JP2002284963A - Flame-retardant epoxy resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition suitable for copper-clad laminate used for electronic circuit boards and a sealing material, a molding material, a casting material, an adhesive and a material for electrical insulation coating used for electronic parts and capable of providing a halogen-free laminated board excellent in flame retardance without lowering heat resistance. SOLUTION: This flame-retardant epoxy resin composition consists essentially of an epoxy resin (A), a curing agent (B) and a flame retardant (C). As the characteristics of the resin composition, the flame retardant (C) is at least one kind of compound selected from a phosphinate represented by the following formula (1) and/or a diphosphinate represented by the following formula (2) and/or a polymer thereof e.g. flame retardant A: Exolit OP940 (R) [an aluminum salt of phosphinic acid, manufactured by Clariant GmbH (In the formula (1), R1 is methyl group; R2 is ethyl group; M is Al; m is 3)] or flame retardant B: Adekastab FP-600 (R) (phosphate, manufactured by Asahi Denka Kogyo K.K.)} and >=80% of the flame retardant (C) has <=40 μm particle diameter.

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.

[0003]

DISCLOSURE OF THE INVENTION The present invention is 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. An object of the present invention is to provide an epoxy resin composition which provides a laminated board excellent in flame retardancy without halogen, without deteriorating heat resistance.

[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 comprises (1) an epoxy resin (A), a curing agent (B), and a flame retardant (C) as essential components, and is represented by the following formula (1) and / or the following formula (2). At least one of the diphosphinates and / or polymers thereof

Embedded image

Embedded image [Equation (1), in (2), R _1, R ₂ may be the same or different from each other, are linear or branched alkyl group or an aryl group having a carbon number of 1 to 6; R ₃ is A linear or branched alkylene group having 110 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group or an arylalkylene group;
a, Al, Sb, Sn, Ge, Ti, Zn, Fe, Z
a metal selected from at least one of the group consisting of r, Ce, Bi, Sr, Mn, Li, Na and K; m
Is an integer from 1 to 4; n is an integer from 1 to 4; and x is an integer from 1 to 4. ], A flame-retardant epoxy resin composition characterized in that 80% or more of its particle size is 40 [mu] m or less, (2) the flame retardancy according to (1) above, wherein the curing agent (B) is a phenol. Epoxy resin composition.
(3) The flame-retardant epoxy resin composition according to the above (1), wherein the curing agent (B) is a guanidine. (4) a varnish obtained by dissolving and / or dispersing the flame-retardant epoxy resin composition according to any one of the above (1) to (3) in a solvent, (5)
(6) A cured product obtained by curing the flame-retardant epoxy resin composition according to any one of (1) to (3); (6) a cured product obtained by curing the epoxy resin composition according to any one of (1) to (3). A printed wiring board having a layer of an epoxy resin composition, (7) a sheet having a layer of the epoxy resin composition according to any one of the above (1) to (3) on both surfaces or one surface of a planar support,
(8) The sheet according to (7), wherein the planar support is a polyimide film, (9) the sheet according to (7), wherein the planar support is a metal foil, and (10) the planar support is peeled. The sheet according to the above (7), which is a film, (11)
The present invention relates to a sheet-like adhesive having a release film layer on both sides of the epoxy resin composition or the varnish layer according to any one of the above (1) to (4).

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The epoxy resin (A) used in the present invention includes:
For example, a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound, a polyfunctional epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester-based epoxy resin, and a glycidylamine-based epoxy Examples include, but are not limited to, resins.
Here, the polyfunctional epoxy resin is an epoxy resin having two or more glycidyl groups.

Specific examples of the polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound 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-te
rt-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, glycidyl ethers of polyphenol compounds such as phenolized polybutadiene And polyfunctional epoxy resins.

Specific examples of the polyfunctional epoxy resin which is a glycidyl etherified product of various novolak resins include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and the like. Novolak resin using various phenols such as naphthols, phenol novolak resin containing xylylene skeleton, phenol novolak resin containing dicyclopentadiene skeleton, phenol novolak resin containing biphenyl skeleton, phenol novolak resin containing fluorene skeleton, phenol novolak resin containing furan skeleton, etc. Glycidyl etherified products of various novolak resins.

Specific examples of the usable alicyclic epoxy resin include alicyclic epoxy resins having an aliphatic skeleton such as cyclohexane. Specific examples of the usable aliphatic epoxy resin include 1,4 and 4. -Butanediol, 1,6
Glycidyl ethers of polyhydric alcohols such as hexanediol, polyethylene glycol and pentaerythritol. Specific examples of the usable heterocyclic epoxy resin include a heterocyclic epoxy resin having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring, and specific examples of the usable glycidyl ester-based epoxy resin include hexahydrophthalic acid. Examples of the epoxy resin include carboxylic acids such as acid diglycidyl ester. Specific examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylation of amines such as aniline and toluidine.

[0009] Among these epoxy resins, which epoxy resin is used is appropriately selected depending on required characteristics, and a glycidyl ether type epoxy resin is preferable.
More preferably, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, novolak type epoxy resin having phenol skeleton and naphthol skeleton, novolak type epoxy having phenol skeleton and biphenyl skeleton Resin, novolak epoxy resin having triphenylmethane skeleton, novolak epoxy resin having dicyclopentadiene skeleton, alkyl novolak epoxy resin, styrenated phenol novolak epoxy resin, bisphenol novolak epoxy resin, aralkylphenol novolak epoxy resin And the like. These epoxy resins are
They 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.

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 acid 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: 3 adduct of methylimidazole isocyanuric acid, 2-phenylimidazole isocyanurate Acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2
-Phenyl-3,5-dicyanoethoxymethylimidazole, various imidazoles, and a variety of imidazoles such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid, etc. And salts with polyvalent carboxylic acids.

[0015] Among these curing agents, which curing agent is used is appropriately selected depending on required characteristics, but phenols or guanidines are preferable. The amount of these curing agents to be used is generally 0.3 to 2.0, preferably 0.1 to 2.0, in terms of the equivalent ratio of the curing agent to the epoxy group of the epoxy resin (A).
It is used in the range of 4-1.6, more preferably in the range of 0.5-1.3. The above curing agents can be used as a mixture of two or more kinds. The above imidazoles are also used as a curing accelerator described below.

As the flame retardant (C) used in the present invention, at least one of a phosphinate represented by the following formula (1) and / or a diphosphinate represented by the following formula (2) and / or a polymer thereof is provided.

Embedded image

Embedded image Is mentioned. [Equation (1), in (2), R _1, R ₂ may be the same or different from each other, are linear or branched alkyl group or an aryl group having a carbon number of 1 to 6; R ₃ is Linear or branched carbon number 1
An alkylene group of 10, an arylene group having 6 to 10 carbon atoms,
M is Mg, Ca, Al, Sb, Sn, Ge, Ti,
Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, N
a is a metal selected from at least one of the group consisting of a and K; m is an integer from 1 to 4; n is an integer from 1 to 4; and x is an integer from 1 to 4] It is. In the above, specific examples of R ₁ and R ₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group and a phenyl group. As R ₃ , examples of the alkylene group include a phenylene group and a naphthylene group. Examples of the alkylarylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a tertiary butylene group, an n-pentylene group, an n-octylene group, and an n-dodecylene group. Examples of the arylene group include, for example, a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group, a tert-butylnaphthylene group, and the like.As the arylalkylene group, a phenylmethylene group Phenylethylene group, phenylpropylene group, phenylbutylene group and the like.

The amount of the flame retardant (C) used in the present invention is:
It is 5 to 70% by weight, preferably 7 to 70% by weight of the whole composition. When the amount of the flame retardant (C) is less than 5% by weight of the whole composition, sufficient flame retardancy is not exhibited. These flame retardants (C) can be used alone or in combination of two or more.

In the present invention, the particle size of the flame retardant (C) is preferably at least 80% of the particle size, not more than 40 μm, more preferably at least 80% of the particle size is not more than 20 μm, and still more preferably not more than 8 μm.
0% or more is 10 μm or less, particularly preferably 80% of the particle size
The above is 5 μm or less. 80 μm or more of particle size is 40 μm
When it exceeds, the amount used increases to express sufficient flame retardancy, which is economically disadvantageous. Such a flame retardant imparting agent (C) is commercially available.

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,
Heptadecylimidazole, 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: 3 adduct of methylimidazole isocyanuric acid, 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; 1,8-
Diaza compounds such as diaza-bicyclo (5.4.0) undecene-7 and their phenols, salts with the above polycarboxylic acids or phosphinic acids, and phosphines such as triphenylphosphine and tetraphenylphosphoniumtetraphenylborate; And 2,4,6-trisaminomethylphenol, phenolic 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 depending on the properties 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
A coloring agent, a coupling agent, a leveling agent and the like can be appropriately added according to the purpose. There is no particular limitation on the coloring agent, and phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, various azomethine-based organic dyes, titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome Inorganic pigments such as vermilion, valve shell, cobalt violet, navy blue, ultramarine, carbon black, chrome green, chromium oxide, cobalt green and the like.

As coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexylethyltrimethoxysilane) Methoxysilane, 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, and 3-chloropropyltrimethoxysilane Ring agent, isopropyl N-ethylaminoethylamino titanate, isopropyl triisostearoyl titanate, titanium didioctyl pyrophosphate oxyacetate, tetraisopropyl didioctyl phosphate Ito titanate, neoalkoxy tri-N-beta-aminoethyl-amino phenyl
Titanium-based coupling agents such as titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxytris neodecanoyl zirconate, neoalkoxytris dodecanoyl benzenesulfonyl zirconate, neoalkoxytris ethylene Zirconium such as diaminoethyl zirconate, neoalkoxytris-aminophenyl zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum-based coupling agent, but a silicon-based coupling agent is preferred. preferable. 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
000 oligomers, epoxidized soybean fatty acid, epoxidized aviethyl alcohol, hydrogenated castor oil, modified silicone, anionic / nonionic surfactant, and the like.

The epoxy resin (A), the curing agent (B) and the flame retardant (C) of the present invention and, if necessary, a curing accelerator, a filler, a coupling agent, a flame retardant, a coloring agent and a leveling agent. After mixing using a Henschel mixer, 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 is obtained by dissolving and / or dispersing the components (A) to (C) and, if necessary, the above optional components in a solvent. Further, the epoxy resin composition once prepared by the above method may be dissolved in a solvent. Specific examples of solvents that can be used include γ-butyrolactones, N-methylpyrrolidone (NMP), N, N-dimethylformamide (D
MF), amide solvents such as N, N-dimethylacetamide, N, N-dimethylimidazolidinone, sulfones such as tetramethylene sulfone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, propylene Examples thereof include ether solvents such as glycol monomethyl ether monoacetate, tetrahydrofuran, and dioxane; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and aromatic solvents such as toluene and xylene. The solid content concentration in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight, more preferably 30 to 65% by weight.
% By weight.

A prepreg can be produced by applying 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. Further, the resin composition of the present invention can be applied to a film or the like to form a film with an adhesive. The film with the adhesive is obtained by drying the varnish obtained by the method described above on a substrate by various coating methods such as a gravure coating method, a screen printing method, a metal mask method, and a spin coating method known per se. The thickness is obtained by coating and drying to a predetermined thickness, for example, 20 to 100 μm, and which coating method is used depends on the type, shape, size, and film thickness of the base material. It is appropriately selected. As the base material of the film used, for example, polyamide, polyamide imide, polyarylate, polyethylene terephthalate, polybutylene terephthalate,
Films made of various polymers such as polyetheretherketone, polyetherimide, polyetherketone, polyketone, polyethylene, polypropylene and / or copolymers thereof, or various metal foils such as copper and aluminum.

The sheet-like adhesive of the present invention is used by forming the above-mentioned film with the adhesive into a sheet having a predetermined thickness, for example, 20 to 100 μm by a roll, a press or the like. In addition, the varnishes on the release sheet is a gravure coating method known per se, a screen printing method, a metal mask method,
It is applied by various coating methods such as spin coating, and then another release sheet is superimposed on the applied surface and dried to obtain a sheet adhesive having release layers on both sides of the adhesive layer. Since these are further cut and punched or cut into a desired shape and size in accordance with a predetermined shape and size of the semiconductor and used, a small-sized semiconductor device can be accurately bonded to a substrate.

[0028]

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.

Example 1 An epoxy resin composition having the composition shown in the column of Example 1 in Table 1 (the numerical value is "parts") was prepared by adding 1 part of N, N'-dimethylformamide (DMF) to methyl isobutyl ketone (DMF). MEK) was dissolved in 1 part of a mixed solvent to prepare a 60% varnish. This varnish has a thickness of 180 μm and a size of 50 ×
50 mm glass cloth (trade name, manufactured by Nitto Boseki Co., Ltd., W
EA18W105F115N), impregnated at 130 ° C x 5
The solvent was removed under the drying conditions of 150 ° C. × 2 minutes to obtain a prepreg.

Example 2, Comparative Example 1 Examples 2 and Comparative Example 1 in Table 1 were used as epoxy resin compositions.
A prepreg was prepared in the same manner as in Example 1 except that the composition shown in each column was used.

Test Example Using three prepregs obtained in Examples 1 and 2 and Comparative Example 1 and a thickness of 35 μm, 170 ° C. × 60 minutes, 30 kg / cm ²
Under the conditions described above, to produce a three-layer laminate. The following tests were carried out on the obtained laminates for heat resistance and flame retardancy, and the results are shown in Table 2. (Heat resistance) Laminates prepared in Examples and Comparative Examples were processed at a rate of 2 per minute.
Glass transition temperature (Tg) by TMA method under temperature rise condition of ℃
Was measured. (Flame retardancy test) The laminates prepared in Examples and Comparative Examples were UL
It evaluated based on -94V.

[0032]

Epoxy resin A: EOCN-104S (Novolak type epoxy resin; manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent: 214 g / eq) Epoxy resin B: RE-310S (bisphenol A type epoxy resin; manufactured by Nippon Kayaku Co., Ltd.) Epoxy equivalent: 1
85 g / eq) Curing agent A: H-1 (phenol novolak resin; manufactured by Meiwa Kasei Co., Ltd.) Curing agent B: DICY7 (dicyandiamide; manufactured by Yuka Shell Epoxy Co., Ltd.) Accelerator: 2-phenyl-4-methyl-5 -Hydroxymethylimidazole Flame retardant A: Exolit OP940 (aluminum salt of phosphinic acid; manufactured by Clariant Co., Ltd. (R ₁ in formula (1); methyl group, R ₂ ; ethyl group, M; Al, m; 3) Flame retardant B: ADK STAB FP-600 (phosphate ester; manufactured by Asahi Denka Kogyo KK)

[0034]

[0035]

According to the present invention, it is possible to provide a halogen-free resin composition having sufficient flame retardancy (for example, V-0 in UL94 test) without lowering the glass transition temperature of the cured product. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 85/02 C08L 85/02 4J040 C09D 7/12 C09D 7/12 4M109 163/00 163/00 C09J 7 / 02C09J 7/02 Z 11/00 11/00 163/00 163/00 H01L 23/29 H05K 1/03 610L 23/31 610R H05K 1/03 610 H01L 23/30 RF term (reference) 4F100 AB01C AB33C AK01A AK01D AK01E AK49B AK53A BA02 BA03 BA07 BA10A BA10B BA10C BA10D BA10E CA02A CA08A GB43 JJ07 JL14D JL14E 4J002 AC11X CC04X CC05X CC06X CC07X CD01W CD011 CD02W CD021 CD04W CD041 CD05W CD051 CD06W CD061 CD07W CD071 CD10W CD101 CD11W CD111 CD13W CD131 CE00X CH05X CQ013 EJ017 EJ037 EJ047 EL137 EN037 EN077 EN127 EQ027 ER027 ET007 EU117 EV077 EV217 EW136 FD010 FD090 FD133 FD136 FD14X FD147 FD150 FD200 GF00 GH01 GJ01 GQ01 HA05 4J004 AA13 AB05 CA03 CA04 CA06 CA08 CC02 DB02 FA05 4J036 AA01 DA01 DC26 FA12 FB07 JA01 JA05 JA06 JA07 JA08 KA01 4J038 DA052 DA072 DA102 DB011 DB031 DB041 DB05 DB01 DB07 JA07 JB08 JB17 JB18 JB20 JB32. HD27 JA09 JB02 KA03 KA16 KA36 LA03 LA08 MA02 MA10 MB03 NA19 NA20 PA23 PA30 4M109 AA01 EA02 EB02 EB07

Claims (11)

[Claims] An epoxy resin (A), a curing agent (B) and a flame retardant (C) are essential components, and the flame retardant (C) is represented by the following formula (1):
And / or a diphosphinate represented by the following formula (2) and / or a polymer thereof: Embedded image [Equation (1), in (2), R _1, R ₂ may be the same or different from each other, are linear or branched alkyl group or an aryl group having a carbon number of 1 to 6; R ₃ is A linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group or an arylalkylene group;
a, Al, Sb, Sn, Ge, Ti, Zn, Fe, Z
a metal selected from at least one of the group consisting of r, Ce, Bi, Sr, Mn, Li, Na and K; m
Is an integer from 1 to 4; n is an integer from 1 to 4; and x is an integer from 1 to 4. ], A flame-retardant epoxy resin composition characterized in that 80% or more of its particle size is 40 [mu] m or less. 2. The flame-retardant epoxy resin composition according to claim 1, wherein the curing agent (B) is a phenol. 3. The flame-retardant epoxy resin composition according to claim 1, wherein the curing agent (B) is a guanidine. 4. A varnish obtained by dissolving and / or dispersing the flame-retardant epoxy resin composition according to any one of claims 1 to 3 in a solvent. 5. A cured product obtained by curing the flame-retardant epoxy resin composition according to any one of claims 1 to 3. 6. A printed wiring board having a layer of the epoxy resin composition according to claim 1. 7. The method according to claim 1, wherein both sides or one side of the planar support are provided.
A sheet having a layer of the epoxy resin composition according to any one of claims 1 to 3. 8. The sheet according to claim 7, wherein the planar support is a polyimide film. 9. The sheet according to claim 7, wherein the planar support is a metal foil. 10. The sheet according to claim 7, wherein the planar support is a release film. 11. A sheet adhesive having a release film layer on both sides of the epoxy resin composition or varnish layer according to any one of claims 1 to 4.