyl (2 to 4 carbon atoms) of the above polyamine. A) Aliphatic or heterocyclic ring-containing aliphatic polyamine (C5 to C18), aromatic ring-containing aliphatic polyamine (C8 to C15) 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 (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, and methyliminobispropylamine.
Examples of the alicyclic or heterocyclic-containing aliphatic polyamine include 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.
Examples of the aromatic ring-containing aliphatic polyamine include xylylenediamine and tetrachloro-p-xylylenediamine.

Examples of the alicyclic polyamine (k2) include 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, and 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline).
Examples of the polyamide polyamine (k3) include, for example, Mw 80 to 2 obtained by condensation of a dicarboxylic acid (such as dimer acid) with an excess (2 moles or more per mole of acid) of a polyamine (such as the above alkylene diamine or polyalkylene polyamine). 2,000 polyamide polyamines and the like are used.
Examples of commercially available polyamide polyamines (trade names) include Polymide (Sanyo Kasei Kogyo), Tomide (Fuji Kasei), Versamide (Henkel Hakusui), Larkamide (Dainippon Ink), and Sanmide (Sanwa Chemical). .

Examples of the polyether polyamine (k4) include hydrides of cyanoethylated polyether polyols (2 to 6 valent, Mw 90 to 2,000) [for example, polyalkylenes (2 to 8 carbon atoms) glycol and the like]. Can be
In the monomer (m) having a secondary amino group, the primary amino group (-NH2 group) in (k) is replaced with -NH-R (R is an alkyl group having 1 to 4 carbon atoms). Those which can be used include, for example, di (methylamino) ethylene, di (ethylamino) hexane and 1,3-di (methylamino) cyclohexane.

Examples of the monomer (n) having only a carboxyl group include divalent to hexavalent or more aromatic polycarboxylic acids (C6 to 20 or more) (n1) and divalent to hexavalent or more. Or an alicyclic polycarboxylic acid (C6 to C20 or more) (n2) or the like.
Examples of the aromatic polycarboxylic acid (n1) include phthalic acid, isophthalic acid, terephthalic acid, hymic acid and trimellitic acid.
As the aliphatic or alicyclic polycarboxylic acid (n2), for example, an aromatic nucleus water additive of (n1), dimer acid, oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid , Tricarballylic acid and dodecenyl succinic acid.

Examples of the monomer (o) having only a hydroxyl group include dihydric phenol (o1) having 6 to 30 carbon atoms and polyhydric phenol (trivalent to 6 carbon atoms having 6 to 50 or more carbon atoms and Mw of 110 to 5,000). (O2) dihydric alcohol (alkylene glycol having 2 to 6 or more carbon atoms or AO 1 to 90 mol adduct of dihydric phenol having 6 to 24 or more carbon atoms) (o3) and 3 A polyhydric alcohol having a valence of 7 to 7 or more (C3 to 50 or more, Mw of 76 to 10,000) (o4) or the like 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- Examples include dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4′-dihydroxybiphenyl, tetramethylbiphenyl, and 9,9′-bis (4-hydroxyphenyl) fluorene.

  Examples of the polyhydric phenol (o2) include pyrogallol, dihydroxynaphthylcresol, tris (hydroxyphenyl) methane, dinaphthyltriol, tetrakis (4-hydroxyphenyl) ethane, trismethyl-tert-butyl-butylhydroxymethane, and 4,4. '-Oxybis (1,4-phenylethyl) tetracresol, 4,4'-oxybis (1,4-phenylethyl) phenyl and bis (dihydroxynaphthalene).

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), and polytetraol. Examples include methylene glycol (Mw 200 to 5,000), neopentyl glycol, and an adduct of bisphenol A with EO and / or PO (1 to 20 mol).
Examples of the polyhydric alcohol (o4) include trimethylolpropane, ditrimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, and poly (polymerization degree 2 to 5) glycerin.

  Examples of the monomer (p) having only an isocyanate group include an aromatic polyisocyanate (p1) having 6 to 20 carbon atoms (excluding the carbon in the NCO group; the same applies hereinafter) and a fatty acid having 2 to 18 carbon atoms. Aromatic polyisocyanate (p2), alicyclic polyisocyanate having 4 to 15 carbon atoms (p3), araliphatic polyisocyanate having 8 to 15 carbon atoms (p4), and modified products of the above polyisocyanates (urethane group, 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, 2,4′- or 4 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Isocyanatodiphenylmethane, crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine] Phosgenated product: polyaryl polyisocyanate (PAPI)], 1 5-naphthylene diisocyanate, 4,4 ', 4 "- triphenylmethane triisocyanate and m- or p- isocyanatophenyl sulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate (p2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. , Lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexano Eat and the like.

Examples of the alicyclic polyisocyanate (p3) include, for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis ( 2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.
Examples of the araliphatic polyisocyanate (p4) include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

  Examples of the modified polyisocyanate (p5) include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. And a mixture of two or more of these [for example, a combined use of a modified MDI and a urethane-modified TDI (isocyanate-containing prepolymer)]. The polyol used in the production of the urethane-modified polyisocyanate [free isocyanate (reactive functional group) -containing resin (prepolymer) obtained by reacting an excess of polyisocyanate (TDI, MDI, etc.) with a polyol] has an equivalent weight 30 to 200 polyols can be used. For example, glycols (such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol), triols (such as trimethylolpropane and glycerin), high-functional polyols (such as pentaerythritol and sorbitol) and their AOs (EO and / or PO 1 to 20 mol) ) Adducts and the like.

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.

  As the monomer (s) having a hydroxyl group and a (meth) acryloyl group, a mono (meth) acrylate (Mw 300 to 3,000) having a polyalkylene (2 to 8 carbon atoms) glycol chain can be used. , Polyethylene glycol (Mw300) mono (meth) acrylate, polypropylene glycol (Mw500) mono (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (Meth) acrylate, pentaerythritol mono (meth) acrylate, polyglycerin (polymerization degree same as above) mono (meth) acrylate and the like.

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, one in which at least a part of the primary amino group (-NH2 group) in (k) is replaced by -NH-R (R is an allyl group) can be used, For example, di (allylamino) ethylene, di (allylamino) propylene, 4,7,10-triazatrideca-1,12-diene, 4,7,10,13-tetraazahexadeca-1,15-diene, di (allylamino) ) Hexane, N, N-diallylxylylenediamine, N, N-di (allylamino) cyclohexane, N, N-diallylisophoronediamine and the like.

  As the monomer (w) having a propenylamino group, a monomer in which at least a part of the primary amino group (-NH2 group) in (k) is replaced by -NH-R (R is a propenyl group) can be used. 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-dipropenylxylylenediamine, 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), more preferably (a), (b) and (f) ), Most preferably (a) and (f). These monomers can be used alone, in combination of two or more, and / or with other copolymerized monomers.

As other copolymerized monomers, the following (aa) to (ww) can be used.
Examples of the monomer (aa) copolymerizable with the monomer (a) having only an epoxy group include a hydrocarbon oxide (aa1) having 4 to 24 carbon atoms and a monoglycidyl ether of a hydrocarbon (3 to 21 carbon atoms). (Aa2), an aliphatic carboxylic acid having 1 to 18 carbon atoms (aa3), an aromatic carboxylic acid having 7 to 18 carbon atoms (aa4), an alcohol having 1 to 18 carbon atoms (aa5), and a phenol having 6 to 18 carbon atoms (Aa6), an aliphatic amine having 1 to 18 carbon atoms (aa7), an aromatic amine having 6 to 18 carbon atoms (aa8) and the like are used.

Examples of the hydrocarbon oxide (aa1) include EO, PO, butene oxide, α-olefin oxides having 5 to 18 carbon atoms (eg, pentane oxide, decene oxide, octadecene oxide, and the like), and styrene oxide.
Examples of the monoglycidyl ether (aa2) of a hydrocarbon (having 4 to 21 carbon atoms) include methyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and octadecyl glycidyl ether. .

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 naphthalene carboxylic 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-, 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 having 4 to 20 carbon atoms (bb1) and a polymerizable unsaturated double having 8 to 18 carbon atoms. Aromatic compound having a bond (bb2), alkyl (meth) acrylate 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 (bb5) ) Etc. are used.
Examples of the olefin (bb1) include ethylene, propylene, butene, 1-octene, 1-decene, 1-eicosene, 6-methyl-1,4: 5,8-dimetano-1,4,4a, 5,6 , 7,8,8a-octahydronaphthalene, norbornene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like.

  Examples of the aromatic compound (bb2) having a polymerizable unsaturated double bond include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, p-decylstyrene, and o-bromo. Styrene, m-bromostyrene, p-iodostyrene, p-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,6-dichlorostyrene, , 6-difluorostyrene, 2,3,4,5,6-pentafluorostyrene, divinylbenzene and the like.

  Examples of the alkyl (meth) acrylate (bb3) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, undecyl (meth) acrylate, octadecyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, 3-methylcyclohexyl (meth) acrylate, cyclopentenyl (meth) acrylate and cyclohexenyl (meth) acrylate.

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, isobonyl vinyl ether, adamantyl vinyl ether, 3-methylcyclohexyl vinyl ether, cyclopentenyl vinyl ether, and cyclohexenyl vinyl ether.

Monomer (cc) copolymerizable with monomer (c) having only vinyloxy group, monomer (dd) copolymerizable with monomer (d) having only allyloxy group, and having only propenyloxy group As the monomer (ee) copolymerizable with the monomer (e), (bb) and the like are used.
As the monomer (ff) copolymerizable with the monomer (f) having an epoxy group and a (meth) acryloyl group, (aa) and (bb) are used.
Examples of the monomer (gg) that can be copolymerized with the monomer (g) having an epoxy group and a vinyl group include (aa) and (bb).
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.

As the monomer (jj) that can be copolymerized with the monomer (j) having a (meth) acryloyl group and a propenyloxy group, (bb) and the like are used.
Examples of the monomer (kk) that can be copolymerized with the monomer (k) having a primary amino group include (aa1) to (aa4).

Examples of the monomer (mm) that can be copolymerized with the monomer (m) having a secondary amino group include (aa1) to (aa4).
As the monomer (nn) that can be copolymerized with the monomer (n) having only a carboxyl group, (aa1), (aa2), and (aa5) to (aa8) are used.
As the monomer (oo) copolymerizable with the monomer (o) having only a hydroxyl group, (aa1) to (aa4) and the like are used.

As the monomer (pp) copolymerizable with the monomer (p) having only an isocyanate group, (aa) and the like are used.
As the monomer (qq) copolymerizable with the monomer (q) having a nitrile group and a vinyloxy group, (bb) and the like are used.
As the monomer (rr) copolymerizable with the monomer (r) having a nitrile group and a (meth) acryloyl group, (bb) and the like are used.
Examples of the monomer (ss) copolymerizable with the monomer (s) having a hydroxyl group and a (meth) acryloyl group include (aa1) to (aa4) and (bb).

As the monomer (tt) that can be copolymerized with the monomer (t) having a (meth) acryloyl group and an isocyanate group, (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). Is used.
As the monomer (vv) that can be copolymerized with the monomer (v) having an allylamino group, (aa1) to (aa4) and (bb) are used.
As the monomer (ww) that can be copolymerized with the monomer (w) having a propenylamino group, (aa1) to (aa4) and (bb) are used.

Among these other comonomer, (aa) and (bb) are preferable, more preferably (bb), particularly preferably (bb1) and (bb2) from the viewpoint of heat resistance, electric properties and resin strength. And (bb3), 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 can be used alone or in combination of two or more.

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

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

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

In addition, a reaction initiator (C) can be used, and (C) is not particularly limited and those used in a usual reaction are used. Depending on the type of a crosslinkable functional group, a radical reaction initiation catalyst ( C1), a cationic polymerization initiation catalyst (C2), an esterification catalyst (C3), an amidation catalyst (C4), an epoxy ring-opening catalyst (C5), an isocyanate reaction catalyst (C6), and the like.
As the radical reaction initiation catalyst (C1), a thermal radical reaction initiation catalyst (C11), a photoradical reaction initiation catalyst (C12) and the like can be used.
From the viewpoint of storage stability, 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, and is preferably a peroxide or an azo compound. Used.

  Examples of the peroxide include t-butylperoxyacetate, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide). Oxy) hexyne-3, cumene hydroperoxide, benzoyl peroxide, bis (t-butylperoxy) diisopropylbenzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxide) Oxy) hexane, t-butylcumyl peroxide, P-menthane hydroperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, dicumyl peroxide and the like.

Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and 1,1′-azobis (1-cyclohexanecarbonitrile). No.
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, and methylbenzoyl phenol. And isopropylthioxanthone.

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

As the cationic polymerization catalyst (C2), a thermal cationic polymerization catalyst (C21) and a photocationic polymerization catalyst (C22) can be used.
As the thermal cationic polymerization catalyst (C21), an onium salt-based catalyst (for example, a triarylsulfonium salt and a diaryliodonium salt) can be used, and for example, San Aid SI series (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be used. No.

  Examples of the photocationic polymerization catalyst (C22) include 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-methyl Ethyl) benzene] -Fe- hexafluorophosphate and diaryliodonium hexafluoroantimonate, and the like.

  These can be easily obtained from the market. For example, SP-150, SP-170 (trade name, manufactured by Asahi Denka Co., Ltd.), Irgacure 261 (trade name, manufactured by Ciba Geigy), UVR-6974, UVR-6990. (Trade name 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.

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

  Examples of the epoxy ring-opening catalyst (C5) include, for example, imidazole catalysts (2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-). 2-methylimidazole and 1-cyanoethyl-2-methylimidazole, etc., tertiary amines (benzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine and DBU And onium salts (manufactured by Sanshin Chemical Industry Co., Ltd., San-Aid SI series, etc.).

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

Further, in order to leave at least two crosslinkable functional groups in the resin (A), a polymerization inhibitor can be used. The polymerization inhibitor is not particularly limited and those 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 and copper (II) chloride.
When a polymerization inhibitor is used, the amount of the polymerization inhibitor used is preferably from 0.1 to 5.0% by weight, more preferably from 0.1 to 2.0% by weight, based on the total weight of the monomers. And particularly preferably 0.5 to 1.0.

(ii) The method of converting a crosslinkable functional group by reacting a monomer having a crosslinkable functional group with a resin having a crosslinkable functional group is not particularly limited, and an ordinary method can be applied. A method of producing a resin having a reactive functional group by using the compound (qw) and reacting the monomer (kp) to convert the resin, or a method of preparing the crosslinkable functional group produced by the method (i). A method of reacting a monomer (a-j) or a monomer (qw) with a resin having at least two resins can be applied.
The reaction temperature, aging time, solvent, reaction initiator (C) and polymerization inhibitor are the same as in the method (i).
For example, by subjecting a resin obtained by copolymerizing hydroxyethyl (meth) acrylate (20 to 80 parts by weight) and styrene (80 to 20 parts by weight) to an esterification reaction of (meth) acrylic acid, A hydroxyl group can be converted to a (meth) acryloyl group.

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

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

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

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

  Examples of the polyepoxide (y) include glycidyl ether of vinylcyclohexene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, phenol or cresol novolak resin (Mw 400 to 3,000), and limonene phenol novolak resin (Mw 400 3,000) glycidyl ether, polyglycidyl ether of polyphenol (Mw 400 to 3,000) obtained by condensation reaction of phenol with glyoxal, glutaraldehyde or formaldehyde, Mw 400 to 3,000 obtained by condensation reaction of resorcinol and acetone. Polyglycidyl ether of 3,000 polyphenols, (co) polymer of glycidyl (meth) acrylate (polymerization degree is, for example, 2 to 10), epoxy equivalent of 130 to , 000 epoxidized polybutadiene (Mw170~3000), and epoxidized soybean oil (Mw170~3,000), and the like.

Examples of the curing agent (z) include a monomer (n) having only a carboxyl group, an acid anhydride of an aliphatic carboxylic acid (aa3) or an aromatic carboxylic acid (aa4), and the like.
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), more preferably (a), (b), (n), (f), (G) and (s), particularly preferably (a), (b), (n) and (f).
When a monoepoxide (x), a polyepoxide (y), a curing agent (z), or the like is used, the amount of these used is not particularly limited, but from the viewpoint of heat resistance and resin strength, the weight of all monomers used is reduced. On the basis thereof, it is preferably 20 to 80% by weight, 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 preferably from 10 to 95: 5 to 90, more preferably from 20 to 90:10 to 80, particularly preferably from 30 to 80:20 to 70. is there.

The curable film of the present invention may contain other additives (D), other resins (E), rubbers (F), fillers (G), and the like.
Examples of the other additives (D) include a phenolic antioxidant, a phosphorus antioxidant, a flame retardant, a phenolic thermal deterioration inhibitor, a benzophenone ultraviolet stabilizer, and an antistatic agent.
When (D) is used, the content of (D) is the total weight of (A) and (B) divided by the weight of only (A) when (B) is not used. The same applies hereinafter. Based on｝, it is preferably 0.001 to 3.0% by weight, more preferably 0.01 to 2.0% by weight, and particularly preferably 0.05 to 1.0% by weight.

As the other resin (E), those used for ordinary insulators can be used. For example, ABS resin, polystyrene, polycarbonate, polyamide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyimide, polysulfone , Polyether sulfones and polyarylates.
The Mw of the other resin is preferably from 10,000 to 500,000, more preferably from 20,000 to 100,000, particularly preferably from 40,000 to 60,000.
When (E) is used, the content of (E) is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, particularly preferably from 1 to 10% by weight, based on the total weight of (A) and (B). Preferably it is 2 to 8% by weight, most preferably 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.
The elongation of rubber (JIS K6301 (1995) 3. Tensile test) is preferably from 500 to 2,000%, more preferably from 700 to 1,500%, particularly preferably from 800 to 1,000%.
When (F) is used, the content of (F) is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably, based on the total weight of (A) and (B). 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 preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably, based on the total weight of (A) and (B). 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 50 μm. .

The curable film of the present invention is obtained by uniformly mixing (A) and, if necessary, (B) to (G) and / or a solvent by a usual method, and then using a usual molding method, for example, a curtain coater or a knife. It can be produced by a method of applying to a support or a substrate using a coater, a spray gun, a roll coater, a spin coater, a dispenser, a bar coater, a screen printer, or the like, or a dipping method or an injection molding method.
Among these molding apparatuses, a method using a curtain coater, a knife coater, a spray gun or a roll coater is preferable, a method using a curtain coater or a knife coater is more preferable, and a method using a knife coater is particularly preferable.

At the time of film formation, the viscosity can be adjusted using a solvent or the like, if necessary.
The solvent is not particularly limited as long as it can dissolve, emulsify, or disperse the curable resin composition containing (A). For example, a solvent that can be used when producing the curable resin (A) is used It is.
When a solvent is used, the solvent may not be removed in the polymerization of (A) and may be left as it is. The same or different solvent as used in (1) may be added, or (B) and the solvent may be mixed and mixed 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 easily forms a film. %, More preferably from 10 to 80% by weight, particularly preferably from 30 to 70% by weight.

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

When a support is used, the film on the support can be transferred to a substrate or the like, and when the substrate or the like is used, it can be cured as it is.
After the application of the composition, heating is preferably performed for the purpose of drying the solvent and the like. The heating conditions are, for example, temperature: 10 to 150 ° C (preferably 20 to 120 ° C) and time: 1 to 60 minutes (preferably 2 to 40 minutes).
The curable film of the present invention is easily softened by heating (hot press or the like), has good penetration into minute portions (such as uneven portions) of a base material, and has excellent workability.

(2) Regarding the second and third aspects of the present invention The difference between the solubility parameter (hereinafter abbreviated as SP) value of the curable resin composition (X) and the thermoplastic resin (Y) is 0.5 to 3 0.0, preferably 0.6 to 2.5, more preferably 0.7 to 2.0, particularly preferably 0.8 to 1.8, still more preferably 0.9 to 1.5, and most preferably 0.9 to 1.5. Preferably it is 1.0 to 1.2. When the solubility parameter is in this range, an insulator excellent in thermal shock resistance can be easily obtained.
The SP value of the curable resin composition (X) is preferably from 5.0 to 12.0, more preferably from 6.0 to 11.5, particularly preferably from 7.0 to 11.0, and still more preferably from 8 to 1. 0.0 to 10.5, most preferably 9.0 to 10.0.

The SP value is represented by the following equation.
In the formula, ΔH represents the heat of molar evaporation (cal), and V represents the molar volume (cm 3). ΔH and V are the sum of the molar evaporation heats (△ ei) of the atomic groups described in “POLYMER ENGINEERING AND FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. The sum (V) of (ΔH) and molar volume (△ vi) can be used.
Mw of (Y) is from 3,000 to 1,000,000, preferably from 5,000 to 800,000, more preferably from 10,000 to 600,000, and particularly preferably from 50,000 to 400,000. , Most preferably from 60,000 to 100,000.

The dielectric constant after curing of (X) is preferably 3.5 or less, more preferably 2 to 3.5, particularly preferably 2.2 to 3.4, and still more preferably 2.4 to 3.3. Most preferably, it is 2.7-3.2.
When the dielectric constant after curing is in this range, the reliability is further improved when used as an insulator, and when applied to an integrated circuit of electronic components, signal delay hardly occurs and the performance of the circuit is easily improved. Tends to be.
The curing conditions and the method of measuring the dielectric constant are the same as those of the curable resin (A).
The boiling water absorption after curing of (X) is preferably 3% or less, more preferably 3.00 to 0.001, and particularly preferably 2.5 to 0.005 from the viewpoint of thermal shock resistance and electrical insulation. , Most preferably 2 to 0.001%.
The curing conditions are the same as for the dielectric constant after curing. The boiling water absorption is measured in accordance with JIS K7209 (2000) 6.3B method.

The dielectric constant of the curable resin material after curing is preferably 2.4 to 3.2, more preferably 2.5 to 3.2, particularly preferably 2.5 to 3.0, and still more preferably 2. 6 to 2.9, most preferably 2.6 to 2.8. When the dielectric constant after curing is in this range, the reliability is further improved when used as an insulator, and when applied to an integrated circuit of electronic components, signal delay hardly occurs and the performance of the circuit is easily improved. Tends to be.
The curing conditions and the method of measuring the dielectric constant are the same as those of the curable resin (A).

As the curable resin composition (X), a resin curable 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 (X1) containing the curable resin (A) and the low molecular weight compound (B) described above.
(2) a copolymer (H) having α-olefin (Ha) and cyclic olefin (Hb) as structural units and having a carbon-carbon double bond, and a carbon-carbon double bond Curable resin composition (X2) comprising, as an essential component, a crosslinking agent (I) having

  (3) Monomer (f) having an epoxy group and a (meth) acryloyl group, monomer (g) having an epoxy group and a vinyl group, monomer having a (meth) acryloyl group and a vinyloxy group (H), a monomer (i) having a (meth) acryloyl group and an allyloxy group, a monomer (j) having a (meth) acryloyl group and a propenyloxy group, and a monomer (v) having an allylamino group ) And at least one monomer (fgw) selected from the group consisting of monomers (w) having a propenylamino group; and a monomer (345) represented by Formulas (3) to (5): If necessary, an aromatic compound (bb2) having a polymerizable unsaturated double bond having 8 to 18 carbon atoms, an alkyl (meth) acrylate (bb3) having 5 to 22 carbon atoms, and a vinyl ether having 4 to 20 carbon atoms ( bb5) A curable resin composition (X3) comprising a copolymer (J) with at least one monomer (bb235) selected from the group, wherein the (J) has a Mw of 2,000 to 1,000,000. .

(3) In the formula, n represents an integer of 1 to 10.

(4) In the formula, 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.

(5) In the formula, 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) 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 from 0.001 to 3.0% by weight, more preferably from 0.01 to 3.0% by weight, based on the total weight of (A) and (B). 2.0% by weight, particularly preferably 0.05 to 1.0% by weight.
When (E) is used, the content of (E) is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, particularly preferably from 1 to 10% by weight, based on the total weight of (A) and (B). Preferably it is 2 to 8% by weight, most preferably 3 to 5% by weight.
When (F) is used, the content of (F) is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably, based on the total weight of (A) and (B). 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, and particularly preferably, based on the total weight of (A) and (B). 8 to 30% by weight.

Further, (X1) can contain a solvent.
As the solvent, the same solvents as those used in the polymerization of (A) can be used.
(X1) may be used as it is without removing the solvent at the time of the polymerization of (A), and after removing the solvent at the time of the polymerization of (A), it is used for the polymerization of (A) at the time of producing (X1). The same or different solvents may be added, or (B) and the solvent may be mixed and mixed with (A).
When a solvent is used, the content of the solvent is preferably from 5 to 90% by weight, more preferably from 10 to 80% by weight, based on the total weight of (A) (the weight not including the solvent) and (B). And particularly preferably 30 to 70% by weight.

(X1) can be easily produced by uniformly mixing (A) and (B), and if necessary, (D) to (G) and / or a solvent by an ordinary method. It can be manufactured by the methods 1) to 3).
(1) A method in which (A) and (B) are blended and then (D) to (G) and / or a solvent are mixed as necessary.
(2) A method in which (A) is blended with (D) to (G) and / or a solvent as required, and then (B) is mixed.
(3) A method of simultaneously mixing (A) and (B) with (D) to (G) and / or a solvent as necessary.

  As a method of adjusting the dielectric constant after curing of (X1), there is a method of adjusting according to the type of a monomer which is a production raw material of (A), and for example, ethylene, propylene, butadiene, isoprene, carbon number 4 or more The dielectric constant tends to decrease when the content ratio of all the monomers such as (meth) acrylate and styrene increases, and the dielectric constant tends to increase when the content of (meth) acrylic acid and acrylonitrile increases. It is in. 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 mixture (equivalent ratio) 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 novolak resin (2- to 8-nuclear), styrene / glycidyl (meth) acrylate = 10-55 / 90- Mixing 45 parts by mass of bisphenol A diglycidyl ether Things, a mixture of styrene / glycidyl (meth) acrylate = 10 to 55/90 to 45 parts by weight of phenol Bono rack polyglycidyl ether.

Next, the curable resin composition (X2) will be described.
The carbon number of the α-olefin (Ha) is preferably 2 to 20, more preferably 3 to 18, and particularly preferably 3 to 12.
Examples of (Ha) include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-hexene. Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.
The number of carbon-carbon double bonds of 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 (Hb1) represented by the formula (6), a cyclic olefin (Hb2) represented by the formula (7), a cyclic olefin (Hb3) represented by the formula (8), and These mixtures and the like are used.

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.
Examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a butyl group and a t-butyl group.
As R ^{7 to} R ¹⁷ , a hydrogen atom, a methyl group and an ethyl group are preferable from the viewpoint of heat resistance.
N represents an integer of 0 to 5, and preferably an integer of 0 to 2 from the viewpoint of mechanical strength (tensile strength, tensile elongation, and the like).
Examples of (Hb1) include dicyclopentadiene (in the case where n is 0 and all of R ^{7 to} R ¹⁷ are hydrogen atoms in the formula (6)), tricyclopentadiene (in the formula (6), 1, and all of R ^{7 to} R ¹⁷ are hydrogen atoms) and tetracyclopentadiene (where n is 2 in the formula (6) and all of R ^{7 to} R ¹⁷ are hydrogen atoms).

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

In the formula (8), R ^{22 to} R ²⁹ are the same as R ^{7 to} R ^{17 in} the formula (6), and the preferred range is also the same.
R ³⁰ and R ³¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 (preferably 1 to 2) carbon atoms.
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.
As R ³⁰ and R ³¹ , a methyl group, an ethyl group, an ethylidene group and a vinylidene group are preferred from the viewpoint of heat resistance.

M represents an integer of 0 to 5, and preferably 0 to 2 from the viewpoint of mechanical strength (tensile strength, tensile elongation, etc.).
(Hb3) includes, for example, 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene and 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,5. 8,8a-octahydronaphthalene and the like.
Of these (Hb), (Hb3) is preferred, and more preferably 5-ethylidene-2-norbornene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,5. 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, and particularly preferably 30/70 to 60/40. . When it is in this range, the thermal shock resistance of the cured resin tends to be further improved.

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

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

Examples of the (meth) acrylate include a monomer (b) having only a (meth) acryloyl group, a monomer (f) having an epoxy group and a (meth) acryloyl group, and a (meth) acryloyl group and a vinyloxy group. Monomer (h), monomer (i) having a (meth) acryloyl group and an allyloxy group, monomer (j) having a (meth) acryloyl group and a propenyloxy group, hydroxyl group and (meth) Monomer (s) having an acryloyl group, monomer (t) having a (meth) acryloyl group and an isocyanate group, monomer (u) having a (meth) acryloyl group and a carboxyl group, (meth) ) Acrylic acid alkyl esters (bb3) and phenoxy group-containing (meth) acrylates are used.
Examples of the phenoxy group-containing (meth) acrylate include phenoxyethyl (meth) acrylate, (meth) acrylate of a phenol EO 2 mol adduct, and (meth) acrylate of a phenol EO 2 mol PO 2 mol adduct.

Examples of the unsaturated hydrocarbon include an aromatic compound having a polymerizable unsaturated double bond (bb2), an α-olefin (Ha), an aliphatic non-conjugated polyene having 5 to 10 carbon atoms, and a cyclic olefin having 5 to 10 carbon atoms. And cyclic olefin oligomers.
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.

  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, trimer and tetramer of cyclopentadiene, 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-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and 1,4: 5,10: 6,9-trimethano-1,2,3,3 4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene and the like.

  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). be able to.

Examples of the alkenyl ether include vinyl ether having 4 to 10 carbon atoms, propenyl ether having 5 to 12 carbon atoms, and allyl ether having 5 to 12 carbon atoms.
Examples of the vinyl ether 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.

  As propenyl ethers, for example, 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 dipropenyl ether And the like.

  Examples of the allyl ether include ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether, propylene glycol diallyl ether, dipropylene glycol diallyl ether, and butylene glycol diallyl ether.

(I) preferably contains 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 ether. And more preferably cyclic olefins, cyclic olefin oligomers, vinyl ethers, propenyl ethers and allyl ethers, particularly preferably propenyl ethers.
The boiling point of (I) is preferably at least 250 ° C, more preferably 250 to 350 ° C, and particularly preferably 280 to 300 ° C.

These crosslinking agents (I) can be used alone or in combination of two or more.
In addition, since the copolymer (H) itself has at least one carbon-carbon double bond, a part thereof acts as a cross-linking agent, and the (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 from 99/1 to 20/80, more preferably from 90/10 to 40/60, and particularly preferably from 85/15 to 50/50. .
Within this range, crosslinking will proceed sufficiently, and the cured resin will tend to have better thermal shock resistance.

(X2) 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 from 0.001 to 3.0% by weight, more preferably from 0.01 to 3.0% by weight, based on the total weight of (H) and (I). 2.0% by weight, particularly preferably 0.05 to 1.0% by weight.
When (E) is used, the content of (E) is preferably from 1 to 45% by weight, more preferably from 5 to 40% by weight, and particularly preferably based on the total weight of (H) and (I). Is 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, and particularly preferably, based on the total weight of (H) and (I). Is 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, and particularly preferably, based on the total weight of (H) and (I). Is 8 to 30% by weight.

Further, (X2) can contain a solvent.
As the solvent, the same solvents as those used in the polymerization of (A) can be used.
When a solvent is used, the content of the solvent is preferably from 5 to 90% by weight, more preferably from 10 to 80% by weight, based on the total weight of (H) (the weight not containing the solvent) and (I). And particularly preferably 30 to 70% by weight.

(X2) can be easily produced by uniformly mixing (H) and (I), and if necessary, (D) to (G) and / or a solvent by a usual method. It can be manufactured by the methods 1) to 3).
(1) A method in which (H) and (I) are blended, and then (D) to (G) and / or a solvent are mixed as necessary.
(2) A method in which (H) is mixed with (D) to (G) and / or a solvent as required, and then (I) is mixed.
(3) A method of simultaneously mixing (H) and (I) with (D) to (G) and / or a solvent if necessary.

As a method of adjusting the dielectric constant after curing of (X2), a method of adjusting the dielectric constant according to the type of the crosslinking agent (I), for example, when the content of α-olefin, cyclic olefin and cyclic olefin oligomer is increased, the dielectric constant is increased. Tends to decrease, and when the content of (meth) acrylate, alkenyl ether and the like increases, the dielectric constant tends to increase.
Examples of a composition having a dielectric constant of 2 to 3.5 include a mixture of 1-hexene / 5-ethylidene-2-norbornene copolymer and ethylene glycol diallyl ether, and 1-hexene / 5-ethylidene-2-norbornene. Mixture of copolymer and ethylene glycol dimethacrylate, mixture of 1-hexene / dicyclopentadiene copolymer and ethylene glycol diallyl ether, mixture of 1-hexene / dicyclopentadiene copolymer and ethylene glycol dimethacrylate, etc. Is mentioned.

Next, the curable resin composition (X3) will be described.
The monomer (345) represented by the formulas (3) to (5) will be described in order.
In the formula (3), n is preferably an integer of 2 to 6, more preferably an integer of 2 to 4.
Examples of the monomer represented by the formula (3) include perfluoromethyl perfluorovinyl ether, perfluoroethyl perfluorovinyl ether, perfluoropropyl perfluorovinyl ether, perfluoroisobutyl perfluorovinyl ether, perfluorohexyl perfluorovinyl ether and 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 preferably Perfluoromethyl perfluorovinyl ether, perfluoroethyl perfluorovinyl ether, perfluoropropyl perfluorovinyl ether and perfluoroisobutyl perfluorovinyl ether.

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

In the formula (5), R3 and R4 are preferably a fluorine atom, and R5 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, tetrafluoroethylene, and hexafluoropropylene.
Of these, from the viewpoint of the dielectric constant, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene are preferable, 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, and from the viewpoints of dielectric constant and heat resistance, styrene, o-methylstyrene, p-methylstyrene, o-fluorostyrene, and m are more preferable. -Fluorostyrene, p-fluorostyrene, 2,6-difluorostyrene and 2,3,4,5,6-pentafluorostyrene.

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

From the viewpoints of dielectric constant, heat resistance and processability, a multi-component copolymer is preferable, a polymer having (f) and / or (g) as an essential constituent monomer, particularly preferably (f) and And / or (g) a polymer containing monomer (4) as an essential constituent monomer, more preferably (f) and / or (g), monomer (4),
And if necessary, a polymer consisting of (bb2), (bb3) and / or (bb5), (f) and / or (g), monomers (3) and (4), and optionally (b)
b2), a polymer consisting of (bb3) and / or (bb5), and (f) and / or (g), monomers (4) and (5), and if necessary, (bb2), (bb3)
And / or a polymer consisting of (bb5), most preferably (f) and / or (g)
, A polymer consisting of monomer (4) and (bb2), (f) and / or (g)
A polymer consisting of monomers (3) and (4) and (bb2); and (f)
And / or (g), monomers (4) and (5), and (bb2).

The weight ratio of monomer (fgw) / monomer (345) is preferably 5/95 to 95/5, more preferably 20/80 to 70/30, and particularly preferably 30/70 to 60/40. is there.
In the case of a multi-component copolymer, from the viewpoint of the dielectric constant, it is preferable that the weight ratio of the monomer (345) is higher. When the monomer (bb235) is used, the monomer (fgw) / monomer (bb235) )) Is preferably from 10/90 to 95/5, more preferably from 30/70 to 90/10, and particularly preferably from 40/60 to 80/20.
The bonding form of these copolymers (J) may be any of block, random and combinations thereof.
The total number of epoxy groups and alkenyl ether groups in the copolymer (J) is preferably 2 to 3,000, more preferably 3 to 1,000, particularly preferably 5 to 500, and most preferably 10 to 500. There are 200.
Mw of (J) is preferably from 2,000 to 1,000,000, more preferably from 3,000 to 700,000, and particularly preferably from 50,000 to 400,000.

  (J) can be easily obtained by copolymerizing the monomer (fgw), the monomer (345) and, if necessary, the monomer (bb235). The polymerization method used in (X1) The same method as the polymerization method (A) is used.

(X3) 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 from 0.001 to 3.0% by weight, more preferably from 0.01 to 2.0% by weight, based on the weight of the copolymer (J). %, Particularly preferably 0.05 to 1.0% by weight.

  When (E) is used, the content of (E) is preferably from 1 to 45% by weight, more preferably from 5 to 40% by weight, particularly preferably from 10 to 40% by weight, based on the weight of the copolymer (J). 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, and particularly preferably 8 to 10% by weight, based on the weight of the copolymer (J). 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, and particularly preferably 8 to 10% by weight, based on the weight of the copolymer (J). 30% by weight.

Further, (X3) can contain a solvent.
As the solvent, the same solvents as those 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 the copolymer (J). is there.

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

As a method of adjusting the dielectric constant after curing of (X3), there is a method of adjusting according to the type of the monomer (ggw), the monomer (345) and the monomer (bb235). , (G) and (bb2) tend to increase the dielectric constant.
Examples of the composition having a dielectric constant of 2 to 3.5 include styrene / propenoxyethyl methacrylate copolymer (weight ratio: 45 to 90/55 to 10), 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 still more preferably 2.0 to 2.6. 5, most preferably 2.1 to 2.3. When the dielectric constant is within this range, the reliability is further improved when used as an insulator, and when applied to an integrated circuit of an electronic component, a signal delay hardly occurs and the performance of the circuit tends to be easily improved. is there.
The curing conditions and the method of measuring the dielectric constant are the same as those of the curable resin (A).

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

When the content of the carbon-carbon double bond or carbon-nitrogen bond is less than this range, the thermoplastic resin on the surface of the insulating layer is hardly eluted by the oxidizing agent, and it is difficult for fine irregularities to be formed. Properties tend not to be good. 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 carbon-nitrogen bond may be present in the main chain skeleton or side chain skeleton of the resin as long as it is present in (Y), but is present in the main chain skeleton of the resin. Is preferred.

As (Y), a thermoplastic resin (Y1) having a carbon-carbon double bond, a thermoplastic resin (Y2) having a carbon-nitrogen bond, and the like can be used.
As the thermoplastic resin (Y1) having a carbon-carbon double bond, (b1), (b3), (c), (d1), (d3), (e1) and / or (e3) are essential constituents. A (co) polymer or the like as a monomer is used.
In the case of copolymers, these copolymers may be of a random type or a block type.

Other copolymerizable monomers can be used for (Y1) in addition to the essential constituent monomers.
Other comonomers include (b2), (b4), (d2), (d4), (d5), (d6), (e2), (e4), (e5), (e6), (F), (g), (h), (i), (j), (q), (r), (s), (t), (u), (v), (w) and (bb) ) And the like.

When using another comonomer, the content of the other comonomer is not particularly limited, but from the viewpoint of heat resistance and resin strength, based on the weight of all used monomers, It is preferably from 20 to 80% by weight, more preferably from 35 to 70% by weight, particularly preferably from 50 to 60% by weight.
(Y1) can be easily obtained by the same method as the polymerization method of (A) used in (X1).

  As (Y1), for example, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, and ring-opening polymer of norbornene can be easily obtained as the following commercially available products. Available.

  Examples of commercially available products (trade names) include JSR BR series (manufactured by JSR) as polybutadiene, JSR IR series (manufactured by JSR) as polyisoprene, and JSR TR series (manufactured by JSR) as styrene-butadiene copolymer. Examples of the styrene-isoprene copolymer include the JSR SIS series (manufactured by JSR), and examples of the norbornene ring-opening polymer include the Nosorex series (manufactured by JSR).

Examples of the thermoplastic resin (Y2) having a carbon-nitrogen bond include polyamide, polyurethane, polyurea, polyimide, polyamino acid, and a reaction product of a bifunctional epoxy and a monofunctional primary amine.
As the polyamide, a polyamide obtained by reacting a diamine having 2 to 18 carbon atoms with a dicarboxylic acid having 6 to 20 carbon atoms or more is 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 to obtain the polyamide, other than diamine and dicarboxylic acid, other than diamine in (k) and (m), other than dicarboxylic acid in (aa7), (aa8) and (n), for the purpose of adjusting the molecular weight, etc. , (Aa3) and (aa4) can also be used.

As the polyurethane, those obtained by reacting a dihydric phenol or dihydric alcohol having 2 to 100 or more carbon atoms with a diisocyanate having 6 to 20 carbon atoms are used.
Examples of the dihydric phenol include (o1), and examples of the dihydric alcohol include (o3).
Examples of the diisocyanate include the diisocyanate in (p).
In the reaction for obtaining the polyurethane, for the purpose of adjusting the molecular weight or the like, other than the diisocyanate in (o2), (o4) and (p) can be used.

As the polyurea, those obtained from the reaction of a diamine having 2 to 18 carbon atoms and 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).
In the reaction for obtaining polyurea, for the purpose of adjusting the molecular weight, etc., other than diamine in (k) and (m), and other than diisocyanate in (aa7), (aa8) and (p) can be used. .

As the polyimide, a polyimide obtained by reacting a diamine having 2 to 18 carbon atoms with a polycarboxylic acid having 6 to 20 carbon atoms or more is used.
Examples of the diamine include the diamines in (k) and (m).
Examples of the polycarboxylic acid include (n).
In the reaction for obtaining the polyimide, other than the diamine in (k) and (m), (aa7), (aa8), (aa3) and (aa4) can be used for the purpose of adjusting the molecular weight and the like.

As the polyamino acid, a condensate of an aminocarboxylic acid having 2 to 12 carbon atoms and a ring-opening polymer of a lactam having 6 to 12 carbon atoms can be used.
Examples of the aminocarboxylic acid include amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocaprin Acids, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Examples of the lactam include caprolactam, enantholactam, laurolactam, and undecanolactam.
In the reaction for obtaining a polyamino acid, (k), (m), (aa7), (aa8), (n), (aa3) and (aa4) can be used for the purpose of adjusting the molecular weight and the like.

Examples of the bifunctional epoxy include divalent glycidyl esters in (a11), (a13) and (a2), divalent glycidylamine in (a3) and divalent epoxide in (a4). Can be
Examples of the monofunctional primary amine include the primary amines in (aa7) and (aa8).
In the reaction between the bifunctional epoxy and the monofunctional primary amine, (a), (k), (m), (n), (p), (p), etc. Can also be used.
(Y2) can be easily obtained by the same method as the polymerization method of (A) used in (X1).

  Of these (Y), from the viewpoint of the dielectric constant, (Y1) and a reaction product of a bifunctional epoxy and a monofunctional primary amine are preferable, and polybutadiene, polyisoprene, a styrene-butadiene copolymer, and styrene are more preferable. -Isoprene copolymer, ring-opening polymer of norbornene, and reaction product of bifunctional epoxy and 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). Particularly preferably, it is 0.05 to 1.0% by weight.

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

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

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

Further, (Y) can contain a solvent.
As the solvent, the same solvents as those 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, if necessary, uniformly mixing (D) to (G) and / or a solvent with a usual method.
As a method of adjusting the dielectric constant of (Y), in the case of (Y1), a method of adjusting the amount of the raw material used in (Y1), for example, when the content of butadiene or the like is increased, the dielectric constant tends to decrease. Yes, increasing the amount of styrene or the like tends to increase the dielectric constant.
In the case of (Y2), a method of adjusting the amount of the raw material used in (Y2), for example, using a diamine, dicarboxylic acid, monoalkylamine or the like having a relatively large number of carbon atoms tends to lower the dielectric constant. When a diamine, dicarboxylic acid, monoalkylamine or the like having a relatively small number of carbon atoms is used, the dielectric constant tends to increase.
Examples of the composition having a dielectric constant of the curable resin material of 2 to 3.5 include styrene / butadiene copolymer, styrene / butadiene / acrylonitrile copolymer, and bisphenol A / monododecylamine copolymer. .

The weight ratio of (X) / (Y) is preferably from 40 to 98/2 to 60, more preferably from 65 to 96/4 to 35, from the viewpoint of resin strength, as a weight ratio containing no solvent (in terms of pure components). From the viewpoint of heat resistance, it is particularly preferably from 70 to 90/10 to 30, most preferably from 80 to 85/15 to 20.
The curable resin material may contain a curing catalyst (C) if necessary.
(C) may be added immediately before the use of the curable resin material, or may be added during the production of the curable resin material.
When (C) is used, the content of (C) (excluding those used in adjusting (A), (X1), (X2) and (X3)) is (X) and (Y) 0.001 to 10% by weight, more preferably 0.01 to 8.0% by weight, particularly preferably 0.05 to 5.0% by weight, and most preferably 0.1 to 2% by weight, based on the weight of 0.0% by weight.

The curable resin material may contain another additive (D), another resin (E), a rubber (F), a filler (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 (X) and (Y). 0% by weight, 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, and particularly preferably based on the total weight of (X) and (Y). It is 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, and particularly preferably 8 based on the weight of (X) and (Y). ２５25% by weight.

  When (G) is used, the content of (G) is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 8 based on the weight of (X) and (Y). ３０30% by weight.

Further, the curable resin material can contain a solvent.
As the solvent, the same solvents as those 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 (X) and (Y). It is.

The curable resin material may be composed of (X) and (Y), but (Y) is preferably present uniformly in (X), and (Y) is preferably present in (X). It is preferred that they are uniformly dispersed.
When (Y) is dispersed in (X), the dispersion average particle size of (Y) is not particularly limited, but is preferably from 0.001 to 50 μm, and more preferably from the viewpoint of resin strength. From 0.005 to 20 μm, particularly preferably 0.01 to 10 μm, from the viewpoint of adhesion, more preferably 0.05 to 5 μm, most preferably 0.1 to 2 μm.
The dispersion average particle diameter is obtained by subjecting a curable resin material to a curing treatment 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. Can be

The curable resin material only needs to be uniformly mixed with (X) and (Y) and, if necessary, (C) to (G) and / or a solvent, and can be easily produced by a usual method. The following method can be applied.
(1) A method of uniformly dissolving (X) and (Y) and, if necessary, (C) to (G) in a solvent, and then removing the solvent by an appropriate method.
(2) A method of dissolving (Y) and, if necessary, (C) to (G) in a solvent, polymerizing (X) in this solution, and removing the solvent by an appropriate method.
(3) A method of dissolving (A), (B) and (Y) and (C) to (G) as required in a solvent, and then removing the solvent by an appropriate method.
(4) A method of uniformly dissolving (H), (I) and (Y) and, if necessary, (C) to (G) in a solvent, and then removing the solvent by an appropriate method.
The solvent is not particularly limited as long as it can dissolve both resins. For example, a solvent used in the production of (A) can be used.
No special operation is required for dissolution, polymerization, and solvent removal, but it is preferable to add stirring at 1,000 to 20,000 rpm.

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 50 μm. .
The curable film of the present invention can be produced in the same manner as the first of the present invention, and the preferable range and the like are also the same.

(3) Tensile elastic modulus after curing of the curable film of the present invention for a fourth of the present invention may if 100~250Kgf / mm ^2, preferably 110~240Kgf / mm ^2, more preferably 120 to 230 kgf / mm ² , particularly preferably 130 to 220 kgf / mm ² , particularly preferably 140 to 210 kgf / mm ² , most preferably 150 to 200 kgf / mm ² . When the tensile modulus is in this range, an insulator excellent in thermal shock resistance and the like can be easily obtained.
The tensile modulus is measured according to JIS K7113 (1995).
The dielectric constant of the curable film after curing may be 3.5 or less, but is preferably 1.9 to 3.5, more preferably 2.0 to 3.4, and particularly preferably 2.0 to 3.3. 3, particularly preferably 2.1 to 3.3, most preferably 2.1 to 3.2.
The curing conditions for the curable film are the same as the curing conditions for the dielectric constant.
The composition constituting the curable film of the present invention contains a curable polymer compound.

  The Mw of the curable polymer compound may be 10,000 to 1,000,000, but is preferably 20,000 to 500,000, more preferably 30,000 to 100,000, and particularly preferably 40,000. -500,000, more preferably 50,000-200,000, particularly preferably 60,000-100,000. When Mw is in this range, an insulator excellent in 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-described curable resin materials and the like can be used, and a curable resin material containing (X1) is particularly 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 to 70 μm, particularly preferably 15 to 60 μm, and most preferably 20 to 50 μm. .
The curable film of the present invention can be produced in the same manner as the first of the present invention, and the preferable range and the like are also the same.

(4) the tensile modulus of the insulation of the present invention the fifth invention, 100~250Kgf / mm may be a ^2, but preferably 110~240Kgf / mm ^2, more preferably 120~230Kgf / mm ² , particularly preferably 130~220Kgf / mm ^2, more particularly preferably 140~210Kgf / mm ^2, and most preferably 150~200Kgf / mm2. When the tensile modulus is in this range, the thermal shock resistance is excellent.
The tensile modulus is measured according to JIS K7113 (1995).
The thermal expansion coefficient (α1) of the insulator of the present invention may be 30 to 50 ppm, but is preferably 31 to 49 ppm, more preferably 32 to 48 ppm, particularly preferably 35 to 47 ppm, and still more preferably 38 to 46 ppm. , Most preferably from 40 to 45 ppm. When the coefficient of thermal expansion is in 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, a cured film having a thickness of 40 μm is cut into 20 mm × 2 mm, a load of 5 g is applied, and the temperature is raised from room temperature (about 25 ° C.) to 250 ° C. at a speed of 10 ° C./min. Find the rate.
The dielectric constant of the insulator of the present invention is preferably 3.5 or less, more preferably 1.9 to 3.5, particularly preferably 2.0 to 3.4, and still more preferably 2.0 to 3.3. , More preferably 2.1 to 3.3, most preferably 2.1 to 3.2.
The insulator of the present invention is a curable film (first of the present invention) containing the curable resin (A), a curable film of the curable resin material (second or third of the present invention) or It can be easily manufactured by heat-curing a curable film (the fourth of the present invention) and the like.
The conditions for the heat curing are as follows: 80 to 250 ° C (preferably 120 to 200 ° C, more preferably 150 to 200 ° C) for 0.1 to 15 hours (preferably 0.2 to 5 hours, more preferably 0.1 to 5 hours). 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 0.005%, more preferably 2.00 to 0.01%, and particularly preferably 1. 0 to 0.05%.
The boiling water absorption is measured in accordance with JIS K7209 (2000) 6.3B method.
The volume resistivity of the insulator of the present invention, 1010~1019Ω / cm, and preferably ^{10 12 ~5 × 10 18 Ω /} cm, more preferably 10 ¹⁴ ~10 ¹⁸ Ω / cm, particularly preferably 10 ^16-5 × 10 ¹⁷ Ω / cm, which is excellent in electrical insulation as compared with conventionally used insulating materials such as epoxy resin and polyimide resin.
The volume resistance is measured according to JIS K6011 (1995).

The insulator of the present invention has good adhesion to copper formed by oxidizing agent treatment and electroless copper plating, and has a peel strength (JIS C6481 (1995) 5.7) of 0.8 kgf / cm or more. Show.
On the other hand, the heat resistance of the insulator of the present invention is the same as that of the conventional insulator. Even when the insulator is brought into contact with solder at 300 ° C. for 1 minute, no abnormalities such as sagging, collapse and bulging of the pattern are observed. The chemical resistance to solvents and the like are also very good.
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 specified in JIS K6911 (1995) 5.32. .
Therefore, the insulator of the present invention has a great advantage in increasing the speed and density of an electronic circuit.

The curable film (the first of the present invention) containing the curable resin (A) of the present invention, the curable films (the second and third of the present invention) composed of a curable resin material, and the curable film (the present invention) As a method of using the fourth) as an insulator, for example, when the curable resin (A) or the curable resin material is applied to a substrate, After laminating the conductive films (first to fourth of the present invention), hot pressing is performed, and if necessary, processing such as perforation (roughening, formation of a conductive circuit, etc.), and further laminating the base material, this operation is performed. A method of repeatedly forming a multilayer by heating and curing at the end is exemplified.
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, the curable resin (A) and the curable resin material are applied to the base material, Alternatively, after laminating the curable film of the present invention (first to fourth aspects of the present invention) on a base material, hot pressing is performed, and if necessary, processing such as perforation is performed. In this case, a multi-layer method can be used.
In addition, it can also be used as a printed wiring board as it is, without using a base material.

When used as an interlayer insulating material such as a multilayer circuit board of an electronic circuit, one interlayer insulating layer may be composed of a single layer or multiple layers, and its thickness (after curing) is preferably 1 to 100 μm, more preferably 15 to 100 μm. 50 μm.
The conditions of the hot press include a temperature of 25 to 180 ° C. (preferably 50 to 150 ° C.), a pressure of 0.01 MPa to 10 MPa (preferably 0.1 to 1 MPa), and a time of 1 to 1200 seconds (preferably 10 to 300 seconds). Are preferred.
Holes (via holes, through holes, etc.) for conducting between the layers of the multilayer substrate can be formed by a usual method, and for example, a method using a laser (carbon dioxide, YAG, excimer, etc.), a drill or the like can be used.
Roughening can be performed by a usual method, for example, a method described in JP-B-6-49852 can be used.
The conductive circuit can be formed by an ordinary method, for example, a sputtering method, an electroless method, or the like can be used.

Curable film containing curable resin (A) (first of the present invention), curable film composed of curable resin material (second and third of the present invention), curable film (fourth of the present invention) ) And the insulator (the fifth aspect of the present invention) can be widely used as an insulator, and are suitable, for example, as an overcoat material, an interlayer insulating material, a printed circuit board, etc., and particularly suitable as an overcoat material and an interlayer insulating material. is there.
It is most suitable as an overcoat material or an interlayer insulating material for electronic devices (semiconductor devices, light emitting diodes, various memories, etc.), hybrid ICs, MCMs, electric wiring circuit boards or display components.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. Hereinafter, “part” indicates “part by weight” and “%” indicates “% by weight”.
Synthesis Example 1
50 parts of methyl ethyl ketone was charged into a reaction vessel purged with nitrogen, heated to 80 ° C., and uniformly dissolved in another vessel purged with nitrogen, 200 parts of glycidyl methacrylate, 200 parts of styrene, 200 parts of methyl ethyl ketone, 200 parts of styrene / Butadiene / styrene block copolymer (Y1 (i)) (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) A mixture consisting of 170 parts and 1.5 parts of azobisisobutyronitrile was dropped into the reaction vessel over 4 hours.

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

Synthesis Example 2
A styrene / butadiene / styrene block copolymer is dispersed in the same manner as in Synthesis Example 1 except that 232 parts of glycidyl methacrylate and 168 parts of styrene are used instead of 200 parts of glycidyl methacrylate and 200 parts of styrene used in Synthesis Example 1. A curable resin material (ii) comprising a styrene / glycidyl methacrylate copolymer (styrene / glycidyl methacrylate weight ratio = 42/58, curable resin (A (ii))) was obtained.
Mw of (ii)) is 210,000, Mn is 88,000, and epoxy equivalent is 180. From Mn and epoxy equivalent, the number of crosslinkable functional groups (epoxy groups) of (A (ii)) is 489. Met.
(Ii) was dissolved in methyl ethyl ketone so as to have a solid content of 40% to obtain a curable resin solution ((ii) S).

Synthesis Example 3
The following polymerization experiments were performed in a glove box purged with nitrogen.
100 parts of toluene is charged into a four-necked flask equipped with a stirrer and a temperature controller, and the temperature is adjusted to 30 ° C. while stirring. Then, a hexane solution of diethylaluminum chloride (catalyst concentration of hexane solution: 0.2 mmol / ml) 5 Parts by weight, 5 parts by weight of a hexane solution of vanadium oxytrichloride (catalyst concentration of the hexane solution: 0.02 mmol / ml), 50 parts of 5-ethylidene-2-norbornene and 50 parts of 1-hexene were charged, and polymerized at 30 ° C. for 120 minutes. Thus, a copolymer solution was obtained.
This copolymer solution was added dropwise to 3000 parts of isopropanol with stirring to form a precipitate, and the precipitate was evaporated in a vacuum dryer at 100 ° C. under a reduced pressure of 10 mmHg to obtain a copolymer ( H (i)) 70 parts were obtained.
Mw of (H (i)) is 98,000, Mn is 25,000, and the equivalent of double bond analyzed by NMR is 204. From Mn and double bond equivalent, (H (i)) The number of crosslinkable functional groups (double bonds) was 114.
(H (i)) was dissolved in toluene so as to have a solid content of 40% to obtain a copolymer solution (H (i) S).

Synthesis Example 4
100 parts of the copolymer solution (H (i) S) obtained in Synthesis Example 3, 20 parts of glycidyl methacrylate, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (a product of NOF Corporation) 7.0 parts of Parhexa 25B) was dry-blended at room temperature, and then extruded with a twin-screw extruder at a cylinder temperature of 260 ° C. and a screw rotation speed of 230 rpm to obtain a curable resin (A (iii)).
Mw of (A (iii)) is 117,000, Mn is 29,000, epoxy equivalent is 850, and from Mn and epoxy equivalent, the number of crosslinkable functional groups (epoxy groups) in (A (iii)) is 138.
(A (iii)) was dissolved in toluene to a solid content of 40% to obtain a curable resin solution (A (iii) S).

Synthesis Example 5
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene (MTD) is produced by ring-opening polymerization by a known method. 6. 100 parts of olefin resin (Mw 28,000), 20 parts of glycidyl methacrylate, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: Perhexa 25B, manufactured by NOF CORPORATION) After 0 parts were dry-blended at room temperature, the mixture was extruded with a twin-screw extruder at a cylinder temperature of 260 ° C. and a screw rotation speed of 230 rpm to obtain a curable resin (A (iv)).
Mw of (A (iv)) is 33,000, Mn is 8,400, and epoxy equivalent is 840. From Mn and epoxy equivalent, the number of crosslinkable functional groups (epoxy groups) of (A (iv)) is It was 10.
(A (iv)) was dissolved in toluene so as to have a solid content of 40% to obtain a curable resin solution (A (iv) S).

Synthesis Example 6
A reaction vessel purged with nitrogen was charged with 50 parts of methyl ethyl ketone, the temperature was raised to 80 ° C., and 200 parts of hydroxyethyl methacrylate, 200 parts of styrene, 200 parts of methyl ethyl ketone, and 200 parts of uniformly dissolved in another vessel purged with nitrogen. A mixture consisting of 1.5 parts of azobisisobutyronitrile was dropped into the reaction vessel over 4 hours. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 4 hours to obtain a solution of the hydroxyl group-containing resin in methyl ethyl ketone.
30 parts of acrylic acid was added to 100 parts of a methyl ethyl ketone solution of a hydroxyl group-containing resin, and an esterification reaction was carried out at 100 ° C. for 4 hours under reduced pressure while adding a solvent (methyl ethyl ketone) to obtain a solution of the curable resin (A (v)) in methyl ethyl ketone. Got.
Mw of (A (v)) is 160,000, Mn is 45,000, the equivalent of acryloyl group analyzed by NMR is 610, and the crosslinkable functional group of (A (v)) is obtained from Mn and acryloyl group equivalent. The number of (acryloyl groups) was 74.
(A (v)) was adjusted by adding methyl ethyl ketone so that the solid content became 40%, to obtain a curable resin solution (A (v) S).

Synthesis Example 7
50 parts of methyl ethyl ketone was charged into a reaction vessel purged with nitrogen, heated to 80 ° C., and 120 parts of propenyloxyethyl methacrylate uniformly dissolved in another vessel purged with nitrogen, 280 parts of styrene, 200 parts of methyl ethyl ketone, Styrene / butadiene / styrene block copolymer (Y1 (i)) (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)) A mixture consisting of 170 parts and 1.5 parts of azobisisobutyronitrile was dropped into the reaction vessel over 4 hours. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 4 hours, and the styrene / butadiene / styrene block copolymer was converted to a styrene / propenyloxyethyl methacrylate copolymer (styrene / propenoxyethyl methacrylate weight ratio = 70/30, curable resin). A solution of the curable resin material (iii) dispersed in (A (vi))) was obtained.
Mw of the curable resin material (iii) is 230,000, Mn is 90,000, and a propenyl ether group equivalent analyzed by NMR is 570. From the Mn and the propenyl ether group equivalent, a crosslinkable functional group (iii) ( The number of (propenyl ether groups) was 158.
(Iii) was dissolved in methyl ethyl ketone so as to have a solid content of 40% to obtain a curable resin material solution ((iii) S).

Synthesis Example 8
100 parts of toluene, 100 parts of Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin) and 50 parts of dodecylamine are added to a reaction vessel purged with nitrogen, and the mixture is reacted at 25 ° C. for 4 hours with stirring. Thus, a thermoplastic resin (Y2 (i)) was obtained.
Mw of (Y2 (i)) was 75,000 and Mn was 37,000.
The nitrogen-carbon bond concentration of (Y2 (i)) was 1.9 × 10 ⁻³ mol / g.
Subsequently, (Y2 (i)) was dissolved in toluene so that the solid content was 40%, to obtain a thermoplastic resin solution (Y2 (i) S).

Synthesis Example 9
50 parts of methyl ethyl ketone was charged into a reaction vessel purged with nitrogen, heated to 80 ° C., and 200 parts of glycidyl methacrylate, 200 parts of styrene, and tridecafluorohexyl uniformly dissolved in another vessel purged with nitrogen. ethyl acrylate _{(C 6 F 13 C 2 H} 4 -OCOCH = CH 2) 200 parts, 200 parts of methyl ethyl ketone, styrene / butadiene / styrene block copolymer (Y1 (i)) (JSR Corporation, trade name TR2250 (styrene / butadiene Weight ratio = 52/48, Mw = 90,000, carbon-carbon bond concentration of 8.9 × 10 ⁻³ mol / g)) A mixture comprising 170 parts and 1.5 parts of azobisisobutyronitrile was placed in a reaction vessel. For 4 hours. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 4 hours to obtain a styrene / glycidyl methacrylate / tridecafluorohexylethyl acrylate copolymer (monomer containing styrene / butadiene / styrene block copolymer (Y1 (i)) dispersed therein). A curable resin material (iv) comprising a curable resin (A (vii)) with a weight ratio of 50/50/50 was obtained.
The Mw of (A (vii)) is 120,000, the number average molecular weight by GPC (hereinafter, abbreviated as Mn) is 60,000, the epoxy equivalent is 325, and (A (vii)) The number of crosslinkable functional groups (epoxy groups) in) was 185.
(Iv) was dissolved in methyl ethyl ketone so as to have a solid content of 40% to obtain a curable resin material solution (A (vii) S).

Example 1 (example composed of X1 and Y1)
30 parts of resorcinol diglycidyl ether (B (i)) and 6 parts of 2-ethyl-4-methylimidazole (C (i)) are added to 175 parts of the thermosetting resin material solution ((i) S) and stirred. Then, a solution of the curable resin material (iv) of the present invention was obtained.
This solution was applied on a 50 μm-thick PET film (257 mm × 364 mm) using a knife coater (manufactured by Yasui Seiki Co., Ltd .; knife coater SNC-300), dried at 60 ° C. for 30 minutes, and the solvent was removed. A curable film ((iv) F) was prepared on the film. The thickness of the curable film ((iv) F) was 47 ± 2 μm.
The curable film ((iv) F) was brought into contact with a BT substrate (CCL-HL830, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., 100 mm x 100 mm, which is obtained by removing each half of the copper foil on both sides) by etching at 120 ° C. After hot-pressing at 0.4 kg / cm ² for 5 minutes, the PET film was peeled off and cured by heating at 180 ° C. for 3 hours to obtain an insulator ((iv) Z).

The insulator ((iv) Z) was cut with a diamond cutter, and the cross section was observed with a scanning electron microscope to calculate the average particle diameter of the (Y1 (i) (styrene / butadiene block copolymer)) particles. 0.4 μm.
Using this insulator ((iv) Z), the temperature is raised to 125 ° C. in 10 seconds after continuing at −55 ° C. for 30 seconds, and the temperature is lowered to −55 ° C. in 10 seconds, maintaining 125 ° C. for 30 seconds. A temperature cycle pattern was defined as one cycle, and a thermal cycle test was repeated. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles.
Further, in the same manner as described in the example of Japanese Patent Publication No. 6-49852, the cured surface of the insulator ((iv) Z) is roughened, copper-plated, and then peeled off (JIS C6481 (JIS C6481)). (1995) 5.7) was 0.8 kg / cm.
The curable film ((iv) F) was cured by heating at 170 ° C. for 90 minutes, and the dielectric constant after curing at 1 GHz measured according to JIS K6911 (1995) 5.14 was 2. 9, the dielectric loss tangent was 0.009, and the volume resistance was 5.1 × 10 ¹⁶ Ω / cm. Further, the cured tensile modulus (JIS K7113 (1995)) of ((iv) F) was 16,000 kgf / mm ² .
The thermal expansion coefficient (TMA tensile load method) after curing of ((iv) F) was 45 ppm / ° C.
The SP value of the styrene / butadiene / styrene block copolymer (Y1 (i)) was 9.1, and the styrene / glycidyl methacrylate copolymer (curable resin (A (i))) and resorcinol diglycidyl were used. The SP value of the curable resin composition (X1 (i)) comprising the ether (B (i)) was 11.0. Therefore, the difference in SP value between (Y1 (i)) and (X1 (i)) was 1.9.

Example 2 (example composed of X1 and Y1)
Example 1 was repeated in the same manner as in Example 1 except that 175 parts of the thermosetting resin material solution ((ii) S) was used instead of 175 parts of the thermosetting resin material solution ((i) S). And a solution of the curable resin material (v), a curable film ((v) F) and an insulator ((v) Z). The thickness of the curable film ((v) F) was 47 ± 2 μm.
The average particle diameter of the (Y1 (i) (styrene / butadiene / styrene block copolymer)) particles of the insulator ((v) Z) calculated in the same manner as in Example 1 was 0.4 μm.
A thermal cycle test was performed in the same manner as in Example 1. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles.
Further, the peel strength was measured in the same manner as in Example 1, and it was 0.8 kg / cm.
Further, the cured dielectric constant of ((v) 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 / cm. . Further, the cured tensile modulus of ((v) F) was 17,400 kgf / mm ² .
The thermal expansion coefficient of ((v) F) after curing was 46 ppm / ° C.
The difference in SP value between (Y1 (i)) and (X1 (i)) was 1.9 as in Example 1.

Example 3 (example composed of X2 and Y1)
30 parts of ethylene glycol diallyl ether (I (i)), 2 parts of p-menthane hydroperoxide (C (ii)), styrene / butadiene / styrene block in 175 parts of copolymer solution (H (i) S) 15 parts of the copolymer (Y1 (i)) (TR2250 manufactured by JSR) was added and stirred to obtain a solution of a curable resin material ((vi)).
Using this solution of the curable resin material ((vi)), a curable film ((vi) F) was prepared in the same manner as in Example 1, and using this, an insulator was formed in the same manner as in Example 1. ((Vi) Z) was obtained. The thickness of the curable film ((vi) F) was 47 ± 2 μm.
The average particle diameter of the (Y1 (i) (styrene / butadiene / styrene block copolymer)) particles of the insulator ((vi) Z) calculated in the same manner as in Example 1 was 0.3 μm.
Using this insulator (Z (vi)), a thermal cycle test evaluated in the same manner as in Example 1 showed no blistering or peeling failure.
Further, the peel strength was measured in the same manner as in Example 1, and it was 0.8 kg / cm.
The cured ((vi) F) had a dielectric constant of 2.4, a dielectric loss tangent of 0.006, a volume resistance of 4.1 × 10 ¹⁷ Ω / cm, and a tensile elasticity measured in the same manner as in Example 1. The rate was 18,400 kgf / mm ² and the coefficient of thermal expansion was 47 ppm / ° C.
The SP value of the styrene / butadiene / styrene block copolymer (Y1 (i)) is 9.1, and the copolymer solution (H (i) S) and ethylene glycol diallyl ether (I (i)) The SP value of the curable resin composition (X2 (i)) composed of was 9.9. Therefore, the difference in SP value between (Y1 (i)) and (X2 (i)) was 0.8.

Example 4 (example composed of X1 and Y2)
To 175 parts of the curable resin solution (A (iii) S), 30 parts of resorcinol diglycidyl ether (B (i)), 6 parts of 2-ethyl-4-methylimidazole (C5 (i)), and a thermoplastic resin 15 parts of the solution (Y2 (i) S) was added and stirred to obtain a solution of the curable resin material (vii).
A curable film ((vii) F) was prepared in the same manner as in Example 1 using the solution of the curable resin material (vii), and the insulator ((vii) was used in the same manner as in Example 1 using this. ) Z) was obtained. The thickness of the curable film ((vii) F) was 47 ± 2 μm.
The average particle diameter of (Y2 (i)) of the insulator ((vii) Z) calculated in the same manner as in Example 1 was 0.8 μm.
A thermal cycle test using this insulator ((vii) Z) in the same manner as in Example 1 showed no blistering or peeling failure.
Further, the peel strength was measured in the same manner as in Example 1, and it was 0.8 kg / cm.
The cured ((vii) F) had a dielectric constant of 2.5, a dielectric loss tangent of 0.006, a volume resistance of 4.3 × 10 ¹⁷ Ω / cm, and a tensile elasticity measured in the same manner as in Example 1. The rate was 18,800 kgf / mm ² and the coefficient of thermal expansion was 47 ppm / ° C.
The curable resin (Y2 (i)) has an SP value of 13.5, and is a curable resin composition comprising the curable resin (A (iii)) and resorcinol diglycidyl ether (B (i)). The SP value of (X1 (ii)) was 11.2. Therefore, the difference in SP value between (Y2 (i)) and (X1 (ii)) was 2.3.

Example 5 (example composed of X1 and Y2)
A curable resin was prepared in the same manner as in Example 4 except that 175 parts of the curable resin solution (A (iv) S) was used instead of 175 parts of the curable resin solution (A (iii) S) of Example 4. A solution of material (viii) was obtained.
A curable film ((viii) F) was prepared in the same manner as in Example 1 using the solution of the curable resin material (viii), and the insulator ((viii) was used in the same manner as in Example 1 using this. ) Z) was obtained. The thickness of the curable film ((viii) F) was 47 ± 2 μm.
The average particle diameter of (Y2 (i)) of the insulator ((viii) Z) calculated in the same manner as in Example 1 was 0.8 μm.
Using this insulator ((viii) Z), a thermal cycle test evaluated in the same manner as in Example 1 showed no swelling or peeling failure. Further, the peel strength was measured in the same manner as in Example 1, and it was 0.8 kg / cm.
The cured dielectric constant of ((viii) 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 elasticity. The rate was 16,800 kgf / mm ² and the coefficient of thermal expansion was 46 ppm.
The curable resin (Y2 (i)) has an SP value of 13.5, and is a curable resin composition comprising the curable resin (A (iv)) and resorcinol diglycidyl ether (B (i)). The SP value of (X1 (iii)) was 10.2. Therefore, the difference in SP value between (Y2 (i)) and (X1 (iii)) was 3.5.

Example 6 (example composed of X1 and Y2)
To 175 parts of the curable resin solution (A (v) S), 30 parts of ethylene glycol dimethacrylate (B (ii)), 2 parts of p-menthane hydroperoxide (C (ii)), and the thermoplastic resin solution (Y2 (i) 15 parts of S) were added and stirred to obtain a solution of the curable resin material (ix).
A curable film ((ix) F) was prepared in the same manner as in Example 1 using the solution of the curable resin material (ix), and the insulator ((ix) F was used in the same manner as in Example 1 using this. ) Z) was obtained. The thickness of the curable film ((ix) F) was 47 ± 2 μm.
The average particle diameter of (Y2 (i)) of the insulator ((ix) Z) calculated in the same manner as in Example 1 was 0.5 μm.
Using this insulator ((ix) Z), a thermal cycle test evaluated in the same manner as in Example 1 showed no blistering or peeling failure. Further, the peel strength was measured in the same manner as in Example 1, and it was 0.8 kg / cm.
The cured ((ix) F) had a dielectric constant of 2.9, a dielectric loss tangent of 0.009, a volume resistance of 4.6 × 10 ¹⁶ Ω / cm, and a tensile elasticity measured in the same manner as in Example 1. The rate was 18,200 kgf / mm ² and the coefficient of thermal expansion was 47 ppm.
The curable resin (Y2 (i)) has an SP value of 13.5, and is a curable resin composition comprising the curable resin (A (v)) and ethylene glycol dimethacrylate (B (ii)). The SP value of (X1 (iv)) was 10.4. Therefore, the difference in SP value between (Y2 (i)) and (X1 (iv)) was 3.1.

Example 7 (example composed of X1 and Y1)
175 parts of the curable resin material solution ((iii) S) and 5.0 parts by weight of a cationic photopolymerization initiator (“UVR-6990” manufactured by Union Carbide) are stirred to obtain a solution of the curable resin material (x). Was.
A curable film ((x) F) was prepared in the same manner as in Example 1 using the solution of the curable resin material (x).
The curable film ((x) F) was irradiated with ultraviolet rays at 150 ° C. for 1 minute (using a high-pressure mercury lamp of 80 W / cm, at a distance of 10 cm and an irradiation intensity of 160 mW / cm ² ). Heat treatment was performed for 3 hours to obtain an insulator ((x) Z). The thickness of the curable film ((x) F) was 47 ± 2 μm.
The average particle diameter of (Y1 (i)) of the insulator ((x) Z) calculated in the same manner as in Example 1 was 0.4 μm.
Using this insulator ((x) Z), a thermal cycle test evaluated in the same manner as in Example 1 showed no blistering or peeling failure. Further, the peel strength was measured in the same manner as in Example 1, and it was 0.8 kg / cm.
The cured ((x) F) had a dielectric constant of 2.9, a dielectric loss tangent of 0.009, a volume resistance of 6.7 × 10 ¹⁶ Ω / cm, and a tensile elasticity measured in the same manner as in Example 1. The rate was 22000 kgf / mm ² and the coefficient of thermal expansion was 45 ppm.
((X) F) was irradiated with ultraviolet rays at 150 ° C. for 1 minute (using a high-pressure mercury lamp of 80 W / cm, at a distance of 10 cm and an irradiation intensity of 160 mW / cm ² ), and further at 150 ° C. for 3 hours. The dielectric constant after curing by heat treatment was 2.9. The SP value of the curable resin (Y1 (i)) is 9.1, and the SP value of the curable resin composition (X1 (v)) composed of the curable resin (A (vi)) is 10. It was 2.
Therefore, the difference in SP value between (Y1 (i)) and (X1 (v)) was 1.1.

Example 8 (example composed of X3 and Y1)
30 parts of resorcinol diglycidyl ether (B (i)) and 6 parts of 2-ethyl-4-methylimidazole (C (i)) are added to 175 parts of the thermosetting resin material solution ((vii) S) and stirred. Then, a solution of the curable resin material (xi) of the present invention was obtained.
This solution was applied on a 50 μm-thick PET film (257 mm × 364 mm) using a knife coater (manufactured by Yasui Seiki Co., Ltd .; knife coater SNC-300), dried at 60 ° C. for 30 minutes, and the solvent was removed. A curable film ((xi) F) was prepared on the film. The thickness of the curable film ((xi) F) was 47 ± 2 μm.
The curable film ((xi) F) was brought into contact with a BT substrate (CCL-HL830, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., 100 mm × 100 mm, which is obtained by removing each half of the copper foil on both sides) by etching at 120 ° C. After hot-pressing at 0.4 kg / cm ² for 5 minutes, the PET film was peeled off and heat-cured at 180 ° C. for 3 hours to obtain an insulator ((xi) Z). The average particle diameter of (Y1 (i)) of the insulator ((xi) Z) calculated in the same manner as in Example 1 was 0.5 μm.
Using this insulator ((xi) Z), a thermal cycle test evaluated in the same manner as in Example 1 showed no blistering or peeling failure. Further, the peel strength was measured in the same manner as in Example 1, and it was 0.8 kg / cm.
The cured ((xi) F) had a dielectric constant of 2.7, a dielectric loss tangent of 0.007, a volume resistance of 5.7 × 10 ¹⁶ Ω / cm, and a tensile elasticity measured in the same manner as in Example 1. The rate was 19000 kgf / mm ² and the coefficient of thermal expansion was 43 ppm.
The SP value of the curable resin (Y1 (i)) is 9.1, and the SP value of the curable resin composition (X1 (v)) composed of the curable resin (A (vii)) is 9.1. It was 7.
Therefore, the difference in SP value between (Y1 (i)) and (X1 (v)) was 0.6.

Comparative Example 1
To 100 parts of Epicoat 828 (trade name of Yuka Shell Epoxy Co., Ltd .; bisphenol A type epoxy resin), 85 parts of 4-methylcyclohexane-1,2-dicarboxylic acid was added, and the mixture was stirred and mixed. On a BT substrate (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., CCL-830, 100 mm × 100 mm, half of each of the front and rear copper foils removed by etching) using a knife coater SNC-300). After coating with a thickness of 62 ± 2 μm, it was cured by heating at 180 ° C. for 3 hours to obtain a comparative insulator (1).
Using this comparative insulator (1), a thermal cycle test was performed in the same manner as in Example 1, but cracks occurred at a rate of 1 piece / cm ^{2 in} 500 cycles.
Further, the peel strength after the roughening and copper plating treatment was measured in the same manner as in Example 1, and it was 0.2 kg / cm.
The dielectric constant of the comparative insulator (1) measured in the same manner as in Example 1 was 3.6, the dielectric loss tangent was 0.020, the volume resistance was 4.8 × 10 ¹⁶ Ω / cm, and the tensile elasticity was 38000 kgf / mm ² , and the coefficient of thermal expansion was 60 ppm.

Comparative Example 2
To 100 parts of cresol novolak epoxy resin having an Mw of 1040, 95 parts of 4-methylcyclohexane-1,2-dicarboxylic acid was added, and the mixture was stirred and mixed.
B using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300)
T substrate (Mitsubishi Gas Chemical Industry Co., Ltd., CCL-830, 100 mm × 100
and a thickness of 62 ± 2 μm, and cured by heating at 180 ° C. for 3 hours to obtain a comparative insulator (2).
Using this comparative insulator (2), a thermal cycle test was performed in the same manner as in Example 1, but cracks occurred at a rate of 1 piece / cm ^{2 in} 700 cycles. Further, the peel strength after the roughening and copper plating treatment was measured in the same manner as in Example 1, and it was 0.2 kg / cm.
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 modulus was 35,000 kgf / mm ² , and the coefficient of thermal expansion was 70 ppm / ° C.

The curable resin, the curable resin material, and the curable film of the present invention are particularly suitable as an overcoat material or an interlayer insulating material used for a circuit board used for various electric devices, electronic components, or semiconductor elements.
The curable resin, the curable resin material, and the curable film of the present invention are not limited to the use in the technical field such as a circuit board, and can be used in various fields, and can be used particularly for forming a thin film. It is an excellent material that can be used.

Claims (11)

It has at least two crosslinkable functional groups selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group and an alkenyloxy group in a molecule, and has a glass transition temperature before curing of 50 to 150. C., containing a curable resin (A) having a weight average molecular weight of 10,000 to 1,000,000, and having a dielectric constant of 3.2 or less after curing of (A). Curable film. The curable film according to claim 1, wherein the crosslinkable functional group is an epoxy group. (A) is styrene, ethylene, propylene, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, norbornene, dicyclopentadiene 3. The curable film according to claim 1, wherein at least one monomer selected from the group consisting of and 5-ethylidene-2-norbornene is used as an essential constituent monomer. Furthermore, it has at least two crosslinkable functional groups selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group and an alkenyloxy group in a molecule, and has a weight average molecular weight of 170 to 3 The curable film according to any one of claims 1 to 3, comprising a low molecular weight compound (B) of 2,000, and having a dielectric constant of 3.5 or less after curing. It comprises a curable resin composition (X) and a thermoplastic resin (Y), and the difference between the solubility parameters of (X) and (Y) is 0.5 to 3.0, A curable film comprising a curable resin material having a weight average molecular weight of 5,000 to 1,000,000 of Y). It contains a curable resin composition (X) and a thermoplastic resin (Y), and the difference between the solubility parameters of (X) and (Y) is 1.0 to 3.0, and the (X) ) Comprising a curable resin material having a solubility parameter of 5.0 to 12.0. The curable film according to claim 5, wherein the curable resin composition (X) contains the curable resin (A) and / or (B).
Curable resin (A): having at least two crosslinkable functional groups selected from the group consisting of an epoxy group, a (meth) acryloyl group, an alkenylamino group, and an alkenyloxy group in a molecule; 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 (B): an epoxy group, a (meth) acryloyl group, an alkenylamino group and an alkenyloxy group Low molecular weight compound having at least two crosslinkable functional groups selected from the group consisting of at least two in the molecule A film comprising a composition containing a curable polymer having a weight average molecular weight of 10,000 to 1,000,000, wherein the cured film has a tensile modulus of 100 to 250 kgf / mm ² after curing. A curable film having a later dielectric constant of 3.5 or less. An insulator having a tensile modulus of elasticity of 100 to 250 kgf / mm ² and a coefficient of thermal expansion α1 of 30 to 50 ppm. Tensile modulus is 150~200kgf / mm ^2, an insulator of claim 12, wherein the thermal expansion coefficient α1 is 35～45Ppm. An insulator obtained by curing the curable film according to claim 1.