JP3685998B2 - Curable resin composition and insulator comprising the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a curable resin composition and an insulator comprising the same. More specifically, the present invention relates to a curable resin composition suitable as an overcoat material or an interlayer insulating material for circuit boards used for various electric devices, electronic components, semiconductor elements, and the like, and an insulator made thereof.
[0002]
[Prior art]
Insulation materials such as epoxy resin composition and polyimide resin have moisture resistance, defects such as dielectric properties in high frequency range, polyolefin resin and polyphenylene ether resin have heat resistance, solvent resistance, etc. In order to solve the problem, for example, a copolymer of norbornene monomer and ethylene is subjected to sulfur crosslinking, organic oxide crosslinking, electron beam crosslinking, or radiation crosslinking (Japanese Patent Laid-Open No. 62-34924), propargyl group or allyl. Examples using polyphenylene ether substituted with a group, polyphenylene ether containing a double bond, and unsaturated carboxylic acid or acid anhydride-modified polyphenylene ether (JP-A-1-69628, JP-A-1-69629, JP-A-1-113425, JP-A-1-113426, JP-A-1-239 17 No., etc.) and the like are known.
[0003]
[Problems to be solved by the invention]
However, the former has a problem in application to insulating materials such as overcoat materials and interlayer insulating materials because the dielectric constant is as high as 3.7 or more.
In the latter case, allyl group, olefinically unsaturated group or unsaturated carboxylic acid is used as the curing functional group, so that curing reactivity, particularly curing reactivity in oxygen (in air) is inferior, and thermal shock Lack of sex.
That is, an object of the present invention is to provide a curable resin composition capable of producing an insulator excellent in thermal shock resistance and dielectric properties.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have reached the present invention as a result of intensive studies to achieve the above object. That is, the curable resin composition of the present invention is characterized by a resin (A) having at least two crosslinkable functional groups in the molecule, and at least 2 crosslinkable functional groups of the same type as (A) in the molecule. A low molecular weight compound (B) having a number, (A) has a weight average molecular weight of 3,000 to 1,000,000, (B) has a weight average molecular weight of 170 to 3,000, The dielectric constant after curing is 3.5 or less.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the crosslinkable functional group possessed by (A) include an epoxy group, a (meth) acryloyl group, a vinyl group, an allyl group, a propenyl group, a primary amino group, a secondary amino group, a nitrile group, a carboxyl group, Hydroxyl groups and isocyanate groups can be used.
Examples of the epoxy group include a glycidyl group and a cyclohexenyl monooxide group.
(Meth) acryloyl means a methacryl group and an acryloyl group, and the primary amino group is -NH.₂Means.
[0006]
The secondary amino group means an N-alkylamino group, and the alkyl group is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Etc.
Of these crosslinkable functional groups, epoxy groups, (meth) acryloyl groups, vinyl groups, allyl groups, propenyl groups, and nitrile groups are preferable from the viewpoint of electrical characteristics, and epoxy groups, (meth) acryloyl groups are preferable from the viewpoint of heat resistance. More preferred are glycidyl and cyclohexenyl oxide groups.
[0007]
The number of crosslinkable functional groups in (A) is at least 2, preferably 2 to 5,000, more preferably 3 to 3,000, particularly preferably 5 to 1,000, and even more preferably. Is 7 to 500, and most preferably 10 to 200. The weight average molecular weight of (A) is 3,000 to 1,000,000, preferably 30,000 to 600,000, and more preferably 50,000 to 400,000. If the weight average molecular weight is less than 3,000, the resin strength tends to be weak, and if it exceeds 1,000,000, resin processing such as forming a film of the curable resin composition tends to be difficult.
The weight average molecular weight is measured by gel permeation chromatography (hereinafter abbreviated as GPC) and is hereinafter abbreviated as Mw.
[0008]
(A) is (1) a method of (co) polymerizing a monomer having a crosslinkable functional group, or (2) reacting a monomer having a crosslinkable functional group with a resin having a crosslinkable functional group. And can be easily produced by a method of converting a crosslinkable functional group.
The monomer having a crosslinkable functional group is not limited as long as it has at least two crosslinkable functional groups, and includes an epoxy group, a (meth) acryloyl group, a vinyl group, an allyl group, a propenyl group, A monomer having at least one functional group selected from the group consisting of primary amino group, secondary amino group, nitrile group, carboxyl group, hydroxyl group and isocyanate group can be used.
[0009]
For example, as a crosslinkable functional group, a monomer (a) having only an epoxy group, a monomer (b) having only a (meth) acryloyl group, a monomer (c) having only a vinyl group, Monomer (d) having only an allyl group, monomer (e) having only a propenyl group, monomer (f) having a primary amino group, single monomer having a secondary amino group A monomer (h) having only a carboxyl group, a monomer (i) having only a hydroxyl group, a monomer (j) having only an isocyanate group, a nitrile group and a vinyl group Monomer (k) having nitrile group and (meth) acryloyl group (m), monomer having hydroxyl group and (meth) acryloyl group (n), epoxy group and (meth) Monomer (o) having an acryloyl group, monomer (p) having an epoxy group and a vinyl group, (meth) acrylic Monomer (q) having an yl group and a vinyl group, monomer (r) having a (meth) acryloyl group and an isocyanate group, and a monomer (s) having a (meth) acryloyl group and a carboxyl group , Monomer (t) having (meth) acryloyl group and allyl group, monomer (u) having (meth) acryloyl group and propenyl group, monomer having secondary amino group and allyl group The body (v), the monomer (w) having a secondary amino group and a propenyl group, and the like are used.
[0010]
As the monomer (a) having only an epoxy group as a crosslinkable functional group, a polyepoxide having 2 to 7 or more epoxy groups in the molecule can be used, for example, (a1) a glycidyl ether type polyepoxide, (A2) Glycidyl ester type polyepoxide, (a3) glycidylamine type polyepoxide, (a4) alicyclic polyepoxide and the like are used.
[0011]
As the (a1) glycidyl ether type polyepoxide, for example, the following (a11) to (a14) can be used.
(A11) Diglycidyl ether of dihydric phenol (having 6 to 30 carbon atoms)
For example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin di Glycidyl 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 glyci Diglycidyl ether obtained from ether and bisphenol A2 moles and 3 moles of epichlorohydrin in the reaction.
[0012]
(A12) Polyglycidyl ether of polyhydric phenol {having 6 to 50 or more carbon atoms, and Mw of 110 to 5,000, trivalent to hexavalent or more}
For example, pyrogallol triglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, trismethyl-tert-butyl-butyl Hydroxymethane triglycidyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) phenylglycidyl ether and bis (dihydroxynaphthalene) tetraglycidyl Examples include ether.
[0013]
(A13) Dihydric alcohol (2 to 100 or more carbon atoms, Mw 62 to 5,000) [Alkylene glycol having 2 to 6 or more carbon atoms or alkylene oxide of dihydric phenol (6 to 24 carbon atoms) (carbon Diglycidyl ether of (2-4) (hereinafter, C2-C4 alkylene oxide is abbreviated as AO) 1-90 mol adduct]
For example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (Mw 150-4,000) diglycidyl ether, polypropylene glycol (Mw 180-5) , 000) diglycidyl ether, polytetramethylene glycol (Mw 200-5,000) diglycidyl ether, neopentyl glycol diglycidyl ether and ethylene oxide of bisphenol A (hereinafter, ethylene oxide is abbreviated as EO) and / or propylene oxide ( Hereinafter, propylene oxide is abbreviated as PO.) (1 to 20 mol) Addition diglycidyl ether and the like.
[0014]
(A14) A polyglycidyl ether of a trihydric to 7-valent or higher polyhydric alcohol (having 3 to 50 or more carbon atoms and Mw of 76 to 10,000)
Examples include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, and poly (degree of polymerization 2 to 5) glycerin polyglycidyl ether.
[0015]
As the (a2) glycidyl ester type polyepoxide, for example, the following (a21) to (a22) can be used.
(A21) Polyglycidyl ester of divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms)
Examples thereof include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and trimellitic acid triglycidyl ester.
(A22) Polyglycidyl ester of divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acid (having 6 to 20 or more carbon atoms)
For example, (a21) aromatic nucleus water additive, dimer acid diglycidyl ester, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and tri And carbaryl acid triglycidyl ester.
[0016]
As the (a3) glycidylamine type polyepoxide, for example, the following (a31) to (a34) can be used.
(A31) Polyglycidyl aromatic amine having 2 to 10 or more glycidyl groups (aromatic amine having 6 to 20 or more carbon atoms)
For example, N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyldiaminodiphenylsulfone, N , N, N ′, N′-tetraglycidyldiethyldiphenylmethane and N, N, O-triglycidylaminophenol.
[0017]
(A32) A polyglycidyl aliphatic or araliphatic amine having 2 to 10 or more glycidyl groups (6 to 20 or more carbon atoms of an aliphatic or araliphatic amine)
Examples thereof include N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidylhexamethylenediamine.
(A33) Polyglycidyl alicyclic amine having 2 to 10 or more glycidyl groups (alicyclic amine having 6 to 20 or more carbon atoms)
Examples thereof include hydrogenated compounds of N, N, N ′, N′-tetraglycidylxylylenediamine.
(A34) A polyglycidyl heterocyclic amine having 2 to 10 or more glycidyl groups (6 to 20 or more carbon atoms of the heterocyclic amine)
For example, trisglycidyl melamine can be used.
[0018]
As the (a4) alicyclic polyepoxide, for example, alicyclic epoxide having 6 to 50 or more carbon atoms, Mw of 98 to 5,000, and 2 to 4 or more epoxy groups can be used.
For example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4 epoxy-6-methylcyclohexylmethyl 3 ′, 4 Examples include '-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine.
[0019]
As the monomer (b) having only a (meth) acryloyl group as a crosslinkable functional group, (b1) diglycidyl ether of dihydric phenol (6 to 30 carbon atoms), (b2) polyhydric phenol {carbon number 6 to 50 or more, Mw 110 to 5,000 trivalent to hexavalent or more} poly (meth) acrylate, (b3) dihydric alcohol (2 to 100 or more carbon atoms, Mw 62 to 5, 000) di (meth) acrylate of [C2-C6 or higher alkylene glycol or dihydric phenol (AO1-90 mol adduct of C6-24)], and (b4) trivalent to 7-valent or Poly (meth) acrylates or the like of polyhydric alcohols (3 to 50 or more carbon atoms and Mw 76 to 10,000) are used.
[0020]
(B1) (Meth) acrylate of dihydric phenol
For example, bisphenol F di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol B di (meth) acrylate, bisphenol AD di (meth) acrylate, bisphenol S di (meth) acrylate, halogenated bisphenol A di (meth) Acrylate (for example, tetrachlorobisphenol A di (meth) acrylate), catechin di (meth) acrylate, resorcinol di (meth) acrylate, hydroquinone di (meth) acrylate, 1,5-dihydroxynaphthalenedi (meth) acrylate, dihydroxybiphenyl Di (meth) acrylate, octachloro-4,4′-dihydroxybiphenyl di (meth) acrylate, tetramethylbiphenyl di (meth) acrylate and 9,9′-bis ( - hydroxyphenyl) furo Orange (meth) acrylate.
[0021]
(B2) Poly (meth) acrylate of polyphenol
For example, pyrogallol tri (meth) acrylate, dihydroxynaphthylcresol tri (meth) acrylate, tris (hydroxyphenyl) methane tri (meth) acrylate, dinaphthyltriol tri (meth) acrylate, tetrakis (4-hydroxyphenyl) ethanetetra (meth) acrylate , Trismethyl-tert-butyl-butylhydroxymethane tri (meth) acrylate, 4,4′-oxybis (1,4-phenylethyl) tetracresol (meth) acrylate, 4,4′-oxybis (1,4-phenylethyl) ) Phenyl (meth) acrylate and bis (dihydroxynaphthalene) tetra (meth) acrylate.
[0022]
(B3) (Meth) acrylate of dihydric alcohol
For example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol (Mw 150 to 4,000) di ( Meth) acrylate, polypropylene glycol (Mw 180-5,000) di (meth) acrylate, polytetramethylene glycol (Mw 200-5,000) di (meth) acrylate, neopentyl glycol di (meth) acrylate and bisphenol A EO and And / or di (meth) acrylates of PO (1 to 20 mol) adducts.
[0023]
(B4) Poly (meth) acrylates of trihydric to 7 or higher polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, sorbitol hexa ( Examples include meth) acrylate and poly (degree of polymerization 2 to 5) glycerin poly (meth) acrylate.
[0024]
Examples of the monomer (c) having only a vinyl group as a crosslinkable functional group include hydrocarbon compounds having 4 to 20 carbon atoms, such as butadiene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, trivinylbenzene, and the like. In addition to these, divinyl sulfide, divinyl sulfone, divinyl sulfoxide, and the like can also be used.
[0025]
As the monomer (d) having only an allyl group as a crosslinkable functional group, (d1) diallyl ether of dihydric phenol (carbon number 6 to 30), (d2) polyhydric phenol {carbon number 6 to 50 or Further, a polyallyl ether having a Mw of 110 to 5,000 and a trivalent to hexavalent or higher}, (d3) dihydric alcohol (having 2 to 100 or more carbon atoms, Mw of 62 to 5,000) [carbon number 2 Diallyl ether of AO 1-90 mol adduct of ˜6 or more alkylene glycol or dihydric phenol (carbon number 6-24), (d4) trivalent to 7 valent or more polyhydric alcohol (carbon number 3) A polyallyl ether having a molecular weight of ˜50 or more and Mw of 76 to 10,000), (d5) a polyarylic acid having 6 to 20 or more aromatic polycarboxylic acids having 6 to 20 or more carbon atoms. Ester, and (d6) polyallyl esters of bivalent to hexavalent or more aliphatic or cycloaliphatic polycarboxylic acid (6-20 or more carbon atoms) is used.
[0026]
(D1) Diallyl ether of dihydric phenol
For example, bisphenol F diallyl ether, bisphenol A diallyl ether, bisphenol B diallyl ether, bisphenol AD diallyl ether, bisphenol S diallyl ether, halogenated bisphenol A diallyl ether, tetrachlorobisphenol A diallyl ether, catechin diallyl ether, resorcinol diallyl ether, hydroquinone Diallyl ether, 1,5-dihydroxynaphthalenediallyl ether, dihydroxybiphenyl diallyl ether, octachloro-4,4′-dihydroxybiphenyl diallyl ether, tetramethylbiphenyl diallyl ether and 9,9′-bis (4-hydroxyphenyl) furorange allyl Examples include ether.
[0027]
(D2) polyallyl ether of polyphenol
For example, pyrogallol triallyl ether, dihydroxynaphthylcresol triallyl ether, tris (hydroxyphenyl) methane triallyl ether, dinaphthyltriol triallyl ether, tetrakis (4-hydroxyphenyl) ethanetetraallyl ether, trismethyl-tert-butyl-butyl Hydroxymethane triallyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol allyl ether, 4,4′-oxybis (1,4-phenylethyl) phenyl allyl ether and bis (dihydroxynaphthalene) tetraallyl Examples include ether.
[0028]
(D3) Diallyl ether of dihydric alcohol
For example, ethylene glycol diallyl ether, propylene glycol diallyl ether, tetramethylene glycol diallyl ether, 1,6-hexanediol diallyl ether, polyethylene glycol (Mw 150-4,000) diallyl ether, polypropylene glycol (Mw 180-5,000) diallyl ether , Polytetramethylene glycol (Mw 200 to 5,000) diallyl ether, neopentyl glycol diallyl ether, EO and / or PO (1 to 20 mol) adduct of bisphenol A, and the like.
[0029]
(D4) Polyallyl ether of a trihydric to heptovalent or higher polyhydric alcohol
Examples thereof include trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, sorbitol hexaallyl ether, and poly (degree of polymerization 2 to 5) glycerin polyallyl ether.
[0030]
(D5) Polyallyl ester of aromatic polycarboxylic acid
Examples thereof include phthalic acid diallyl ester, isophthalic acid diallyl ester, terephthalic acid diallyl ester, and trimellitic acid triallyl ester.
(D6) Polyallyl ester of aliphatic or alicyclic polycarboxylic acid
For example, (d5) aromatic nucleus water additive, dimer acid diallyl ester, diallyl oxalate, diallyl malate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, and triallylic acid triallyl ester Can be mentioned.
[0031]
As the monomer (e) having only a propenyl group as a crosslinkable functional group, (e1) dipropenyl ether of a dihydric phenol (having 6 to 30 carbon atoms), (e2) a polyhydric phenol {having 6 to 50 carbon atoms) Or higher, Mw 110 to 5,000 trivalent to hexavalent or higher polypropenyl ether, (e3) dihydric alcohol (2 to 100 or more carbon atoms, Mw 62 to 5,000) [carbon number Dipropenyl ether of 2 to 6 or more alkylene glycol or AO 1 to 90 mol adduct of dihydric phenol (carbon number 6 to 24)], (e4) trihydric to 7 or more polyhydric alcohol (carbon A polypropenyl ether having 3 to 50 or more and Mw of 76 to 10,000), (e5) a divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 carbon atoms or Poly propenyl ester, and (e6) poly propenyl esters of bivalent to hexavalent or more aliphatic or cycloaliphatic polycarboxylic acid (6-20 or more carbon atoms) is used in which higher).
[0032]
(E1) Dipropenyl ether of dihydric phenol
For example, bisphenol F dipropenyl ether, bisphenol A dipropenyl ether, bisphenol B dipropenyl ether, bisphenol AD dipropenyl ether, bisphenol S dipropenyl ether, halogenated bisphenol A dipropenyl ether, tetrachlorobisphenol A dipropenyl ether, catechin di Propenyl ether, resorcinol dipropenyl ether, hydroquinone dipropenyl ether, 1,5-dihydroxynaphthalenedipropenyl ether, dihydroxybiphenyl dipropenyl ether, octachloro-4,4'-dihydroxybiphenyl dipropenyl ether, tetramethylbiphenyl dipropenyl ether and 9 , 9'-Bis (4-hydroxyphenyl) furorange pro Vinyl ether, and the like.
[0033]
(E2) polypropenyl ether of polyhydric phenol
For example, pyrogallol tripropenyl ether, dihydroxynaphthylcresol tripropenyl ether, tris (hydroxyphenyl) methane tripropenyl ether, dinaphthyltriol tripropenyl ether, tetrakis (4-hydroxyphenyl) ethanetetrapropenyl ether, trismethyl-tert-butyl-butyl Hydroxymethane tripropenyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol propenyl ether, 4,4′-oxybis (1,4-phenylethyl) phenylpropenyl ether and bis (dihydroxynaphthalene) tetrapropenyl Examples include ether.
[0034]
(E3) Dipropenyl ether of dihydric alcohol
For example, ethylene glycol dipropenyl ether, propylene glycol dipropenyl ether, tetramethylene glycol dipropenyl ether, 1,6-hexanediol dipropenyl ether, polyethylene glycol (Mw 150-4,000) dipropenyl ether, polypropylene glycol (Mw 180-5) , 000) dipropenyl ether, polytetramethylene glycol (Mw 200 to 5,000) dipropenyl ether, neopentyl glycol dipropenyl ether, dipropenyl ether of EO and / or PO (1 to 20 mol) adduct of bisphenol A, etc. Is mentioned.
[0035]
(E4) A polypropenyl ether of a trihydric to 7-valent or higher polyhydric alcohol
Examples thereof include trimethylolpropane tripropenyl ether, glycerin tripropenyl ether, pentaerythritol tetrapropenyl ether, sorbitol hexapropenyl ether, and poly (polymerization degree 2 to 5) glycerin polypropenyl ether.
[0036]
(E5) Polypropenyl ester of aromatic polycarboxylic acid
Examples thereof include phthalic acid dipropenyl ester, isophthalic acid dipropenyl ester, terephthalic acid dipropenyl ester, trimellitic acid tripropenyl ester, and the like.
(E6) Polypropenyl ester of aliphatic or alicyclic polycarboxylic acid
For example, (d5) aromatic nucleus water additive, dimer acid dipropenyl ester, dipropenyl oxalate, dipropenyl malate, dipropenyl succinate, dipropenyl glutarate, dipropenyl adipate, dipropenyl pimelate and tri And carbaryl acid tripropenyl ester.
[0037]
As the monomer (f) having a primary amino group as a crosslinkable functional group, (f1) an aliphatic polyamine (2 to 18 carbon atoms, 2 to 7 amino groups), (f2) an alicyclic polyamine ( Carbon number 4-15, amino group number 2-3), (f3) polyamide polyamine, (f4) polyether polyamine, etc. are used.
[0038]
(F1) As aliphatic polyamine, C2-C6 alkylene diamine, polyalkylene (C2-C6) polyamine, alkyl of said polyamine (C1-C4) or hydroxyalkyl (C2-C4) ) Substituents, alicyclic or heterocyclic ring-containing aliphatic polyamines (5 to 18 carbon atoms) and aromatic ring-containing aliphatic polyamines (8 to 15 carbon atoms) can be used.
Examples of the alkylene diamine include ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the polyalkylene polyamine include diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
[0039]
Examples of the alkyl or hydroxyalkyl substituted product of polyamine include dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, and methyliminobispropylamine.
Examples of the alicyclic or heterocyclic ring-containing aliphatic polyamine include 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.
Examples of the aromatic ring-containing aliphatic polyamine include xylylenediamine and tetrachloro-p-xylylenediamine.
[0040]
Examples of (f2) alicyclic polyamines include 1,3-diaminocyclohexane, isophorone diamine, mensen diamine, and 4,4'-methylene dicyclohexane diamine (hydrogenated methylene dianiline).
(F3) As the polyamide polyamine, for example, Mw 80 to 2 obtained by condensation of dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mol of acid) polyamine (alkylene diamine, polyalkylene polyamine etc.). 1,000 polyamide polyamines and the like are used.
Specifically, for example, commercially available tomide (manufactured by Fuji Kasei Co., Ltd.), versamide (manufactured by Henkel Hakusui Co., Ltd.), rakermide (manufactured by Dainippon Ink Co., Ltd.), sunmide (manufactured by Sanwa Chemical Co., Ltd.) and polymide (manufactured by Sanyo Chemical Industries, Ltd.) Etc.
[0041]
Examples of the polyether polyamine (f4) include hydrides of cyanoethylated polyether polyols (2 to 6 valence, Mw 90 to 2,000) [for example, polyalkylene (carbon number 2 to 8) glycol and the like]. It is done.
[0042]
As the monomer (g) having a secondary amino group as a crosslinkable functional group, the primary amino group (—NH) of (f) is used.₂Group) can be used in which -NH-R (R is an alkyl group having 1 to 4 carbon atoms), such as di (methylamino) ethylene, di (ethylamino) hexane and 1,3-di (methyl). Amino) cyclohexane and the like.
[0043]
As the monomer (h) having only a carboxyl group as a crosslinkable functional group, (h1) a divalent to hexavalent or higher aromatic polycarboxylic acid (having 6 to 20 or more carbon atoms), and ( h2) Divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acids (having 6 to 20 or more carbon atoms) are used.
(H1) Aromatic polycarboxylic acid
Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, hymic acid and trimellitic acid.
(H2) Aliphatic or alicyclic polycarboxylic acid
Examples include (h1) aromatic nucleus water additive, dimer acid, oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, tricarballylic acid and dodecenyl succinic acid.
[0044]
As the monomer (i) having only a hydroxyl group as a crosslinkable functional group, (i1) a dihydric phenol having 6 to 30 carbon atoms, (i2) a polyhydric phenol (having 6 to 50 or more carbon atoms, Mw110 (I3) dihydric alcohol (2 to 100 or more carbon atoms, Mw 6 to 5,000) [alkylene glycol having 2 to 6 or more carbon atoms, or Dihydric phenol (AO 1 to 90 mol adduct of 6 to 24 carbon atoms)], and (i4) a trihydric to 7 or higher polyhydric alcohol (having 3 to 50 or more carbon atoms, Mw 76 to 10, 000) or the like.
[0045]
(I1) Examples of the divalent phenol include bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A (for example, tetrachlorobisphenol A), catechin, resorcinol, hydroquinone, 1,5- Examples include dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4′-dihydroxybiphenyl, tetramethylbiphenyl, and 9,9′-bis (4-hydroxyphenyl) fluorene.
[0046]
(I2) Examples of the polyhydric phenol include pyrogallol, dihydroxynaphthylcresol, tris (hydroxyphenyl) methane, dinaphthyltriol, tetrakis (4-hydroxyphenyl) ethane, trismethyl-tert-butyl-butylhydroxymethane, 4,4 Examples include '-oxybis (1,4-phenylethyl) tetracresol, 4,4'-oxybis (1,4-phenylethyl) phenyl and bis (dihydroxynaphthalene).
[0047]
(I3) Examples of the dihydric alcohol 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 polytetra Examples include methylene glycol (Mw 200 to 5,000), neopentyl glycol, and EO and / or PO (1 to 20 mol) adducts of bisphenol A.
[0048]
Examples of (i4) polyhydric alcohol include trimethylolpropane, ditrimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, and poly (degree of polymerization 2 to 5) glycerin.
[0049]
As the monomer (j) having only an isocyanate group as a crosslinkable functional group, (j1) an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same applies hereinafter), ( j2) an aliphatic polyisocyanate having 2 to 18 carbon atoms, (j3) an alicyclic polyisocyanate having 4 to 15 carbon atoms, (j4) an araliphatic polyisocyanate having 8 to 15 carbon atoms, and (j5) the above polyisocyanate. Modified products (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product, etc.).
[0050]
(J1) As the aromatic polyisocyanate, for example, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 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; a mixture of diaminodiphenylmethane and a trifunctional or higher polyamine of a small amount (for example, 5 to 20% by mass)] ] Phosgenates: polyallyl polyisocyanate (PAPI)], 1, - naphthylene diisocyanate, 4,4 ', 4 "- triphenylmethane triisocyanate and m- and p- isocyanatophenyl sulfonyl isocyanate.
[0051]
(J2) Examples of the aliphatic polyisocyanate 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 Eate.
[0052]
(J3) Examples of the alicyclic polyisocyanate include 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.
(J4) Examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).
[0053]
(J5) Examples of the modified polyisocyanate include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, and the like. And a mixture of two or more kinds thereof [for example, combined use of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)].
As the polyol used for the production of the urethane-modified polyisocyanate [free isocyanate-containing prepolymer obtained by reacting excess polyisocyanate (TDI, MDI, etc.) and polyol], a polyol having an equivalent weight of 30 to 200 can be used. For example, glycol (ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc.), triol (trimethylolpropane, glycerin, etc.), high functional polyol (pentaerythritol, sorbitol, etc.) and their AO (EO and / or PO1-20) Mol) adducts and the like.
[0054]
Examples of the monomer (k) having a nitrile group and a vinyl group as a crosslinkable functional group include cyanobutene and cyanostyrene.
Examples of the monomer (m) having a nitrile group and a (meth) acryloyl group as a crosslinkable functional group include (meth) acrylonitrile and cyanoethyl (meth) acrylate.
[0055]
As the monomer (n) having a hydroxyl group and a (meth) acryloyl group as a crosslinkable functional group, a mono (meth) acrylate (Mw 300 to 3,000) having a polyalkylene (2 to 8 carbon atoms) glycol chain may be used. For example, polyethylene glycol (Mw300) mono (meth) acrylate, polypropylene glycol (Mw500) mono (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, Examples include trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and polyglycerin (degree of polymerization as described above) mono (meth) acrylate.
[0056]
Examples of the monomer (o) having an epoxy group and a (meth) acryloyl group as a crosslinkable functional group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
Examples of the monomer (p) having an epoxy group and a vinyl group as a crosslinkable functional group include vinylcyclohexene monooxide and butadiene monooxide.
Examples of the monomer (q) having a (meth) acryloyl group and a vinyl group as a crosslinkable functional group include vinyl methacrylate and vinyloxyethyl (meth) acrylate.
[0057]
Examples of the monomer (r) having a (meth) acryloyl group and an isocyanate group as a crosslinkable functional group include 2- (meth) acryloylethyl isocyanate and (meth) acryloylpropyl isocyanate.
Examples of the monomer (s) having a (meth) acryloyl group and a carboxyl group as a crosslinkable functional group include (meth) acrylate, maleic acid, maleic anhydride, and the like.
Examples of the monomer (t) having a (meth) acryloyl group and an allyl group as a crosslinkable functional group include allyl methacrylate and allyloxyethyl (meth) acrylate.
Examples of the monomer (u) having a (meth) acryloyl group and a propenyl group as a crosslinkable functional group include propenyl methacrylate and propenyl ethyl (meth) acrylate.
[0058]
As the monomer (v) having a secondary amino group and an allyl group as a crosslinkable functional group, the primary amino group (-NH) of (f) is used.₂In which at least a part of the group is replaced by —NH—R (R is an allyl group), such as di (allylamino) ethylene, di (allylamino) hexane, 1,3-di (allylamino) cyclohexane, etc. Can be mentioned.
[0059]
As the monomer (w) having a secondary amino group and a propenyl group as a crosslinkable functional group, the primary amino group (—NH) of (f) is used.₂In which at least a part of the group) is replaced by —NH—R (R is a propenyl group), such as di (propenylamino) ethylene, di (propenylamino) hexane, and 1,3-di (propenylamino). And cyclohexane.
[0060]
Of these monomers having a crosslinkable functional group, (n), (o), (p), (q), (s), (t) and (u) are preferable, and (n) is more preferable. , (O), (p) and (s), particularly preferably (n) and (o).
These monomers can be used alone, in combination of two or more, and / or with other copolymerizable monomers.
[0061]
When combining two or more of these, combinations of monomers that can be copolymerized are as follows.
Monomers that can be copolymerized with (a) include (f), (g), (h), (i), (j), (n), (o), (p), (r), ( s), (v) and (w) are used.
Monomers that can be copolymerized with (b) include (c), (d), (e), (k), (m), (n), (o), (p), (q), ( r), (s), (t), (u), (v) and (w) are used.
[0062]
Monomers that can be copolymerized with (c) include (b), (d), (e), (k), (m), (n), (o), (p), (q), ( r), (s), (t), (u), (v) and (w) are used.
Monomers that can be copolymerized with (d) include (b), (c), (e), (k), (m), (n), (o), (p), (q), ( r), (s), (t), (u), (v) and (w) can be used.
Monomers that can be copolymerized with (e) include (b), (c), (d), (k), (m), (n), (o), (p), (q), ( r), (s), (t), (u), (v) and (w) are used.
[0063]
Monomers that can be copolymerized with (f) include (a), (g), (h), (i), (j), (n), (o), (p), (r), ( s), (v) and (w) are used.
Monomers that can be copolymerized with (g) include (a), (f), (h), (i), (j), (n), (o), (p), (r), ( s), (v), (w), etc. are used.
Monomers that can be copolymerized with (h) include (a), (f), (g), (i), (j), (n), (o), (p), (r), ( s), (v) and (w) are used.
[0064]
Monomers that can be copolymerized with (i) include (a), (f), (g), (h), (j), (n), (o), (p), (r), ( s), (v) and (w) are used.
Monomers that can be copolymerized with (j) include (a), (f), (g), (h), (i), (n), (o), (p), (s), ( v) and (w) are used.
Monomers that can be copolymerized with (k) include (b), (c), (d), (e), (m), (n), (o), (p), (q), ( r), (s), (t), (u), (v) and (w) are used.
[0065]
Monomers that can be copolymerized with (m) include (b), (c), (d), (e), (k), (n), (o), (p), (q), ( r), (s), (t), (u), (v) and (w) are used.
Monomers that can be copolymerized with (n) include (a), (b), (c), (d), (e), (f), (g), (h), (i), ( j), (k), (m), (o), (p), (q), (r), (s), (t), (u), (v), and (w) are used. .
[0066]
Monomers that can be copolymerized with (o) include (a), (b), (c), (d), (e), (f), (g), (h), (i), ( j), (k), (m), (n), (p), (q), (r), (s), (t), (u), (v), and (w) are used. .
Monomers that can be copolymerized with (p) include (a), (b), (c), (d), (e), (f), (g), (h), (i), ( j), (k), (m), (n), (o), (q), (r), (s), (t), (u), (v), and (w) are used. .
[0067]
Monomers that can be copolymerized with (q) include (b), (c), (d), (e), (k), (m), (n), (o), (p), (p r), (s), (t), (u), (v) and (w) are used.
Monomers that can be copolymerized with (r) include (a), (b), (c), (d), (e), (f), (g), (h), (i), ( j), (k), (m), (n), (o), (p), (q), (s), (t), (u), (v), and (w) are used. .
[0068]
Monomers copolymerizable with (s) include (a), (b), (c), (d), (e), (f), (g), (h), (i), ( j), (k), (m), (n), (o), (p), (q), (r), (t), (u), (v), and (w) are used. .
Monomers that can be copolymerized with (t) include (b), (c), (d), (e), (k), (m), (n), (o), (p), (p q), (r), (s), (u), (v) and (w) are used.
Monomers that can be copolymerized with (u) include (b), (c), (d), (e), (k), (m), (n), (o), (p), (p q), (r), (s), (t), (v) and (w) are used.
[0069]
Monomers that can be copolymerized with (v) include (a), (b), (c), (d), (e), (f), (g), (h), (i), ( j), (k), (m), (n), (o), (p), (q), (r), (s), (t), (u), and (w) are used. .
Monomers that can be copolymerized with (w) include (a), (b), (c), (d), (e), (f), (g), (h), (i), ( j), (k), (m), (n), (o), (p), (q), (r), (s), (t), (u), and (v) are used. .
[0070]
As other copolymerizable monomers, the following (aa) to (ww) can be used.
As the monomer (aa) copolymerizable with (a), a hydrocarbon oxide (aa1) having 4 to 24 carbon atoms, a monoglycidyl ether (aa2) having a hydrocarbon (3 to 21 carbon atoms), 18 aliphatic carboxylic acid (aa3), C7-C18 aromatic carboxylic acid (aa4), C1-C18 alcohol (aa5), C6-C18 phenol (aa6), C1-C1 18 aliphatic amines (aa7), C6-C18 aromatic amines (aa8), and the like are used.
[0071]
Examples of (aa1) hydrocarbon oxide include EO, PO, butene oxide, α-olefin oxide having 5 to 18 carbon atoms (eg, pentane oxide, decene oxide, octadecene oxide, etc.), styrene oxide, and the like.
(Aa2) Monoglycidyl ether of hydrocarbon (having 4 to 21 carbon atoms) includes, for example, methyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and octadecyl glycidyl ether .
[0072]
Examples of (aa3) aliphatic carboxylic acid include acetic acid, butanoic acid, 2-ethylhexanoic acid, undecanoic acid, and octadecanoic acid.
Examples of (aa4) aromatic carboxylic acid include benzoic acid, p-methylbenzoic acid and naphthalenecarboxylic acid.
Examples of (aa5) alcohol include methanol, isopropanol, butanol, 2-ethylhexanol, tetradecyl alcohol, octadecyl alcohol, and benzyl alcohol.
(Aa6) Phenols include, for example, phenol, o-, m- or p-cresol and p-ethylphenol.
[0073]
Examples of (aa7) aliphatic amine include methylamine, dimethylamine, methylbutylamine, undecylamine, decalylamine, and octadecylamine.
Examples of (aa8) aromatic amine include aniline, p-methylaniline, p-undecylaniline, m-methoxyaniline, and naphthylamine.
[0074]
  The monomer (bb) that can be copolymerized with (b)2-20 olefin (bb1), aromatic compound (bb2) having a polymerizable unsaturated double bond having 8 to 18 carbon atoms, (meth) acrylic acid alkyl ester (bb3) having 5 to 22 carbon atoms and 4 carbon atoms ~ 20 polymerizable fatty acid ester (bb4) and the like are used.
  (Bb1) As the olefin, for example, ethylene, propylene, butene, 1-octene, 1-decene, 1-eicocene, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6 , 7,8,8a-octahydronaphthalene, norbornene, dicyclopentadiene, 5-ethylidene-2-norbornene and the like.
[0075]
(Bb2) Examples of aromatic compounds having a polymerizable unsaturated double bond include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, p-decylstyrene, and p-chloro. Examples include styrene and divinylbenzene.
Examples of (bb3) (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, undecyl (meth) acrylate, and octadecyl (meth) acrylate.
Examples of the (bb4) polymerizable fatty acid ester include vinyl acetate, vinyl propanoate, vinyl octadecanoate, allyl acetate, allyl butanoate, propenyl acetate, and propenyl hexanoate.
[0076]
As the monomer (cc) copolymerizable with (c), (bb1), (bb2), (bb3) and (bb4) are used.
As the monomer (dd) copolymerizable with (d), (bb1), (bb2), (bb3), (bb4) and the like can be used.
As the monomer (ee) copolymerizable with (e), (bb1), (bb2), (bb3), (bb4) and the like are used.
As the monomer (ff) copolymerizable with (f), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7) and (aa8) are used. It is done.
[0077]
As the monomer (gg) copolymerizable with (g), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7) and (aa8) are used. It is done.
As the monomer (hh) copolymerizable with (h), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7) and (aa8) are used. It is done.
As the monomer (ii) copolymerizable with (i), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7) and (aa8) are used. It is done.
[0078]
As the monomer (jj) copolymerizable with (j), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7) and (aa8) are used. It is done.
As the monomer (kk) copolymerizable with (k), (bb1), (bb2), (bb3) and (bb4) are used.
Examples of the monomer (mm) that can be copolymerized with (m) include (bb1), (bb2), (bb3), and (bb4).
As the monomer (nn) copolymerizable with (n), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7), (aa8), (bb1) ), (Bb2), (bb3) and (bb4).
[0079]
As the monomer (oo) copolymerizable with (o), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7), (aa8), (bb1) ), (Bb2), (bb3) and (bb4).
As the monomer (pp) copolymerizable with (p), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7), (aa8), (bb1) ), (Bb2), (bb3) and (bb4).
Examples of the monomer (qq) that can be copolymerized with (q) include (bb1), (bb2), (bb3), and (bb4).
[0080]
As the monomer (qq) copolymerizable with (r), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7), (aa8), (bb1) ), (Bb2), (bb3) and (bb4).
As the monomer (ss) copolymerizable with (s), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7), (aa8), (bb1) ), (Bb2), (bb3) and (bb4).
As the monomer (tt) copolymerizable with (t), (bb1), (bb2), (bb3), (bb4) and the like are used.
[0081]
As the monomer (uu) copolymerizable with (u), (bb1), (bb2), (bb3), (bb4) and the like are used.
As the monomer (vv) copolymerizable with (v), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7), (aa8), (bb1) ), (Bb2), (bb3) and (bb4).
As the monomer (ww) copolymerizable with (w), (aa1), (aa2), (aa3), (aa4), (aa5), (aa6), (aa7), (aa8), (bb1) ), (Bb2), (bb3) and (bb4).
[0082]
Of these other copolymerizable monomers, (nn), (oo), (pp), (qq), (ss), (tt), and (uu) from the viewpoint of heat resistance, electrical properties, and resin strength. ), More preferably (nn), (oo), (pp), (qq) and (ss), particularly preferably (nn) and (oo), most preferably styrene, ethylene, propylene, 6-methyl -1,4: 5,8-octahydronaphthalene, norbornene, dicyclopentadiene and 5-ethylidene-2-norbornene.
These other copolymerizable monomers can be used alone or in combination of two or more.
[0083]
When other copolymerizable monomers are used, the amount of other copolymerizable monomers is not particularly limited, but is based on the weight of all monomers used from the viewpoint of heat resistance and resin strength. 20 to 80% by weight is preferable, more preferably 35 to 70% by weight, and particularly preferably 50 to 60% by weight.
[0084]
(1) The method for (co) polymerizing a monomer having a crosslinkable functional group is not particularly limited, and a normal method can be applied. For example, in a reaction vessel substituted with nitrogen as necessary, a crosslinkable property can be used. A method in which a monomer having a functional group and, if necessary, a monomer copolymerizable therewith are dropped and then aged for an appropriate time can be applied.
The reaction temperature is generally 0 to 180 ° C, preferably 60 to 150 ° C. The aging time is usually 0 to 50 hours, preferably 4 to 15 hours.
When two or more kinds of monomers are used, the polymerization type may be a block type or a random type.
[0085]
For the polymerization, a solvent can be used, and the solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the monomer and the resin to be formed. For example, an aromatic solvent (for example, toluene and xylene) Etc.), ketone solvents (for example, acetone, methyl ethyl ketone and methyl isobutyl ketone), ether solvents (for example, diethyl ether, dioxane and tetrahydrofuran) and halogen solvents (for example, chloroform, carbon tetrachloride and dichloromethane, etc.) are used. .
When the 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 60% by weight based on the total weight of the monomers.
[0086]
Further, a reaction initiator (C) can be used, and (C) is not particularly limited, and those used for ordinary reactions are used. Depending on the type of the crosslinkable functional group, a radical reaction initiation catalyst ( C1), cationic polymerization initiation catalyst (C2), esterification catalyst (C3), amidation catalyst (C4), epoxy ring-opening catalyst (C5), isocyanate reaction catalyst (C6) and the like are used.
As the radical reaction initiation catalyst (C1), a thermal radical reaction initiation catalyst (C11), a photo radical reaction initiation catalyst (C12), or the like can be used.
As the thermal radical reaction initiation catalyst (C11), those having a 10-hour half-life temperature of 80 ° C. or higher are preferred from the viewpoint of storage stability, more preferably those having a temperature of 120 ° C. or higher, such as peroxides and azo compounds. Used.
[0087]
Examples of the peroxide include t-butyl peroxyacetate, t-butyl peroxybenzoate, 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.
[0088]
Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), and the like. Can be mentioned.
Examples of the photoradical reaction initiation catalyst (C12) include benzoin alkyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, and methylbenzoylpho Mate and isopropylthioxanthone.
[0089]
Further, a sensitizer can be used together with these photoradical reaction initiation catalysts (C12), and nitro compounds (for example, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p, p′- Carbonyl compounds such as tetramethyldiaminobenzophenone and chloranil, nitrobenzene, p-dinitrobenzene and 2-nitrofluorene), aromatic hydrocarbons (eg anthracene and chrysene), sulfur compounds (eg diphenyl disulfide etc.) and nitrogen compounds (For example, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene, etc.) and the like.
[0090]
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), onium salt catalysts (for example, triarylsulfonium salts and diaryliodonium salts) can be used. For example, Sun Aid SI series (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) Can be mentioned.
[0091]
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, Examples include UVR-6990 (trade name, manufactured by Union Carbide), CI-2855 (trade name, manufactured by Nippon Soda Co., Ltd.), CD-1012 (trade name, manufactured by Sartomer), and the like.
[0092]
Examples of the esterification catalyst (C3) and amidation catalyst (C4) include acid catalysts (hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroborane, etc.), alkalis (for example, sodium hydroxide) , Potassium hydroxide, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU, manufactured by San Apro, registered trademark), and metal complexes (for example, tetrapropyltitanium, etc.).
[0093]
Examples of the epoxy ring-opening catalyst (C5) include imidazole catalysts (2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl- 2-methylimidazole and 1-cyanoethyl-2-methylimidazole), 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., Sun-Aid SI series, etc.).
[0094]
As the isocyanate reaction catalyst (C6), organometallic compounds (for example, trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, lead oleate) , Lead 2-ethylhexanoate, lead naphthenate, lead octenoate, bismuth octoate, bismuth naphthenate, cobalt naphthenate and phenylmercurypropionate, etc., and tertiary amines (eg DBU, N-methylmorpholine, N-ethylmorpholine, methyldibutylamine, triethylamine, and carbonates thereof and organic acid salts having 1 to 8 carbon atoms (such as formate salts)).
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.% based on the total weight of the monomers. It is 0% by weight, particularly preferably 0.05 to 1.0% by weight.
[0095]
Moreover, 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 for ordinary reactions are used. For example, diphenylhydrazyl, tri-p-nitrylphenylmethyl, 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 polymerization inhibitor used is preferably 0.1 to 5.0% by weight, more preferably 0.1 to 2.0% by weight, based on the total weight of monomers. Particularly preferred is 0.5 to 1.0.
[0096]
(2) A method for converting a crosslinkable functional group by reacting a resin having a crosslinkable functional group with a resin having a crosslinkable functional group is not particularly limited, and a normal method can be applied. A method in which a monomer having a crosslinkable functional group is dropped onto a resin having at least two crosslinkable functional groups produced by the method 1 and then aged for an appropriate time can be applied.
The reaction temperature, aging time, solvent, reaction initiator and polymerization inhibitor are the same as in method (1).
[0097]
Moreover, you may make it react with all the crosslinkable functional groups in resin, and you may make it react only with the one part. The reaction with a part thereof can be easily achieved by limiting the amount of the monomer having a crosslinkable functional group.
For example, the resin obtained by copolymerizing hydroxyethyl (20-80 parts by weight) with methacrylic acid (20-80 parts by weight) and styrene (80-20 parts by weight) is cross-linked with (meth) acrylic acid by esterification reaction The functional group can be converted from a hydroxyl group to a (meth) acryloyl group.
[0098]
In place of the resin produced by the method (1), a monomer having a crosslinkable functional group may be introduced into a resin having no crosslinkable functional group by a graft reaction.
For example, 30 mol parts of propylene, 70 mol parts of 5-ethylidene-2-norbornene and a solvent are charged in a reaction vessel substituted with nitrogen, and a transition metal compound (for example, titanium compound) / aluminum compound catalyst is used. After addition copolymerization, a copolymer is obtained, and then a monomer having a crosslinking functional group such as glycidyl (meth) acrylate, vinylcyclohexene monooxide, or 3,4-epoxycyclohexylmethyl (meth) acrylate is grafted onto the polymer. Thus, a crosslinkable functional group can be introduced.
[0099]
The Mw of the low molecular compound (B) is 170 to 3,000, and preferably 200 to 1,500 from the viewpoint of the strength after curing of the resin composition of the present invention and the viscosity thereof.
The crosslinking functional group (B) is the same type as (A), and preferred ones are also the same.
The number of 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 even more preferably. Is 7 to 500, and most preferably 10 to 200. As (B), for example, in addition to (a) to (w), as a monomer having one crosslinkable functional group, (aa1) to (aa8) and (bb1) to (bb4) can be used. In addition to these, the following monoepoxide (x), polyepoxide (y), curing agent (z) and the like can be used.
[0010]
As the monoepoxide (x), a glycidyl ester (x1) of a monocarboxylic acid (having 3 to 30 carbon atoms) and a cyclohexene monooxide group-containing compound (x2) are used.
Examples of the glycidyl ester (x1) of monocarboxylic acid include glycidyl (meth) acrylate, epihalohydrin (eg, epichlorohydrin, epibromohydrin, etc.), hydroxyl group-containing oxide (eg, glycidol, etc.), and the like.
[00101]
Examples of the cyclohexene monooxide group-containing compound (x2) include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxymethylcyclohexanecarboxylate and 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4. Examples include '-epoxy-6'-methylcyclohexanecarboxylate.
[0102]
Examples of the polyepoxide (y) include vinylcyclohexene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, glycidyl ether of phenol or cresol novolak resin (Mw 400 to 3,000), limonene phenol novolak resin (Mw 400). ˜3,000) glycidyl ether, phenol and glycoxal, polyphenol obtained by condensation reaction of glutaraldehyde or formaldehyde (Mw 400 to 3,000), polyglycidyl ether of Mw 400˜3,000 obtained by condensation reaction of resorcin and acetone Polyglycidyl ether of 3,000 polyphenols, (co) polymer of glycidyl (meth) acrylate (degree of polymerization 2 to 10 for example), epoxy equivalent 130 to , 000 epoxidized polybutadiene (Mw170~3,000), and epoxidized soybean oil (Mw170~3,000), and the like.
[0103]
Examples of the curing agent (z) include acid anhydrides (h), (aa3), and (aa4).
Among these low molecular compounds (B), (a), (b), (c), (d), (e), (m), (n), (o), (p), (q) , (R), (s), (t), (u), (h), (aa3) and (aa4), more preferably (a), (b), (n), (o), (P) and (s), particularly preferably (a), (b), (n) and (o).
[0104]
When using a monoepoxide (x), a polyepoxide (y), a curing agent (z), etc., these used weights are not particularly limited, but from the viewpoint of heat resistance and resin strength, the weight of all monomers used. 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) used between (A) and (B) is preferably 10 to 95: 5 to 90, more preferably 20 to 90:10 to 80, and particularly preferably 30 to 80:20 to 70. It is.
[0105]
A reaction initiator (C) can be used in the curable resin composition of the present invention. (C) may be added immediately before use of the curable resin composition of the present invention, or may be added during the production of the curable resin composition.
When (C) is used, the amount used of (C) (not including (A) used during preparation) is 0.001 to 10 based on the total weight of (A) and (B). % By weight is preferable, more preferably 0.01 to 8% by weight, particularly preferably 0.05 to 5% by weight, and most preferably 0.1 to 2% by weight.
[0106]
The curable resin composition of the present invention can contain other additives (D), other resins (E), rubber (F), fillers (G), and the like.
Examples of the other additive (D) include a phenol-based anti-aging agent, a phosphorus-based anti-aging agent, a flame retardant, a phenol-based heat deterioration preventing agent, a benzophenone-based UV stabilizer, and an antistatic agent.
When (D) is used, the amount of (D) used is preferably from 0.001 to 3.0% by weight, more preferably from 0.01 to 3.0%, based on the total weight of (A) and (B). It is 2.0% by weight, particularly preferably 0.05 to 1.0% by weight.
[0107]
Examples of the other resin (E) include ABS resin, polystyrene, polycarbonate, polyamide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyimide, polysulfone, polyethersulfone, and polyarylate.
When (E) is used, the amount of (E) used is preferably 1 to 45% by weight, more preferably 5 to 40% by weight, particularly preferably based on the total weight of (A) and (B). Is 10 to 30% by weight.
[0108]
Examples of the rubber (F) include isoprene rubber, butadiene rubber, styrene-butadiene rubber, styrene / isoprene rubber, nitrile rubber, chloroprene rubber, and ethylene-propylene rubber.
When (F) is used, the amount of (F) used is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, particularly preferably based on the total weight of (A) and (B). Is 8 to 25% by weight.
[0109]
Examples of the filler (G) include silica, alumina, calcium carbonate, barium sulfate, and titanium oxide.
When (G) is used, the amount of (G) used is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably based on the total weight of (A) and (B). Is 8-30% by weight.
[0110]
Furthermore, the curable resin composition of the present invention can contain a solvent.
As the solvent, the same solvent as that which can be used in the polymerization of (A) can be used. The curable resin composition of the present invention may be used as it is without removing the solvent during the polymerization of (A), and after the solvent is removed during the polymerization of (A), the curable resin composition of the present invention is produced. Sometimes the same or different solvents used in the polymerization of (A) may be added, and (B) and the solvent may be mixed and mixed with (A).
When the solvent is used, the amount of the solvent used is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, based on the total weight of (A) (weight not including the solvent) and (B). Particularly preferred is 30 to 70% by weight.
[0111]
The curable resin composition of the present invention can be easily produced by uniformly mixing (A) and (B) and, if necessary, (C) to (G) by an ordinary method. It can be produced by the methods 1) to (3).
(1) A method in which (C) to (G) and / or a solvent are mixed as necessary after blending (A) and (B).
(2) A method of mixing (B) with (A) and (C) to (G) and / or a solvent, if necessary.
(3) A method of simultaneously mixing (A) and (B) with (C) to (G) and / or a solvent as required.
[0112]
The dielectric constant (based on JIS K6911 (1995) 5.14) after curing of the curable resin composition of the present invention is 3.5 or less at 1 GHz, and preferably 2 to 3.5. When the dielectric constant exceeds 3.5, when applied to an integrated circuit of an electronic component, there is a tendency that signal delay occurs and it is difficult to improve the performance of the circuit. Further, when the dielectric constant is 2 or more, it is not necessary to disperse the bubbles in the curable resin composition, and the resin strength does not decrease.
[0113]
As a method for adjusting the dielectric constant, a method of adjusting according to the type of monomer used as the production raw material of (A), for example, ethylene, propylene, butadiene, isoprene, (meth) acrylic acid ester having 4 or more carbon atoms, and Increasing the use ratio of all monomers such as styrene tends to lower the dielectric constant, and increasing the use amount of (meth) acrylic acid and acrylonitrile tends to increase the dielectric constant.
For example, as the composition having a dielectric constant of 2 to 3.5, the amount of styrene / glycidyl (meth) acrylate = 10 to 55/90 to 45 parts by mass and 4-methylcyclohexane-1,2-dicarboxylic anhydride A stoichiometric (equivalent ratio) mixture and the like can be mentioned.
In addition, the boiling water absorption after curing of the curable resin composition of the present invention (based on JIS K7209 (2000) 6.3B method) is preferably 3.00 to 0.001%, more preferably 2.50. ˜0.005%, particularly preferably 2.00 to 0.01%.
[0114]
The form of the curable resin composition of the present invention may be, for example, either liquid (including solution) or film (including plate and sheet), and the film thickness is preferably 1 to 100 μm. Preferably it is 5-50 micrometers, Most preferably, it is 15-50 micrometers.
In order to form a film, the liquid curable resin composition of the present invention is subjected to a usual molding method, for example, a curtain coater, a knife coater, a spray gun, a roll coater, a spin coater, a dispenser, a bar coater and a screen printing machine. It can be formed into a film by a method of applying to a support or a substrate by using, a dipping method or an injection molding method.
Even in the case of a film, it is softened by heating (hot pressing or the like), has good penetration into a minute part (such as a concavo-convex part) of a substrate, and is excellent in workability.
When a support is used, the film on the support can be transferred to a substrate or the like, and when a substrate or the like is used, it can be used as it is.
After coating, it is preferable to heat for the purpose of drying the solvent and the like. As heating conditions, for example, temperature: 10 to 150 ° C. (preferably 20 to 120 ° C.), time: 1 to 60 minutes (preferably 2 to 40 minutes).
[0115]
As the support, for example, PET (polyethylene terephthalate), polyethylene, polypropylene, and modified products thereof can be used.
As the substrate, various printed wiring boards having conductive (copper, gold, silver, aluminum, etc.) circuits can be used, for example, resin for substrate production (epoxy resin, bismaleimide triazine resin (BT), polyamide resin, etc.) Is obtained by impregnating a non-woven fabric (glass fiber non-woven fabric, aramid fiber non-woven fabric, etc.) or the like, or by adding a glass fiber to a resin for substrate production and bonding a copper circuit (for example, a BT substrate, glass) Epoxy substrates, paper phenol substrates, paper epoxy substrates, etc.) can be used.
[0116]
The curable resin composition of the present invention can be used as an insulator by being cured by heating, and is suitable as an overcoat material, an interlayer insulating material, a printed circuit board, and the like, and in particular, an overcoat material and an interlayer insulating material It is suitable as.
It is most suitable as an overcoat material or an interlayer insulating material for electronic elements (semiconductor elements, light emitting diodes, various memories, etc.), hybrid ICs, MCMs, electric wiring circuit boards or display components.
The heat curing conditions are 80 to 250 ° C. (preferably 120 to 200 ° C.) and 0.1 to 15 hours (preferably 0.2 to 12 hours).
[0117]
As a method of using the composition of the present invention as an insulator, for example, when used as an interlayer insulating material, the liquid composition of the present invention is applied to a base material, or the film-like composition of the present invention is laminated. After that, heat pressing, drilling as necessary (roughening, conductive circuit formation, etc.) processing, further laminating the base materials, repeating this operation, and finally heat-curing to multi-layer Etc.
In addition, when the composition of the present invention is used as a part of a substrate material of a multilayer substrate, the liquid composition of the present invention is applied to a base material, or the film-shaped composition of the present invention is laminated, Examples of the method include multilayering by hot pressing, performing drilling or the like as necessary, repeating this operation, and finally heat-curing.
In addition, it can also use as a printed wiring board as it is, without using a base material.
[0118]
When used as an interlayer insulating material such as a multilayer circuit board for an electronic circuit, one interlayer insulating layer may be composed of one layer or multiple layers, and the film thickness is preferably 1 to 100 μm, more preferably 15 to 50 μm.
As conditions for hot pressing, the temperature is 25 to 180 ° C. (preferably 50 to 150 ° C.), the pressure is 0.01 MPa to 10 MPa (preferably 0.1 to 1 MPa), and the time is 1 to 1200 seconds (preferably 10 to 300 seconds). Etc. are preferred.
Holes (via holes, through holes, etc.) for conducting the layers of the multilayer substrate can be created by a normal method, 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 normal method, for example, the method described in Japanese Patent Publication No. 6-49852 can be used.
The conductive circuit can be formed by a normal method, for example, a sputtering method or an electroless method can be used.
[0119]
The insulator obtained from the curable resin composition of the present invention has a volume resistance (based on JIS K6011 (1995)) of 10¹⁵-10¹⁷It is Ω / cm, and is superior in electrical insulation as compared with epoxy resins and polyimide resins that are conventionally used insulating materials.
Moreover, the adhesiveness with the copper formed by oxidizing agent processing and electroless copper plating is also favorable, and peel strength (conforming to JIS C6481 (1995) 5.7) shows 0.8 kgf / cm or more.
On the other hand, the heat resistance is the same as that of conventional insulators. Even if it is brought into contact with 300 ° C. solder for 1 minute, no abnormalities such as sagging, breakage and blistering are observed, and crack resistance against various solvents is also observed. Very good.
Moreover, the insulating material in the present invention is excellent in 10% sulfuric acid resistance, 10% hydrochloric acid resistance, 10% nitric acid resistance and 10% sodium hydroxide resistance measured by the method defined in JIS K 6911 (1995) 5.32. .
Therefore, the curable resin composition of the present invention has great advantages for increasing the speed and density of electronic circuits.
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Hereinafter, parts represent parts by mass, and% represents mass%.
Synthesis example 1
50 parts of methyl ethyl ketone was charged in a reaction vessel substituted with nitrogen, heated to 80 ° C., and uniformly dissolved in another nitrogen-substituted vessel, 200 parts of glycidyl methacrylate, 200 parts of styrene, 200 parts of methyl ethyl ketone, and azo A mixture consisting of 1.5 parts of bisisobutyronitrile was dropped into the reaction vessel over 4 hours. After completion of dropping, the mixture was aged at 100 ° C. for 4 hours to obtain a resin (A1) solution of styrene / glycidyl methacrylate = 50 parts / 50 parts.
Mw of (A1) is 160,000, the number average molecular weight by GPC (hereinafter abbreviated as Mn) is 53,000, the epoxy equivalent is 284, and the crosslinkable functional group of (A1) (M1 and epoxy equivalent) The number of epoxy groups was 187.
(A1) was prepared using methyl ethyl ketone so that the solid content was 40%, to obtain a resin solution (A11).
[0120]
Synthesis example 2
The following polymerization experiments were performed in a glove box substituted with nitrogen.
To a four-necked flask equipped with a stirrer and a temperature controller, 100 parts of toluene was charged, and the temperature was adjusted to 30 ° C. with stirring. 5 parts by weight of a hexane solution of vanadium oxytrichloride (catalyst concentration: 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.
The copolymer solution was added dropwise to 3000 parts of isopropanol with stirring to form a precipitate. The precipitate was distilled off in a vacuum dryer at 100 ° C. under a reduced pressure of 10 mmHg to obtain a resin (A2). 70 parts were obtained.
The Mw of (A2) was 98,000.
[0121]
(A2) 100 parts, 20 parts of glycidyl methacrylate and 7.0 parts of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (manufactured by NOF Corporation, trade name: Perhexa 25B) at room temperature After dry blending, a resin (A3) was obtained by extrusion with a twin screw extruder under conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 230 rpm.
Mw of (A3) was 117,000, Mn was 29,000, epoxy equivalent was 850, and the number of crosslinkable functional groups (epoxy groups) of (A3) was 138 from Mn and epoxy equivalent.
(A3) was dissolved in toluene with a solid content of 40% to obtain a resin solution (A33).
[0122]
Synthesis example 3
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-cyclic ring produced by ring-opening polymerization of octahydronaphthalene (MTD) 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 (Nippon Yushi Co., Ltd., trade name: Perhexa 25B) After 0 parts were dry blended at room temperature, the mixture was extruded with a twin screw extruder under conditions of a cylinder temperature of 260 ° C. and a screw rotation number of 230 rpm to obtain a resin (A4).
Mw of (A4) was 33,000, Mn was 8,400, epoxy equivalent was 840, and the number of crosslinkable functional groups (epoxy groups) of (A4) was 10 from Mn and epoxy equivalent.
(A4) was dissolved in toluene so that the solid content was 40% to obtain a resin solution (A44).
[0123]
Synthesis example 4
50 parts of methyl ethyl ketone was charged in a reaction vessel substituted with nitrogen, heated to 80 ° C., and uniformly dissolved in another nitrogen-substituted vessel, 200 parts of hydroxyethyl methacrylate, 200 parts of styrene, 200 parts of methyl ethyl ketone, and A mixture consisting of 1.5 parts of azobisisobutyronitrile was dropped into the reaction vessel over 4 hours.
After completion of dropping, the mixture was aged at 100 ° C. for 4 hours to obtain a methyl ethyl ketone solution of resin (A5).
30 parts of acrylic acid was added to 100 parts of a methyl ethyl ketone solution of resin (A5), and esterification was performed at 100 ° C. for 4 hours under reduced pressure while adding a solvent (methyl ethyl ketone) to obtain a methyl ethyl ketone solution of resin (A6).
Mw of (A6) is 160,000, Mn is 45,000, the equivalent of the acryloyl group analyzed by NMR is 610, and the crosslinkable functional group (acryloyl group) of (A6) is derived from Mn and the acryloyl group equivalent. The number was 74.
(A6) was adjusted by adding methyl ethyl ketone so that the solid content was 40% to obtain a resin solution (A66).
[0124]
Synthesis example 5
30 parts of methacrylic acid was added to 100 parts of the methyl ethyl ketone solution of the resin (A5) obtained in Synthesis Example 4, and the mixture was reacted at 100 ° C. for 4 hours under reduced pressure to obtain a methyl ethyl ketone solution of the resin (A7). .
Mw of (A7) is 160,000, Mn is 45,000, the equivalent of the methacryloyl group analyzed by NMR is 625, and the crosslinkable functional group (methacryloyl group) of (A7) is derived from Mn and the equivalent of methacryloyl group. The number was 72.
(A7) was adjusted by adding methyl ethyl ketone so that the solid content was 40% to obtain a resin solution (A77).
[0125]
Example 1
30 parts of resorcinol diglycidyl ether and 6 parts of 2-ethyl-4-methylimidazole were added to 175 parts of the resin solution (A11) and mixed with stirring.
This was coated on a 50 μm-thick PET film (257 mm × 364 mm) using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300), dried at 60 ° C. for 30 minutes, the solvent was removed, and the PET film was A curable resin composition (1) of the present invention was prepared. The thickness of the curable resin composition (1) was measured and found to be 47 ± 2 μm.
[0126]
The curable resin composition (1) was brought into contact with a BT substrate (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., CCL-830, 100 mm × 100 mm, copper foil on each half of the back and front surfaces removed by etching) and 120 ° C. After hot pressing under conditions of 0.4 kgf for 5 minutes, the PET film was peeled off and heat-cured at 180 ° C. for 3 hours to obtain an evaluation sample (1).
Using the sample for evaluation (1), -55 ° C was continued for 30 minutes and then 125 ° C was continued for 30 minutes (both the temperature rise rate and the temperature fall rate were 100 ° C / min), and a thermal cycle test was repeated. As a result, no cracks, blisters, or peeling defects were observed even after 1000 cycles.
The dielectric constant after curing of the curable resin composition {circle around (1)} at 1 GHz measured according to JIS K6911 (1995) 5.14 was 2.9.
[0127]
Reference example 3
  30 parts of resorcinol diglycidyl ether and 6 parts of 2-ethyl-4-methylimidazole were added to 175 parts of the resin solution (A33) and mixed with stirring.
  This was coated on a 50 μm thick PET film (257 mm × 364 mm) using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300), dried at 60 ° C. for 30 minutes, the solvent was removed, and the PET film was The curable resin composition of the present invention(2)Adjusted. Curable resin composition(2)When the thickness of was measured, it was 47 ± 2 μm.
[0128]
An evaluation sample (2) was obtained using the curable resin composition (2) in the same manner as in Example 1.
Using the evaluation sample (2), a thermal cycle test was conducted in the same manner as in Example 1. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles.
The curable resin composition (2) measured in the same manner as in Example 1 had a dielectric constant after curing of 2.5.
[0129]
Reference example 4
  30 parts of resorcinol diglycidyl ether and 6 parts of 2-ethyl-4-methylimidazole were added to 175 parts of the resin solution (A44) and mixed with stirring.
  This was coated on a 50 μm thick PET film (257 mm × 364 mm) using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300), dried at 60 ° C. for 30 minutes, the solvent was removed, and the PET film was The curable resin composition of the present invention(3)Adjusted. Curable resin composition(3)When the thickness of was measured, it was 47 ± 2 μm.
[0130]
An evaluation sample (3) was obtained using the curable resin composition (3) in the same manner as in Example 1.
Using the evaluation sample (3), a thermal cycle test was conducted in the same manner as in Example 1. As a result, cracking, blistering, and peeling were not observed even after 1000 cycles.
The curable resin composition (3) measured in the same manner as in Example 1 had a dielectric constant after curing of 2.7.
[0131]
  Reference example 1
  To 175 parts of the resin solution (A66), 30 parts of ethylene glycol diacrylate and 5 parts of dicumyl peroxide were added and mixed with stirring.
  This was coated on a 50 μm thick PET film (257 mm × 364 mm) using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300), dried at 60 ° C. for 30 minutes, the solvent was removed, and the PET film was The curable resin composition of the present invention(4)Adjusted. Curable resin composition(4)As a result, the thickness was 47 ± 2 μm.
[0132]
An evaluation sample (4) was obtained using the curable resin composition (4) in the same manner as in Example 1.
When the thermal cycle test was conducted in the same manner as in Example 1 using the sample for evaluation (4), no defects such as cracking, blistering and peeling were observed even after 1000 cycles.
The curable resin composition (4) measured in the same manner as in Example 1 had a dielectric constant after curing of 2.9.
[0133]
Reference example 2
  30 parts of ethylene glycol diacrylate and 5 parts of dicumyl peroxide were added to 175 parts of the resin solution (A77) and mixed with stirring.
  This was coated on a 50 μm thick PET film (257 mm × 364 mm) using a knife coater (manufactured by Yasui Seiki; knife coater SNC-300), dried at 60 ° C. for 30 minutes, the solvent was removed, and the PET film was The curable resin composition of the present invention(5)Adjusted. Curable resin composition(5)As a result, the thickness was 47 ± 2 μm.
[0134]
An evaluation sample (5) was obtained using the curable resin composition (5) in the same manner as in Example 1.
Using this evaluation sample (5), a thermal cycle test was conducted in the same manner as in Example 1. As a result, no cracking, blistering, or peeling failure was observed even after 1000 cycles.
The curable resin composition (5) measured in the same manner as in Example 1 had a dielectric constant after curing of 2.9.
[0135]
Comparative Example 1
85 parts of 4-methylcyclohexane-1,2-dicarboxylic acid was added to 100 parts of Epicoat 828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd .; bisphenol A type epoxy resin), and mixed by stirring. Made on Seiki; knife coater SNC-300) on BT substrate (Mitsubishi Gas Chemical Co., Ltd., CCL-830, 100 mm × 100 mm, with copper foil on each half of the back and front surfaces removed by etching) 62 After coating with a thickness of ± 2 μm, it was heat-cured at 180 ° C. for 3 hours to obtain a comparative evaluation sample (5).
Using the sample for comparative evaluation (5), a thermal cycle test was conducted in the same manner as in Example 1, but 1 piece / cm at 500 cycles.²Cracks occurred at a rate of. The dielectric constant measured in the same manner as in Example 1 was 3.6.
[0136]
Comparative Example 2
95 parts of 4-methylcyclohexane-1,2-dicarboxylic acid was added to 100 parts of cresol novolac epoxy resin of Mw 1040, mixed with stirring, and BT substrate using a knife coater (manufactured by Yasui Seiki; (Mitsubishi Gas Chemical Industry Co., Ltd., CCL-830, 100 mm × 100 mm, copper foil on each side of the back and front surfaces removed by etching) with a thickness of 62 ± 2 μm, then applied at 180 ° C. for 3 hours A sample for comparative evaluation (6) was obtained by heat curing.
Using this comparative evaluation sample {circle around (6)}, a thermal cycle test was conducted in the same manner as in Example 1, but 1 sample / cm at 700 cycles.²Cracks occurred at a rate of. The dielectric constant measured in the same manner as in Example 1 was 3.5.
[0137]
【The invention's effect】
The curable resin composition of the present invention can produce an insulator having excellent thermal shock resistance and dielectric properties.
Furthermore, the curable resin composition of the present invention can form an insulator excellent in adhesiveness, heat resistance, solvent resistance, low water absorption, electrical insulation, chemical resistance, workability, and the like. Therefore, it is most suitable for an overcoat material or an interlayer insulating material used for a circuit board used for various electric devices, electronic components or semiconductor elements.
The curable resin composition of the present invention is not limited to a technical field such as a circuit board, and can be used in various fields, and is a very useful material that can be used particularly for forming a thin film.

Claims (3)

At least one monomer selected from the group consisting of styrene, ethylene and propylene, and a monomer (o) having an epoxy group and a (meth) acryloyl group as a crosslinkable functional group, or an epoxy group and a vinyl group. A monomer (p) having an essential constituent monomer, a resin (A) having at least two epoxy groups in the molecule as crosslinkable functional groups, and at least 2 epoxy groups in the molecule as crosslinkable functional groups A low molecular compound (B) having a number, (A) has a weight average molecular weight of 30,000 to 600,000 , (B) has a weight average molecular weight of 170 to 3,000, and after curing A curable resin composition having a dielectric constant of 3.5 or less.   The curable resin composition according to claim 1, wherein the epoxy group is an epoxy group derived from a glycidyl group or a cyclohexenyl monooxide group. An insulator obtained by curing the curable resin composition according to claim 1 .