JP2002012740A - Flame-retardant epoxy resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant epoxy resin composition which is suitable for a copper-clad laminate to use in an electronic circuit substrate and for a sealing material, a molding material, a casting material, an adhesive material or an electric insulating coating material to use in an electronic parts, and can provide a laminate which is excellent in heat resistance, flame-retardancy, flexibility and an adhesive property. SOLUTION: The flame-retardant epoxy resin composition comprises a phosphorus containing epoxy resin (A), a curing agent (B), and a block copolymer (C), wherein the phosphorus containing epoxy resin is prepared by reacting a setting epoxy resin with a phosphorus compound represented by formula (1) (wherein R is hydrogen, an aliphatic group or an aromatic group, and may be same or different) so that the phosphorus containing epoxy resin may have a phosphorus content of 0.8-8% by weight; and the block copolymer (C) is formed from a phenolic hydroxyl group containing aromatic polyamide oligomer having aminoaryl groups as the both terminals and a poly(butadiene-acrylonitrile) copolymer having carboxyl groups at the both terminals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for producing a copper-clad laminate used for an electronic circuit board and a sealing material, a molding material, a casting material, an adhesive, and an electric insulating material used for an electronic component. The present invention relates to a flame-retardant epoxy resin composition useful as a material for paints and the like.

[0002]

2. Description of the Related Art Epoxy resins are widely used in electronic parts, electric equipment, automobile parts, FRP, sporting goods, etc. because of their excellent adhesiveness, heat resistance and moldability. In particular, copper-clad laminates and encapsulants used in electronic components and electrical equipment are required to have high safety such as prevention and delay of fire. Is used. Despite the problem that the specific gravity is large, flame retardancy is imparted by introducing halogen, particularly bromine, into the epoxy resin, and an excellent cured product having high reactivity of the epoxy group can be obtained. Thus, brominated epoxy resins are positioned as useful electronic and electrical materials. However, when a brominated epoxy resin is used at a high temperature for a long period of time, a halide is dissociated, which may cause corrosion of wiring. Further, the use of halogen has been regarded as a problem from the viewpoint of environmental safety, and alternative materials have been studied. For these reasons, the development and commercialization of flame-retardant epoxy resin curing systems that do not use halogens meet the demands of the times. Epoxy resin has excellent insulation, heat resistance, and adhesion, but is brittle, cracked by thermal shock, peeled by external impact,
There is a problem that cracking easily occurs when bent due to insufficient flexibility. Conventionally, problems such as thermal shock, mechanical shock from the outside, and lack of flexibility have been solved by adding a rubber-like substance to the epoxy resin. Have caused problems such as a decrease in heat resistance and a decrease in adhesiveness after heating at a high temperature.

[0003]

An epoxy resin composition suitable for a sealing material, a molding material, a casting material, an adhesive, and a material for an electrically insulating paint used for a copper-clad laminate used for an electronic circuit board and an electronic component. It is another object of the present invention to provide an epoxy resin composition which provides a laminate excellent in heat resistance, flame retardancy, flexibility and adhesion.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a flame-retardant epoxy resin composition which simultaneously satisfies the above performance can be obtained. is there. That is, the present invention provides (1) a phosphorus-containing epoxy resin (A) obtained by reacting a phosphorus compound represented by the following formula (1) with a curable epoxy resin so that the phosphorus content becomes 0.8 to 8% by weight. , A block copolymer formed from a curing agent (B), a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals, and a poly (butadiene-acrylonitrile) copolymer having carboxyl groups at both terminal groups (C) a flame-retardant epoxy resin composition,

[0005]

Embedded image

(R is a hydrogen atom, an aliphatic group, or an aromatic group, and may be the same or different.)
(2) The component (C) is represented by the following formula (2)

[0007]

Embedded image

(Where x, y, z, l, m and n are average degrees of polymerization, respectively; x = 3-7, y = 1-4,
z = 5 to 15, l + m = integer of 2 to 200, m /
(M + 1) ≧ 0.04. (3) The epoxy resin composition according to the above (1) or (2), wherein the curing agent is a phenol; and (4) the epoxy resin composition according to the above (1) or (2), wherein the curing agent is a phenol. The epoxy resin composition according to the above (1) or (2), wherein the curing agent is a guanidine, and (5) the epoxy resin composition according to any one of the above (1) to (4) is dissolved in a solvent. And / or a dispersed varnish, (6) any one of the above (1) to (4)
Cured product obtained by curing the epoxy resin composition according to the item,
(7) A laminate using the epoxy resin composition according to any one of (1) to (4).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant epoxy resin composition of the present invention contains a phosphorus compound represented by the above formula (1) in a curable epoxy resin so that the phosphorus content is 0.8 to 8% by weight. The reacted phosphorus-containing epoxy resin (A), curing agent (B) and phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals and poly (butadiene-acrylonitrile) having carboxyl groups at both terminals. And a block copolymer (C) formed from the polymer.

Specific examples of the curable epoxy resin which can be used in the present invention include novolak type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcin type epoxy resin and polyglycol type epoxy resin. Resins.
Preferably, it is a novolak type epoxy resin, and specific examples thereof are EPPN-201 (phenol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd.) and EOCN-104.
S, EOCN-1020 (cresol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), NC-7000, NC
-7300 (Nippor Kayaku Co., Ltd. novolak epoxy resin having a phenol skeleton and a naphthol skeleton), E
PPN-501H, EPPN-502H (Novolak type epoxy resin having a triphenylmethane skeleton manufactured by Nippon Kayaku Co., Ltd.), NC-3000 (manufactured by Nippon Kayaku Co., Ltd.)
A novolak type epoxy resin having a phenol skeleton and a biphenyl skeleton), an alkyl novolak type epoxy resin,
A styrenated phenol novolak type epoxy resin, a bisphenol novolak type epoxy resin, an aralkylphenol novolak type epoxy resin and the like are exemplified. These epoxy resins may be used alone or in combination of two or more. Furthermore, a resin obtained by reacting the above-mentioned novolak type epoxy resin with phenols, amines and carboxylic acids can also be used as the epoxy resin.

A specific example of the phosphorus compound represented by the formula (1) is HCA (9,8-dihydro-9-oxa-10-phosphaphenanthrene-10- manufactured by Sanko Chemical Co., Ltd.).
Oxide) and the like.

The reaction between the phosphorus compound represented by the formula (1) and the epoxy resin is known per se. For example, the reaction temperature is 100 ° C. to 200 ° C., preferably 120 ° C. to 180 ° C.
May be performed under stirring. The reaction proceeds by reacting an active hydrogen atom directly bonded to a phosphorus atom of the phosphorus compound represented by the formula (1) with an epoxy group of the epoxy resin. The end point of the reaction is confirmed to be 99% or more of the theoretical epoxy equivalent by tracking the epoxy equivalent. Alternatively, the residual amount of the phosphorus compound represented by the formula (1) is tracked as the acid value of the epoxy resin, and a method for confirming the end point of the reaction or liquid chromatography
There is a method of tracking the remaining phosphorus compound represented by the formula (1) by instrumental analysis such as the above. Either method may be used, but it is necessary to sufficiently react the epoxy resin with the phosphorus compound represented by the formula (1). A catalyst is used as necessary in consideration of the reaction rate. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, and ethyltriphenylphosphonium Phosphonium salts such as bromide, 2
Various catalysts such as imidazoles such as -methylimidazole and 2-ethyl-4-methylimidazole can be used. However, it is necessary to react the phosphorus compound represented by the formula (1) such that the phosphorus content in the epoxy resin is in the range of 0.8 to 8 parts by weight. When the phosphorus content in the epoxy resin is less than 0.8 parts by weight, sufficient flame retardancy cannot be obtained. When the phosphorus content is more than 8 parts by weight, the cross-linking density of the epoxy resin after curing decreases, resulting in heat resistance. Physical properties such as properties and adhesiveness are reduced.

The curing agent (B) used in the present invention includes acid anhydrides, amines, phenols, hydrazides, imidazoles and the like. Specific examples of acid anhydrides that can be used include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, and biphenyltetracarboxylic anhydride. Aromatic carboxylic acid anhydrides such as azelaic acid, sebacic acid, dodecane diacid, etc., tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, hetonic anhydride And alicyclic carboxylic acid anhydrides such as hymic acid anhydride.

Specific examples of amines that can be used include diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, and m-xylylenediamine. Aromatic amines such as ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-
Aliphatic amines such as 3-methyldicyclohexyl) methane and polyetherdiamine, dicyanamide, 1- (o-
Guanidines such as (tolyl) biguanide;

Specific examples of phenols that can be used include:
Bisphenol A, Bisphenol F, Bisphenol S, 4,4'-biphenylphenol, Tetramethylbisphenol A, Dimethylbisphenol A, Tetramethylbisphenol F, Dimethylbisphenol F, Tetramethylbisphenol S, Dimethylbisphenol S, Tetramethyl-4,4 '-Biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,
2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-
Methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenol Resins derived from various phenols such as polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthols, phenol novolak resins containing a xylylene skeleton, dicyclopentadiene Phenol novolak resin containing skeleton, phenol novolak resin containing biphenyl skeleton, phenol novolak resin containing fluorene skeleton, etc. Novolak resins, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolak, chlorinated bisphenol S, halogenated phenols such as chlorinated bisphenol A and the like.

Specific examples of hydrazides that can be used include:
Examples include adipic dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, and maleic dihydrazide.

Specific examples of imidazoles that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole,
1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-
Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4- Diamino-6 (2'-undecylimidazole (1 '))
Ethyl-s-triazine, 2,4-diamino-6 (2 ′
-Ethyl, 4-methylimidazole (1 ')) ethyl-
s-Triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine.isocyanuric acid adduct, 2-methylimidazole 2: 3 adduct of isocyanuric acid, 2-phenylimidazole Isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2
Various imidazoles of -phenyl-3,5-dicyanoethoxymethylimidazole, and those imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid, etc. And salts with polyvalent carboxylic acids.

[0018] Of these curing agents, which curing agent is used is appropriately selected depending on the required properties of the composition and a laminate using the same, but phenols or guanidines are preferred. The amount of these curing agents used is usually 0.3 to 2.0, preferably 0.4 to 1.6 in terms of the equivalent ratio of the curing agent to the epoxy group of the phosphorus-containing epoxy resin (A).
More preferably, it is used in the range of 0.5 to 1.3. The above curing agents can be used as a mixture of two or more kinds. still,
The imidazoles are also used as a curing accelerator described below.

A block copolymer formed from a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals and a poly (butadiene-acrylonitrile) copolymer having carboxyl groups at both terminals used in the present invention. The union (C) is described in JP-A-6-299133.
JP-A No. 2000-209, in which a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends is converted to a poly (butadiene-
(Acrylonitrile) copolymer.

The phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals used as a raw material is synthesized by polycondensation of an aromatic diamine component and an aromatic dicarboxylic acid component. In the reaction, a phenolic hydroxyl group-containing aromatic polyamide oligomer is produced by mixing an aromatic diamine or an aromatic dicarboxylic acid having a hydroxyl group into the aromatic diamine component or the aromatic dicarboxylic acid component. An oligomer having an aminoaryl group at both terminals can be easily obtained by subjecting an aromatic diamine component to a polycondensation reaction in an excess amount to an aromatic dicarboxylic acid component in the above step. Blocking of the thus synthesized oligomer with a poly (butadiene-acrylonitrile) copolymer having carboxyl groups at both ends can be performed by a known method. That is, a direct dehydration polycondensation polymerization method between the carboxyl group of the poly (butadiene-acrylonitrile) copolymer and the amino group of the oligomer, and a polymerization method in which the carboxyl group is acid chlorided with thionyl chloride or the like and then reacted with the amino group. And a synthesis method using a condensation polymerization catalyst of phosphite and pyridine. The poly (butadiene-acrylonitrile) copolymer having carboxyl groups at both ends is commercially available from Goodrich as Hycar CTBN and can be easily obtained.

Specific examples of the aromatic diamine which can be used for producing the phenolic hydroxyl group-containing aromatic polyamide oligomer include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, and 4,4'-diaminodiphenyl ether. , 3,3'-dimethyl-4,4 '
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,
4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3,3'-
Dimethoxy-4,4'-diaminodiphenylthioether, 2,2'-bis (3-aminophenyl) propane,
2,2′-bis (4-aminophenyl) propane, 4,
4'-diaminodiphenylsulfoxide, 4,4 '
-Diaminodiphenyl sulfone, benzidine, 3,
3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 3,3′-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2′-bis (3 -Aminophenoxyphenyl) propane, 2,2'-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4-aminophenoxyphenyl) benzene, 1,3'-bis (3-aminophenoxyf) propane , 4,4 '-(p-phenylenediisopropylidene) bisaniline and the like, and these may be used alone or in combination of two or more.

Specific examples of the aromatic dicarboxylic acid which can be used for producing the above-mentioned phenolic hydroxyl group-containing aromatic polyamide oligomer include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-oxydibenzoic acid, 4,
4'-biphenyldicarboxylic acid, 3,3'-, methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4 '
-Thiodibenzoic acid, 3,3′-carbonyldibenzoic acid,
4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 1,5-naphthalenedicarboxylic acid,
Examples thereof include 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,2-naphthalenedicarboxylic acid, but are not limited thereto.

Further, specific examples of the phenolic hydroxyl group-containing aromatic dicarboxylic acid which can be used for introducing a phenolic hydroxyl group into the aromatic polyamide oligomer include 5
-Hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 3-hydroxyisophthalic acid, 2-hydroxyterephthalic acid and the like. Specific examples of the phenolic hydroxyl group-containing aromatic diamine that can be used include 3,3′-dihydroxy-4,
4'-dianiline, 2,2-bis (3'-amino-4-
(Hydroxyphenyl) propane, 2,4-dihydroxy-1,5-diaminobenzene, 5-hydroxy-1,3
-Diaminobenzene and the like. These aromatic dicarboxylic acids and aromatic diamines are not particularly limited to the above specific examples as long as they have a structure in which two carboxyl groups or two amino groups are bonded to an aromatic ring.

A block copolymer formed from a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminal groups and a poly (butadiene-acrylonitrile) copolymer having both terminal carboxyl groups used in the present invention. (C) is the following formula (2)

[0025]

Embedded image

(Where x, y, z, l, m and n are x =
3-7, y = 1-4, z = 5-15, l + m = 2-20
Indicates an integer of 0, and m / (m + 1) ≧ 0.04. ) Are preferred.

In the present invention, the phenolic hydroxyl group-containing aromatic polyamide-poly (butadiene-acrylonitrile) block copolymer (C) is used in the amount of epoxy resin 1
The amount is usually 2 to 300 parts by weight, preferably 4 to 200 parts by weight based on 00 parts by weight. If the amount is less than 2 parts by weight, the adhesiveness is inferior.

A curing accelerator may be used in the flame-retardant epoxy resin composition of the present invention. Specific examples of the curing accelerator that can be used include the aforementioned 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole,
Heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2
-Undecyl imidazole, 2,4-diamino-6
(2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4
-Diamino-6 (2'-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-
s-Triazine / isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-
3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole,
Various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and those imidazoles and phthalic acid, isophthalic acid,
Salts with polycarboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid; amides such as dicyandiamide;
Diaza compounds such as diaza-bicyclo (5.4.0) undecene-7 and their phenols, salts with the above-mentioned polycarboxylic acids or phosphinic acids, phosphines such as triphenylphosphine and tetraphenylphosphoniumtetraphenylborate; And phenols such as 2,4,6-trisaminomethylphenol, amine adducts, and microcapsule-type curing accelerators in which these curing agents are microencapsulated. The type and amount of these curing accelerators are appropriately selected according to the characteristics required for the obtained flame-retardant epoxy resin composition.

The flame-retardant epoxy resin composition of the present invention may contain a filler. Specific examples of the filler that can be used include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc,
Clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber,
Carbon fiber, molybdenum disulfide, asbestos, etc .; fused silica, crystalline silica, silicon nitride, boron nitride,
Calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina and aluminum hydroxide are preferred. These fillers have an average particle size of 20 μm.
m is preferably 80% by weight or more, more preferably 85% by weight or more, and still more preferably 90% by weight or more. If the content is less than 80% by weight, when the epoxy resin composition is formed into a film, there may be a problem in smoothness such as a rough surface. These fillers may be used alone or in a combination of two or more.

The flame-retardant epoxy resin composition of the present invention comprises
Flame retardants, coloring agents, coupling agents, leveling agents and the like can be appropriately added according to the purpose, but halogen-based flame retardants are not preferred in view of the object of the present invention. Examples of the flame retardant include antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide,
Examples include inorganic flame retardants such as calcium aluminate, and phosphoric flame retardants such as tris (tribromophenyl) phosphate. The colorant is not particularly limited, and may be phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavanthrone, perinone, perylene, dioxazine, condensed azo, various azomethine-based organic dyes, titanium oxide, lead sulfate, chromium yellow, zinc yellow. , Chromium vermillion, valve shell, cobalt violet, dark blue, ultramarine, carbon black, chrome green, chromium oxide, cobalt green, and other inorganic pigments.

As the coupling agent, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- (2-
(Aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N Silane-based cups such as-(2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane Ring agent, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphate) Site) titanate, neoalkoxy tri (p-N- (β- aminoethyl) aminophenyl)
Titanium-based coupling agents such as titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy Tris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, zirconium such as Al-propionate, or an aluminum-based coupling agent. And a silicon-based coupling agent. By using a coupling agent, a cured product having excellent moisture resistance reliability and a small decrease in adhesive strength after moisture absorption can be obtained.

As the leveling agent, acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate having a molecular weight of 4000 to 12 are used.
000 oligomers, epoxidized soybean fatty acid, epoxidized aviethyl alcohol, hydrogenated castor oil, modified silicone, anionic / nonionic surfactant, and the like.

The epoxy resin composition of the present invention is a phosphorus-containing epoxy resin (A), a curing agent (B), a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals, and a poly (carboxyl group-containing terminal polymer). A block copolymer (C) formed from a (butadiene-acrylonitrile) copolymer and, if necessary, a curing accelerator, a filler, a coupling agent, a flame retardant, a coloring agent, a leveling agent, and the like. After mixing using a planetary mixer or the like, it can be obtained by uniformly dispersing with a two-roll, kneader, extruder, sand grinder or the like. When the obtained product is a solid, the mixture is preferably cooled and solidified, and finely pulverized to obtain the epoxy resin composition of the present invention. In order to obtain a cured product of the epoxy resin composition of the present invention, heat curing may be performed under curing conditions according to the curing agent and / or curing accelerator used.

The varnish of the present invention comprises the components (A) to (C)
It is obtained by dissolving and / or dispersing the above optional components in a solvent, if necessary. Further, the epoxy resin composition once prepared by the above method may be dissolved in a solvent. Specific examples of the solvent that can be used include γ-butyrolactones, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-
Amide solvents such as dimethylimidazolidinone, sulfones such as tetramethylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether monoacetate, tetrahydrofuran and dioxane And ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene. Among them, amide-based or sulfone-based solvents are preferable because the component (C) can be easily dissolved. The solid content concentration in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 80% by weight.
It is 70% by weight, more preferably 30 to 65% by weight.

A prepreg can be produced by coating and impregnating a varnish obtained by the above-described method on a fibrous base material such as glass fiber, carbon fiber, or aromatic polyamide fiber, and heating. Further, a plurality of the prepregs may be laminated, and a copper foil may be laminated on one or both sides of the laminated structure, and then heated and pressed under ordinary conditions to obtain the laminated plate of the present invention.

[0036]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” means parts by weight.

The evaluation of the laminates in the examples is based on the UL (Underwriter Laborator).
ics) In accordance with the standard, the copper foil peel strength is JIS C6
481 5.7. The glass transition temperature was measured by TM7000 manufactured by Vacuum Riko Co., Ltd. The bending test was performed by bending the laminated plate at 180 degrees and evaluating whether or not a crack occurred in the bent portion.

Synthesis Example 1 EOCN-1 was placed in a four-necked glass separable flask equipped with a stirrer, thermometer, cooling tube, and nitrogen gas introducing device.
020 (cresol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd.) 843.0 parts, bisphenol A16.
0 parts were charged, stirred while introducing nitrogen gas, and dissolved by heating. Next, 0.02 part of triphenylphosphine was added as a catalyst and reacted at 150 ° C. for 3 hours, and 141.0 parts of the above-mentioned HCA was added to further react. At this time, the content of the novolak-type epoxy resin was 85.6% by weight. The epoxy equivalent of the obtained epoxy resin was 299 g / eq with respect to the theoretical epoxy equivalent of 300 g / eq when HCA was completely reacted, and it was confirmed that HCA was almost completely reacted with the epoxy resin. The phosphorus content was 2.0% by weight.

Synthesis Example 2 The same as Synthesis Example 1 except that 804.0 parts of EPPN-201L (phenol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), 55 parts of bisphenol F, 141 parts of HCA, and 0.02 parts of triphenylphosphine were used. Operation was performed. At this time, the content of the novolak-type epoxy resin was 85.9% by weight. The epoxy equivalent of the obtained epoxy resin is 304 g / eq with respect to the theoretical epoxy equivalent of 300 g / eq when HCA is completely reacted.
It was confirmed that A had almost completely reacted with the epoxy resin. The phosphorus content was 2.0% by weight.

Synthesis Example 3 Phenolic hydroxyl group-containing aromatic polyamide-poly (butadiene-acrylonitrile) block copolymer (hereinafter B)
Synthesis of PAM, 14 mol% of phenolic hydroxyl group contained in aromatic polyamide portion) 19.93 g (120 mmol) of isophthalic acid, 3,
30.63 g (153 mmol) of 4'-oxydianiline, 3.64 g (20 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, calcium chloride 1
2.1 g, 240 ml of N-methyl-2-pyrrolidone and 54 ml of pyridine were placed in a 1-liter four-necked round-bottomed flask and dissolved by stirring.
g was added and reacted at 90 ° C. for 4 hours to produce a phenolic hydroxyl group-containing aromatic polyamide oligomer. A poly (butadiene-acrylonitrile) copolymer having carboxyl groups at both ends (Hycar CTBN, BF G
Made by oodrich. The poly (butadiene-acrylonitrile) part contains 48 g of an acrylonitrile component containing 17 mol% and a molecular weight of about 3600) in 240 ml of N-methyl-2.
After adding a liquid dissolved in pyrrolidone and reacting for an additional 4 hours, the reaction liquid was cooled to room temperature, and the reaction liquid was poured into 20 liters of methanol to contain a poly (butadiene-acrylonitrile) copolymer part used in the present invention. An amount of 50% by weight of an aromatic polyamide-poly (butadiene-acrylonitrile) block copolymer containing about 14 mol% of phenolic hydroxyl groups was precipitated. The precipitated polymer was further purified by washing with methanol and refluxing methanol. The intrinsic viscosity of this polymer was 0.85 dl / g (dimethylacetamide, 30 ° C.). When the infrared spectrum of the polymer powder was measured by a diffuse reflection method,
^-1 to an amide carbonyl group, 2856-2975 cm ^-1
The absorption based on the C—H bond of the butadiene moiety
An absorption based on a nitrile group was observed at 5 cm ^-1 .

Example 1 100.0 parts of the epoxy resin obtained in Synthesis Example 1 and dicyandiamide (manufactured by Nippon Carbide Co., Ltd.) as a curing agent
3.52 parts, 0.05 parts of 2E4MZ (2ethyl 4-methylimidazole manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator and 30.0 parts by weight of BPAM obtained in Synthesis Example 3 were combined with methyl ethyl ketone, methyl cellosolve, and N, N dimethylformamide. Was uniformly dissolved in a mixed solvent (weight ratio 50/10/40). The obtained varnish is used as a glass cloth WEA.
7628 XS13 (Nitto Boseki Co., Ltd. 0.18m
m thickness). The impregnated glass cloth was dried in a hot air circulating oven at 150 ° C. for 6 minutes to obtain a prepreg. Eight pieces of the obtained prepregs were stacked, and 130 ° C. × 15 minutes and 1
Heating and pressing were performed at 70 ° C. × 20 kg / cm ² × 70 minutes to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.

Example 2 100.0 parts of the epoxy resin obtained in Synthesis Example 2, 3.45 parts of dicyandiamide as a curing agent, 0.05 part of 2E4MZ as a curing accelerator, and BPAM obtained in Synthesis Example 3
30.0 parts by weight were uniformly dissolved in the same solvent as in Example 1. The same operation as in Example 1 was performed using the obtained resin varnish to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.

Example 3 100.0 parts of the epoxy resin obtained in Synthesis Example 1 and Kayahard TPM (trishydroxyphenylmethane hydroxyl equivalent of 97 g / e, manufactured by Nippon Kayaku Co., Ltd.) as a curing agent
q) 32.4 parts by weight, 2E4MZ0.
50 parts and 30.0 parts by weight of the BPAM obtained in Synthesis Example 3 were uniformly dissolved in the same solvent as in Example 1. The same operation as in Example 1 was performed using the obtained varnish to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.

Comparative Example 1 100.0 parts of the epoxy resin obtained in Synthesis Example 1, 3.52 parts of dicyandiamide as a curing agent, and 0.05 parts of 2E4MZ as a curing accelerator were uniformly dissolved in the same solvent as in Example 1. The same operation as in Example 1 was performed using the obtained varnish to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.

[0045]

[Table 1]

[0046]

As is clear from the results shown in Table 1, the laminate using the flame-retardant epoxy resin composition of the present invention has heat resistance (determined from a high glass transition temperature) and flame retardancy. It is also excellent in flexibility (determined from the absence of cracks in the bending test) and adhesiveness (determined from large copper foil peel strength).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 77/06 C08L 77/06 H05K 1/03 610 H05K 1/03 610R F-term (reference) 4F100 AG00 AH02A AH07A AK27A AK27J AK29A AK29J AK47A AK53A AK53K AL02A AL05A BA01 CA02A DG12 DH01 GB43 JJ03 JJ07 JK17 JL11 YY00A 4J002 CC043 CC053 CC063 CD011 CD041 CD051 CD061 CD071 CL032 EJ026 EJ036 EJ046 EJ056 EL136 EN036 EN076 EQ026 ER026 EU116 FD143 FD146 GF00 GQ00 4J036 AB01 AB09 AD07 AD08 AF06 AF16 CC02 DA05 DB05 DB07 DB15 DB21 DB22 DC03 DC06 DC10 DC26 DC31 DC35 FB06 FB08 FB13 JA01 JA06 JA08

Claims (7)

[Claims] 1. A phosphorus-containing epoxy resin (A) obtained by reacting a phosphorus compound represented by the following formula (1) with a curable epoxy resin so that the phosphorus content becomes 0.8 to 8% by weight:
A block copolymer (B) formed from a curing agent (B) and a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals and a poly (butadiene-acrylonitrile) copolymer having a carboxyl group at both terminals. A flame-retardant epoxy resin composition containing C). Embedded image (R is a hydrogen atom, an aliphatic group, or an aromatic group, and may be the same or different) The component (C) is represented by the following formula (2): (Where x, y, z, l, m, and n are average polymerization degrees, respectively; x = 3-7, y = 1-4, z = 5-1)
5, 1 + m = integer of 2 to 200, m / (m + 1)
≧ 0.04. 2. The epoxy resin composition according to claim 1, which is a copolymer represented by the formula: 3. The epoxy resin composition according to claim 1, wherein the curing agent is a phenol. 4. The epoxy resin composition according to claim 1, wherein the curing agent is a guanidine. 5. A varnish obtained by dissolving and / or dispersing the epoxy resin composition according to any one of claims 1 to 4 in a solvent. 6. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4. 7. A laminate using the epoxy resin composition according to any one of claims 1 to 4.