JPH06184406A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition excellent in heat stability, impact resistance and toughness suitable for a sealant, etc., and useful as a printed-wiring board material excellent in drillability, adhesion, low water absorption and dielectric properties. CONSTITUTION:Based on 100 pts.wt. epoxy resin, 5 to 50 pts.wt. graft copolymer synthesized from (a) 10 to 70wt.% glycidyl group-containing monomer, (b) 10 to 50wt.% one or two or more kinds of monomers selected from an N- substituted maleimide, an unsaturated dicarboxylic acid anhydride and an alpha- alkylstyrene, (c) 10 to 70wt.% rubbery polymer capable of graft polymerization of the monomers (a) and (b) and (d) 0 to 50wt.% other monomer copolymerizable with these monomers (a), (b) and the rubbery polymer (c) is blended.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, and more specifically, it has excellent heat resistance, impact resistance and toughness, and has hole workability, adhesiveness and low water absorption when used as a printed wiring board material. The present invention relates to an epoxy resin composition having excellent properties and dielectric properties.

[0002]

2. Description of the Related Art Epoxy resin is used for capacitors and dios.
Widely used as a sealing material to protect individual semiconductors such as batteries, transistors and thyristors and integrated circuits such as ICs and LSIs from the mechanical and electrical external environment, and glass impregnated prepreg for printed wiring boards. There is.

In recent years, surface mounting has come to be adopted in response to miniaturization and thinning of electronic parts, and accordingly, the encapsulating material is required to have solder heat resistance. In addition, internal stress generated due to the difference in thermal expansion between the semiconductor element and the encapsulant causes a deviation of the aluminum wiring on the element surface and a crack in the element pellet itself. There is a strong demand to improve the toughness of the stop material.

With respect to the required characteristics of these encapsulating materials, for example, a method of using a polyfunctional epoxy resin in order to improve heat resistance (Japanese Patent Publication No. 63-58852, JP-A No. 60-85852).
199023, JP 63-3015, JP 63
-301219) and a method using an epoxy resin having a naphthalene skeleton (JP-A-61-737).
No. 19) has been proposed, but there are problems that heat resistance is insufficient and impact resistance and toughness decrease.

In order to improve impact resistance and toughness,
Method of adding silicone elastomer (Japanese Patent Application Laid-Open No. 63-
No. 297483), a method of adding a carboxyl group-terminated polybutadiene rubber [Adv. Chem. Se. Two
22, 389-401 (1989)], a method using a terpolymer containing glycidyl methacrylate [Proceedings of the Polymer Society of Japan, vol. 39, no. 4 (1990)]
Although the impact resistance and the toughness are improved, there is a problem that the heat resistance is lowered.

On the other hand, printed wiring board materials have heat resistance as well as high speed and high density mounting of electronic elements.
Improvements in hole workability, adhesiveness, low water absorption, and dielectric properties are required. In this type of material, as a method for improving the heat resistance, usually, a bisphenol type epoxy resin as a main component, a phenol novolak type epoxy resin,
Although a method of adding a cresol novolak type epoxy resin has been put into practical use, sufficient heat resistance has not been obtained.

Further, as a method for further improving the heat resistance, a polyfunctional epoxy resin may be used (see Japanese Patent Laid-Open No. HEI 2-
235919) and a method of adding an appropriate amount of a thermoplastic resin (JP-A-2-221122). Further, as a method of improving the hole workability, a method of reacting an epoxy resin with a tertiary amine, then reacting with triphenylphosphine, and further reacting with formaldehyde (JP-A-1-118520), an epoxy resin A method of adding bisphenols to the mixture
3-312832) and the like are disclosed.

Further, as a method of improving the adhesiveness, a method of providing a primer layer composed of an epoxy resin, a photo-acid generator and a (meth) acrylic acid ester between the base layer and the epoxy resin layer (Japanese Patent Laid-Open No. 3-30083). No. 65341) is disclosed. Further, as a method for improving hygroscopicity, a method of adding calcined kaolin clay (Japanese Patent Laid-Open No. 63-24542).
No. 5) is disclosed.

However, in these conventional improved techniques, even if the individual characteristics are improved, the prints are well balanced in heat resistance, hole workability, adhesiveness, low water absorption and dielectric characteristics. It was difficult to obtain a wiring board material.

[0010]

As described above, none of the conventional epoxy resin compositions satisfy the heat resistance, impact resistance, and toughness required as the sealing material, and the printed wiring board. It has been difficult to obtain a material that is well-balanced in heat resistance, hole workability, adhesiveness, low water absorption, and dielectric properties desired as materials.

In view of the above conventional circumstances, it is an object of the present invention to provide an epoxy resin composition capable of satisfying all of the above various performances required for a sealing material, a printed wiring board material and the like. .

[0012]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a specific amount of a specific graft copolymer is specified in an epoxy resin composition containing an epoxy resin and a curing agent. The inventors have found that what is added has excellent performance required for a sealing material, a printed wiring board material, etc., and have completed the present invention.

That is, the present invention provides an epoxy resin composition containing an epoxy resin and a curing agent, wherein a) 10 to 70% by weight of a monomer having a glycidyl group, and b) N-substituted per 100 parts by weight of the epoxy resin. Maleimide, unsaturated dicarboxylic acid anhydride,
10 to 50% by weight of one or more monomers selected from α-alkylstyrene, and c) 10 to 70% by weight of a rubbery polymer which is graft-polymerizable with the monomers of the above-mentioned a and b components. D) 5 to 50 parts by weight of a graft copolymer composed of 0 to 50% by weight of the monomer of the above a and b and the other monomer copolymerizable with the rubbery polymer of the above c component. The present invention relates to an epoxy resin composition characterized by being included.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The graft copolymer in the present invention is a graft copolymer consisting of the above-mentioned three components a to c or the above four components a to d. This graft copolymer is added to an epoxy resin composition. By including it, heat resistance, impact resistance, toughness, etc. as a sealing material can be improved.
Further, good results can be obtained in improving hole workability, adhesiveness, low water absorption, dielectric properties, etc. as a printed wiring board material.

Examples of the glycidyl group-containing monomer of the component a include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, carbon-carbon double bonds of these monomers (methacryloyl group, acryloyl group,
In some cases, an alkyl chain having 1 to 30 carbon atoms or a polyoxyalkylene such as polyoxyethylene or polyoxypropylene is introduced as a spacer between the allyl group) and the glycidyl group.

These monomers of the component a are used in the range of 10 to 70% by weight, preferably 30 to 70% by weight, based on the total amount of the components a to d, and one or more of them are used. 1
If it is less than 0% by weight, heat resistance as a sealing material and the like and hole workability and adhesiveness as a printed wiring board material are deteriorated. If it exceeds 70% by weight, the toughness as a sealing material and the workability are deteriorated, the flowability of a prepreg as a printed wiring board material is deteriorated, and the water absorption and the dielectric constant are increased.

The N-substituted maleimide of the component b is
Phenyl maleimide, cyclohexyl maleimide, t-
Butyl maleimide and the like. Further, the unsaturated dicarboxylic acid anhydride, maleic anhydride, itaconic anhydride,
Examples thereof include metaconic anhydride and citraconic anhydride. Further, α-alkylstyrene is α-methylstyrene, α-ethylstyrene, α-butylstyrene or the like.

These monomers of component b are used in one or two or more kinds in the range of 10 to 50% by weight, preferably 20 to 50% by weight in the total amount of components a to d. 1
If it is less than 0% by weight, the heat resistance as a sealing material and the like and the hole workability as a printed wiring board material are deteriorated. If it exceeds 50% by weight, impact resistance, toughness and workability as a sealing material are deteriorated, flowability of prepreg as a printed wiring board material is deteriorated, and water absorption and dielectric constant are increased. .

The c-component rubbery polymer may be any polymer which can be graft-polymerized with the above-mentioned a- and b-component monomers, for example, polybutadiene, styrene-butadiene rubber,
Examples include nitrile rubber, maleated rubber, butadiene-acrylonitrile rubber, ethylene-propylene-diene copolymer and ethylene-α-olefin rubber.

The rubbery polymer of the component c is 10 to 70% by weight, preferably 10 to 5% by weight in the total amount of the components a to d.
One or two or more thereof are used within the range of 0% by weight. If it is less than 10% by weight, impact resistance, toughness and workability as a sealing material are deteriorated, and water absorption and dielectric constant as a printed wiring board material are increased. When it exceeds 70% by weight, the heat resistance as a sealing material is lowered.

The other monomer of the component d may be any one as long as it can be copolymerized with the monomer of the components a and b and the rubbery polymer of the component c. For example, the following (a) ~
(Wa) Monomer etc. are mentioned. (A) Acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms such as methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl acrylate, docosyl acrylate, or methacrylic acid having the same alkyl group as above. Alkyl ester (b) Acrylic acid ester or methacrylic acid ester having polyalkylene glycol group such as polypropylene glycol acrylate, polyethylene glycol acrylate, polyethylene glycol methacrylic acid, polypropylene glycol methacrylic acid ( C) Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid (d) Unsaturated dicarboxylic acids such as fumaric acid and itaconic acid (e) Dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, Itako Dibutyl acidate,
Dicarboxylic acid esters such as methyl ethyl fumarate, methyl butyl fumarate, and methyl ethyl itaconate (f) Styrene derivatives such as styrene and chlorostyrene (g) Vinyl halides such as vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride Unsaturated ketones such as vinylidene halide (thi) methyl vinyl ketone and n-butyl vinyl ketone, vinyl esters such as (ri) vinyl acetate and vinyl butyrate, vinyl ethers such as (n) methyl vinyl ether and butyl vinyl ether. ) Vinyl cyanide such as acrylonitrile, methacrylonitrile and vinylidene cyanide (o) Acrylamide and its alkyl-substituted amides (wa) Unsaturated sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid

The other monomers of the component d are a to d.
0 to 50% by weight, preferably 0 to 30 in the total amount of the components
One or two or more thereof are used within the range of weight%. If it exceeds 50% by weight, heat resistance, impact resistance and toughness as a sealing material and the like deteriorate, and hole workability and adhesiveness as a printed wiring board material deteriorate.

The graft copolymer in the present invention can be produced by a known method, for example, as follows.
First, a solvent and a c-component rubbery polymer are placed in a reactor and stirred to uniformly dissolve and mix. Also, the system is replaced with nitrogen gas. Then, after the temperature is raised to a reaction temperature of usually 40 to 120 ° C., a mixed solution of a monomer mixture consisting of a, b two components or a, b, d three components, a polymerization initiator, a molecular weight modifier and a solvent is added. Drop it. After completion of the dropping, aging is performed to complete the reaction. The solvent is distilled off from the reaction solution by a vacuum dryer to obtain a solid substance, which is pulverized to obtain a graft copolymer.

The weight average molecular weight (Mw) of the graft copolymer thus produced is usually 5,000 to 5.
It is preferably in the range of 0,000, and the epoxy equivalent is usually in the range of 140 to 1,700.

Examples of the epoxy resin in the present invention include (I) epoxy compound and (II) glycidyl compound listed below. From one or both, only one kind or a mixture of two or more kinds is used. be able to.

Examples of the epoxy compound (I) include epoxy resins obtained by reacting polyvalent alcohols such as bisphenol A and bisphenol F or alkylene oxide adducts thereof with epichlorohydrin, and phenols. Aromatic epoxy resins represented by novolak type epoxy resins such as lunovolac type and cresol novolak type; representative of epoxy resins obtained by reaction of hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin Alicyclic epoxy resin having alicyclic ring such as cyclohexene oxide group, tricyclodecene oxide group and cyclopentene oxide group; 1,4-butanediol, 1,6-hexanedioe
Of aliphatic polyhydric alcohols such as phenol and its alkylene oxide adducts and polyglycidyl ethers obtained by reaction with epichlorohydrin, and aliphatic epoxies represented by diglycidyl ester of aliphatic long-chain dibasic acid Resins: Tetrabromobisphenol A type epoxy resins, flame-retardant epoxy resins represented by brominated phenol novolak type epoxy resins, and the like.

Examples of the glycidyl compound (II) include methyl glycidyl ether, butyl glycidyl ether, and 2
-Ethylhexyl glycidyl ether, phenyl glycidyl ether, sec-butyl phenyl glycidyl ether
Ter, allyl glycidyl ether and other glycidyl ethers
Ter; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, dimer acid glycidyl ester, glycidyl acrylate, glycidyl methacrylate glycidyl ester; N, N
-Glycidyl amines such as diglycidyl aniline, tetraglycidyl diaminophenyl methane, and triglycidyl p-aminophenol.

Examples of the curing agent in the present invention include the following thermosetting catalysts (1) to (15) and energy ray curing catalysts (16) to (23), one of which is Can be used alone or in admixture of two or more.

<Thermosetting Catalyst> (1) Polymethylenediamine, dipropylenediamine,
Chain-like aliphatic primary diamines such as trimethylhexamethylenediamine (2) Chain-like aliphatic primary polyamines such as iminobispropylamine, 1,3,6-trisaminomethylhexane and tetraethylenepentamine (3) N- Alicyclic polyamines such as aminoethylpiperazine and bis (4-amino-3-methylcyclohexyl) methane (4) Aromatic-containing aliphatic primary amines such as metaxylylenediamine (5) Metaphenylenediamine, 2,4 -Aromatic primary amines such as diaminodiphenylamine and diaminodiphenylsulfone (6) Secondary amines such as dimethylamine and diethylamine (7) Dimethylcyclohexylamine, pyridine, α-
Aromatic acid anhydrides such as tertiary amines such as picoline (8) phthalic anhydride, pyromellitic anhydride, grillerol tris (anhydrotrimeritate) (9) maleic anhydride, methyl tetrahydrophthalic acid Anhydrides, cycloaliphatic acid anhydrides such as methylcyclohexene tetracarboxylic acid anhydride (10) Aliphatic acid anhydrides such as polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride (11) Dimer acid and Polyamide resin obtained by condensation reaction of polyamine (12) 2-methylimidazole, 1-cyanoethyl-2
-Imidazoles such as ethyl-4-methylimidazole and 1-cyanoethyl-2-phenylimidazolinium trimellitate (13) Boron trifluoride-amine complex, organic acid hydrazide, polyamine salts, etc. (14) Liquid polymercaptans, polymercaptans such as polysulfides, etc. (15) Synthetic resin initial condensates such as novolak type phenolic resins and polyvinylphenols

<Energy ray curing catalyst> (16) Phenyl diazonium tetrafluoroborate,
Allyldiazonium salts such as 4-methoxyphenyldiazonium hexafluorophosphate (17) Diphenyliodonium tetrafluoroborate
Diaryl iodonium salts such as di- (4-butylphenyl) iodonium hexafluorophosphate (18) Triphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrafluoroborate, tris (4-methoxyphenate) Trienylsulfonium salts such as (enyl) sulfonium hexafluorophosphate (19) Dialkylphenacylsulfonium salts such as dimethylphenacylsulfonium hexafluorophosphate and phenacyltetramethylenesulfonium tetrafluoroborate (20) 3,5-Dimethyl-4-hydroxyphenylsulfonium tetrafluoroborate, 3,5-dibutyl-
4-Hydroxyphenylsulfonium hexafluoroantimonate and other dialkyl-4-hydroxyphenylsulfonium salts (21) α-hydroxymethylbenzoinsulfonic acid ester, N-hydroxyimide sulfonate, α-sulfonyloxyketone (22) 2- (4-methoxyphenyl) -4,6-di (trichloromethyl) triazine and other triazine compounds (23) Orthodiazonaphthoquinone-4-sulfonate, orthodiazonaphthoquinone-5 -Diazonaphthoquinone compounds such as sulfonates

The epoxy resin composition of the present invention comprises the above-mentioned graft copolymer together with the above-mentioned epoxy resin and curing agent. The amount of the graft copolymer used is
The amount is 5 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the epoxy resin. If the amount is less than 5 parts by weight, heat resistance, impact resistance and toughness as a sealing material are deteriorated, and hole workability as a printed wiring board material,
Adhesiveness decreases and dielectric constant increases. Also, 50
If the amount is more than the weight part, the workability as a sealing material and the flowability of the prepreg as a printed wiring board material deteriorate.

The amount of the curing agent used is usually 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the epoxy resin. Particularly, in the thermosetting catalysts (1) to (15) described above, the epoxy resin 100
0.01 to 5 parts by weight per part by weight, the above (16) to
With the energy ray curing catalyst of (23), epoxy resin 10
It may be 1 to 50 parts by weight per 0 parts by weight.

The epoxy resin composition of the present invention contains the above-mentioned three components of the epoxy resin, the graft copolymer and the curing agent as essential components, and within a range not impairing the effects of the present invention, a curing accelerator and a releasing agent. A mold agent, a softening agent, a coupling agent, a colorant, a flame retardant aid, a filler, a solvent and the like may be added as optional components.

The epoxy resin composition of the present invention can be used as a sealing material or a printed wiring board material by a conventionally known method. For example, in a printed wiring board material, first, a predetermined amount of an epoxy resin, a graft copolymer and a curing agent are uniformly mixed to prepare a resin composition. Then, the glass cloth is impregnated with this, and the epoxy reaction is allowed to proceed slightly through a drying device to obtain a prepreg in the B stage. Then, this prepreg is overlaid on a copper foil and heated and pressed by a laminating press to obtain a copper-clad laminate for a printed wiring board.

[0035]

INDUSTRIAL APPLICABILITY As described above, the epoxy resin composition of the present invention has excellent heat resistance, impact resistance, toughness, etc., as a sealing material, etc., and also has a hole forming property when used as a printed wiring board material. It has excellent properties, adhesiveness, low hygroscopicity, and dielectric properties.

[0036]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The graft copolymers A to K used in the following Examples and Comparative Examples were produced by the methods of Reference Examples 1 and 2 below. Moreover, in the following Examples and Comparative Examples, "parts" means "parts by weight".

Reference Example 1 Stirrer with 6-blade turbine blade, stainless baffle plate 4
300 g of methyl isobutyl ketone and 105 g of polybutadiene rubber [Dien NF-35R] manufactured by Asahi Kasei Kogyo Co., Ltd. were placed in a 2-liter polymerization reaction tank equipped with one plate, and the mixture was stirred and uniformly dissolved and mixed. After replacing the inside of the reaction system with nitrogen gas, the temperature was raised to 65 ° C., and glycidyl methacrylate 21 was added.
A mixed solution of 0 g, phenylmaleimide 105 g, methyl methacrylate 280 g, and 2,2-azobisisobutyronitrile 3.5 g was added dropwise over 3 hours. After completion of dropping, aging was carried out at the same temperature for 3 hours.

After the reaction is carried out in this manner, the reaction solution is mixed with 14
A pressure reduction treatment was performed under the conditions of 0 ° C., 20 Torr and 2 hours to distill off methyl isobutyl ketone. The obtained solid resin was pulverized with a mixer to give a weight average molecular weight (Mw) of 5
Graft copolymer A having an epoxy equivalent of 530 and 50,000 was obtained.

Reference Example 2 The weight average molecular weight and epoxy equivalent shown in the same table were obtained in the same manner as in Reference Example 1 except that the polymerization reaction tank and the charged amount of the dropping solution were changed as shown in Tables 1 to 3. Graft copolymers B to K were obtained. For reference, Table 1 also shows the charging amount of the graft copolymer A and the like. Further, in Tables 1 to 3, each reference numeral indicating a rubbery polymer, a monomer or the like is as follows.

<Rubber Polymer> PBd: Polybutadiene Asahi Kasei Kogyo's "Diene NF-35R" St-Bd rubber: Styrene-butadiene rubber Asahi Kasei Kogyo's "Solvrene 1206" EtO rubber: Ethylene-α- Olefin rubber "JSR EP 21" manufactured by Japan Synthetic Rubber Co., Ltd. <Monomer having glycidyl group> GMA: Glycidyl methacrylate GA: Glycidyl acrylate AGE: Allyl glycidyl ether <N-substituted maleimide monomer > PMI: Phenylmaleimide CHMI: Cyclohexylmaleimide α-MSt: α-methylstyrene <Other monomer> MMA: Methyl methacrylate St: Styrene AN: Acrylonitrile <Polymerization initiator> AIBN: 2,2-azobisiso Butyronitrile

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

Example 1 100 parts of an epoxy resin [“Epicote 828” manufactured by Yuka Shell Epoxy Resin Co., Ltd.] was added to a graft copolymer A; 2
0 part and 35 parts of 4,4-diaminodiphenyl sulfone as a curing agent were mixed and stirred at room temperature for 3 minutes to prepare a thermosetting epoxy resin composition.

Examples 2, 3 The amount of the graft copolymer A used was 5 parts (Example 2), 5 parts.
Two types of thermosetting epoxy resin compositions were prepared in the same manner as in Example 1 except that the amount was changed to 0 part (Example 3).

Examples 4 to 6 Graft copolymer A; instead of 20 parts, graft copolymer B; 30 parts (Example 4), graft copolymer C; 10 parts (Example 5), graft copolymer Combined D: Three types of thermosetting epoxy resin compositions were prepared in the same manner as in Example 1 except that the amount was changed to 50 parts (Example 6).

Comparative Example 1 A thermosetting epoxy resin composition was prepared in the same manner as in Example 1 except that 20 parts of the graft copolymer A was omitted.

Comparative Examples 2 and 3 Graft Copolymer A; Carboxyl group-terminated polybutadiene rubber [manufactured by Ube Industries, Ltd.
B 2000 × 162 ″] 30 parts (Comparative Example 2), 1-methyl [α-methyl-α- (4-glycidoxyphenyl)
Ethyl] -4-[[alpha], [alpha] -bis (glycidoxyphenyl) ethyl] benzene 2 parts in the same manner as in Example 1 except that 30 parts (Comparative Example 3) were used. A composition was prepared.

Comparative Example 4 A thermosetting epoxy resin composition was prepared in the same manner as in Example 1 except that the amount of the graft copolymer A used was changed to 80 parts.

Comparative Examples 5 to 7 Graft Copolymer A; 3 parts (Comparative Example 5), Graft Copolymer H; 10 parts (Comparative Example 6), graft copolymer weight instead of 20 parts Three types of thermosetting epoxy resin compositions were prepared in the same manner as in Example 1 except that the combination I was changed to 30 parts (Comparative Example 7).

In order to evaluate the performance of each of the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 7 as a sealing material and the like, the epoxy resin compositions were poured into a mold for producing a test piece immediately after preparation, and 120 ° C. It was heat-cured under the conditions of × 1 hour and 180 ° C. × 5 hours. For this curing test piece, the following method,
The glass transition temperature, fracture toughness, flexural modulus, shell peel impact strength and spiral flow were investigated.

Among these test items, "glass transition temperature" is heat resistance, "fracture toughness and flexural modulus" is toughness, "shell pie impact strength" is impact resistance, and "spiral flow" is Each becomes an index of workability.

<Glass Transition Temperature> Using a DSC120 manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature was measured at a temperature rising rate of 10 ° C./min.

<Fracture Toughness, Bending Elastic Modulus, Shell Peel Impact Strength> Fracture toughness is in accordance with ASTM E-379-83.
Each was measured according to 6911.

<Spiral Flow> Using an IS 25ED injection molding machine manufactured by Toshiba Machine Co., Ltd., using a 6 mm Archimedes type mold, a pressure of 47% (about 70 kg / c at 175 ° C.).
It was measured under the condition of m ² ).

The results of these tests are shown in Tables 4 to 6 below. For reference, the table also shows the type and amount of the graft copolymer (or its substitute substance) used in each epoxy resin composition. In addition, “C of Comparative Example 2
TBN is a carboxy-terminated polybutadiene rubber [Ube Industries, Ltd. "Hiker CTB 2000 x 16
2 ”and“ MGPEB ”of Comparative Example 3 are 1-methyl [α-
Methyl-α- (4-glycidoxyphenyl) ethyl]-
4- [α, α-bis (glycidoxyphenyl) ethyl]
It is benzene.

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[Table 6]

Example 7 100 parts of an epoxy resin [“Epicote 828” manufactured by Yuka Shell Epoxy Resin Co., Ltd.] was added to a graft copolymer E; 1
0 part and 1 part of triphenylsulfonium hexafluoroantimonate as a curing agent were mixed and stirred at room temperature for 3 minutes to prepare a photocurable epoxy resin composition.

Examples 8 to 11 Graft copolymer E; instead of 10 parts, graft copolymer B; 30 parts (Example 8), graft copolymer F; 50 parts (Example 9), graft copolymer Coalescence G; 30 parts (Example 1
0), graft copolymer C; four kinds of photocurable epoxy resin compositions were prepared in the same manner as in Example 7 except that the content was changed to 10 parts (Example 11).

Comparative Example 8 A photocurable epoxy resin composition was prepared in the same manner as in Example 7 except that the use of 10 parts of graft copolymer E was omitted.

Comparative Examples 9 and 10 Graft Copolymer E; instead of 10 parts, except that graft copolymer J; 30 parts (Comparative Example 9) and graft copolymer K; 10 parts (Comparative Example 10) were used. In the same manner as in Example 7, two types of photocurable epoxy resin compositions were prepared.

Examples 7 to 11 and Comparative Examples 8 to 1 above
In order to evaluate the performance of each epoxy resin composition of 0 as a sealing material, the epoxy resin composition was poured into a mold for producing a test piece immediately after preparation, and a 1Kw mercury lamp was used in a Tosukiya 1000 manufactured by Toshiba Lighting & Technology Corporation. Then, ultraviolet rays were irradiated for 2 minutes at an irradiation distance of 10 cm to cure.

For this cured test piece, the glass transition temperature, fracture toughness, flexural modulus, shell peel impact strength and spiral flow were examined in the same manner as described above. The test results are shown in Tables 7 and 8 below. For reference, the same table also shows the type and amount of the graft copolymer used in each epoxy resin composition.

[0066]

[Table 7]

[0067]

[Table 8]

Next, in order to evaluate the performance of each of the epoxy resin compositions of Examples 7 to 11 and Comparative Examples 8 to 10 as a material for a printed wiring board, glass cloth 7628 / AS431 ( Asahi Siebel Co.) and impregnated with ultraviolet rays for 1 minute from a height of 10 cm using a high pressure mercury lamp of 1 Kw to form a B-stage to prepare a prepreg. 8 pieces of this prepreg and thickness 35μ
m copper foil is overlaid, and 90 at 90 ℃ under the condition of 180 ℃ and 40Kg / cm ^2.
After press molding for 1 minute, a printed wiring board material having a thickness of 1.6 mm was prepared.

With respect to this printed wiring board material, the glass transition temperature, the smear generation rate during drilling, the adhesiveness, the water absorption, the dielectric constant and the flowability of the prepreg were examined. The glass transition temperature was measured in the same manner as above, and the others were measured by the following methods. The test results are shown in Tables 9 and 10 below.
For reference, the same table also shows the type and amount of the graft copolymer used in each epoxy resin composition.

<Smear Occurrence Rate during Drilling> With a 1 mm diameter drill, the rotation speed is 60,000 rpm and the feed rate is 50 μm /
The rate of occurrence of smear (dirt formed by softening and melting of chips) around 5,000 hits was examined after three rotations of one rotation.

<Adhesiveness> According to the method of JIS C 6484, the normal state and the soldering process (after the process of floating on the molten solder at a temperature of 260 ° C. for 20 seconds) were measured.

<Water Absorption> The water absorption was measured after boiling in water at 100 ° C. for 2 hours.

<Dielectric Constant> According to the method of JIS C 6484, the normal state (after being left in air with relative humidity of 65% for 96 hours) and the moisture absorption treatment (after being left in water at 50 ° C. for 48 hours) , Respectively measured.

<Flowability of prepreg> Hiroshi Kakiuchi, "New Epoxy Resin", P.P. 487, Shokoido (1985), according to the resin flowability method, a sample sandwiched between mirror-finished plates was pressed with a press hot plate adjusted to 171 ± 3 ° C.
The mixture was heated and pressed at 4 ± 2 Kg / cm ² for 3 minutes, and the flow rate (% by weight) of the resin flowing out at that time was measured.

[0075]

[Table 9]

[0076]

[Table 10]

Example 12 100 parts of an epoxy resin [“Epicote 828” manufactured by Yuka Shell Epoxy Resin Co., Ltd.] was added to a graft copolymer A; 2
0 part, 30 parts of 4,4-diaminodiphenyl sulfone as a curing agent and 1 part of dicyandiamide were mixed and stirred at room temperature for 3 minutes to prepare a thermosetting epoxy resin composition.

Examples 13 and 14 The amount of the graft copolymer A used was 5 parts (Example 13),
Two types of thermosetting epoxy resin compositions were prepared in the same manner as in Example 12 except that the amount was changed to 50 parts (Example 14).

Examples 15 to 17 Graft copolymer A; instead of 20 parts, graft copolymer B; 30 parts (Example 15), graft copolymer C; 10
Part (Example 16), graft copolymer D; in the same manner as in Example 12 except that 50 parts (Example 17) were used.
Three types of thermosetting epoxy resin compositions were prepared.

Comparative Example 11 A thermosetting epoxy resin composition was prepared in the same manner as in Example 12 except that 20 parts of graft copolymer A was omitted.

Comparative Examples 12 and 13 Graft Copolymer A; 20 parts of polyether sulfone (“VICTREX” manufactured by ICI) and 20 parts of diglycidylaniline (Comparative Example 12) in place of 20 parts, unbaked kaolin clay [Shiraishi] "Poly clay" manufactured by Calcium Co., Ltd.]
Two types of thermosetting epoxy resin compositions were prepared in the same manner as in Example 12 except that the amount was changed to 20 parts (Comparative Example 13).

Comparative Example 14 A thermosetting epoxy resin composition was prepared in the same manner as in Example 12 except that the amount of the graft copolymer A used was changed to 80 parts.

Comparative Examples 15 to 17 Graft Copolymer A; 3 parts (Comparative Example 15), Graft Copolymer H; 10 parts (Comparative Example 16), graft copolymer, instead of 20 parts Combined I; 3 except that the amount was changed to 30 parts (Comparative Example 17).
A variety of thermosetting epoxy resin compositions were prepared.

Examples 12 to 17 and Comparative Example 11 described above
In order to evaluate the performance as a printed wiring board material for each of the epoxy resin compositions Nos. 17 to 17, glass cloth 7628 / AS431 (manufactured by Asahi Sibel Ltd.) was impregnated immediately after preparation, and 100 ° C. × 3 minutes It was dried at 150 ° C. for 3 minutes to be B-staged to prepare a prepreg. This prepreg 8
Overlaid with 35 μm thick copper foil, 180 ℃, 40 kg / cm
Press molding was carried out for 90 minutes under the condition ² to produce a printed wiring board material having a thickness of 1.6 mm.

With respect to this printed wiring board material, the glass transition temperature, the rate of smearing during drilling, the adhesiveness, the water absorption, the dielectric constant and the flowability of the prepreg were examined by the same method as described above. The test results are shown in Tables 11 to 13 below. For reference, the table also shows the type and amount of the graft copolymer (or its substitute substance) used in each epoxy resin composition.

In Table 12, "PES" of Comparative Example 12
Polyethersulfone (ICI "VICTRE
X ”) and the same“ GAN ”are diglycidylaniline, and“ Kaolin clay ”in Comparative Example 13 is unbaked kaolin clay [“ Poly clay ”manufactured by Shiraishi Calcium Co., Ltd.].

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[Table 11]

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[Table 12]

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[Table 13]

From Tables 4 to 8 above, the epoxy resin composition of the present invention has excellent heat resistance, impact resistance, toughness, etc. as a sealing material, and the above Tables 9 to 9 From 13 it is clear that in addition to excellent heat resistance as a printed wiring board material, it also has good hole workability, adhesiveness, hygroscopicity, dielectric properties and the like.

Claims (1)

[Claims] 1. An epoxy resin composition containing an epoxy resin and a curing agent, wherein a) 10 to 70% by weight of a monomer having a glycidyl group, and b) N-substituted maleimide, and unsaturated per 100 parts by weight of the epoxy resin. Dicarboxylic acid anhydride,
10 to 50% by weight of one or more monomers selected from α-alkylstyrene, and c) 10 to 70% by weight of a rubbery polymer which is graft-polymerizable with the monomers of the above a and b components. D) 5 to 50 parts by weight of a graft copolymer composed of 0 to 50% by weight of the monomer of the above-mentioned a and b components and the other monomer copolymerizable with the rubbery polymer of the above-mentioned c component. An epoxy resin composition characterized by being included.