JPH07733B2 - Epoxy resin composition - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to an epoxy resin composition, and more particularly to a stable dispersion of specific silicone resin particles in an epoxy resin matrix, which is particularly resistant to cracking against epoxy resin. TECHNICAL FIELD The present invention relates to a novel epoxy resin composition imparted with toughness and toughness.

As is well known, the epoxy resin composition is excellent in mechanical properties such as tensile strength and bending strength, electrical properties such as dielectric properties and volume resistivity, and therefore, adhesive materials and coating materials. Widely applied to insulation materials for various electric and electronic devices.

However, the epoxy resin, which is the main component, usually lacks crack resistance and toughness, and it is difficult to alleviate the stress caused by shrinkage during curing.Therefore, various efforts have been made to improve these drawbacks. Came. The main measures include, for example, (1) a special epoxy resin that imparts flexibility, such as polyethylene glycol diglycidyl ether, hexanediol diglycidyl ether, urethane-modified epoxy resin, thiochol-modified epoxy resin, dodecenyl succinic quan It is known that hydride, polyazelaic acid polyanhydride or the like is blended, or (2) sesame particles having a low Tg such as modified acrylonitrile-butadiene rubber or acrylic rubber are dispersed. However, the method (1) cannot be sufficiently improved because the curing speed becomes slow, the heat resistant strength is lowered, and the cured product loses flexibility with time. Further, in the method (2), the water absorption rate of the resin becomes large.

As a result of earnestly researching the modification of such an epoxy resin, the present inventors have specific silanol organopolysiloxanes at both ends and a specific epoxy resin having at least two alkoxysilyl groups in one molecule. If an organosilane compound is added and, if necessary, stirred and mixed under heating, the silicone resin particles, which are the cross-linking reaction product of the silanol organopolysiloxane at both ends and the organosilane compound, are dispersed uniformly and stably in the epoxy resin matrix. The present invention has been completed and the present invention has been completed.

Structure and Effect of the Invention That is, the present invention relates to 100 parts (parts by weight, the same applies hereinafter) of epoxy resin, and [Wherein, R ₁ is methyl or phenyl, R ₂ is phenyl, p
Is 9 to 500, and q is 0 or 6% or less of p]. 5 to 200% by weight of a mixture of two or more silanol organopolysiloxanes having both terminals at room temperature which are liquid at room temperature (hereinafter referred to as silicone resin) And the formula (b): Or Wherein, R ₃ is hydrogen, phenyl, benzyl, cyclohexyl, vinyl benzyl or allyl, R ₄ is _{-C 2 H 4 -, - C} 3 H
₆ - or _{-C 2 H 4 SC 2 H 4} -, R 5 and R ₆ are the same or different connexion methyl or ethyl, R ₇ is _{-C 2 H 4 -, - C} 2 H 4 SC 2 H
_{4 -, - C 2 H 4} NHC 2 H 4 - or R ₈ is —C ₂ H ₄ — or —C ₃ H ₆ —, and m is 0 or 1.] (c) Formula: [Wherein R ₅ , R ₆ and m are as defined above, and R ₉ is -C
₃ H ₆ — or —CH ₂ —], (d) Formula: [Wherein R ₅ , R ₆ and m are as defined above, and R ₁₀ is And an epoxysilane compound represented by the formula (e): [Wherein R ₅ , R ₆ and m have the same meanings as described above, and R ₁₁ is-
A- or -Q-NHCOX-A- (wherein A is an alkylene group, preferably a lower alkylene having 2 or more carbon atoms, especially 3 or more carbon atoms such as-(CH ₂ ) ₂ -,-(CH ₂ ) _3-, etc. , Q is a diisocyanate residue, for example, an aromatic diisocyanate residue such as 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated An aliphatic diisocyanate residue such as MDI or hydrogenated TDI, and X is —NH—, —O— or —S—)], and an isocyanate silane compound represented by the formula (f): [Wherein R ₅ is as defined above, R ₁₂ is methyl or ethyl, R ₁₃ is —CH ₂ —, —C ₂ H ₄ — or —C ₃ H ₆ —, and Y is CH _{2
= CH-, C 6 H 5,} CnF 2 n + 1 (n = 1~10), NC- or NC (CH _{2) 3} S-, and r is 0, 1 or 2, m organosilane compound is represented by a 0 or 1 when r is 2] and (g) formula: [Wherein R ₅ and R ₁₂ are as defined above, and R ₁₄ is C _{n ′} H
_{2n '+ 1 (n' =} 1~20), CH 2 = CH- or C ₆ H _5, and r is 0 or 1 when 0, 1 or 2, m is r is 2
And a mixture of one or more selected from the group of organic silane compounds represented by the formula [1] is used, the molar ratio of the hydroxyl group and the alkoxy group: [OR ₆ and / or OR ₁₂ ] / [OH] is
By blending in a ratio of 0.1 to 15 and, if necessary, stirring and mixing under heating, the silicone resin particles, which are the cross-linking reaction product of the silicone resin and the organic silane compound, are dispersed uniformly and stably in the epoxy resin matrix. The present invention provides an epoxy resin composition characterized by being present.

The epoxy resin in the present invention may be a usual epoxy resin and is not particularly limited. The following are mentioned as a specific example, and 1 type or a mixture of 2 or more types is used.

(1) Glycidylamine type epoxy resin N, N-diglycidylamino epoxy resin having at least one N, N, N ', N'-tetraglycidylaminodiphenylmethane, N, N-diglycidyl meta ( Or para)
Aminophenol glycidyl ethers and their condensates. These are marketed as Araldite MY720 (manufactured by Ciba-Geigy) and Epototo YH434, YH120 (manufactured by Toto Kasei).

(2) Novolak type epoxy resin Epicoat as a phenol novolak type epoxy resin
152,154 (Ciel Chemical Co., Ltd.), Dow epoxy resin DEN431,
438,439,485 (manufactured by Dow Chemical Co.), Ciba Geigy EPN11
38,1139 (manufactured by Ciba Geigy) and the like.

Ciba Geigy ECN1235,1273,1280,1299 (made by Ciba Geigy), EOCN as cresol novolac type epoxy resin
102, 103, 104 (made by Nippon Kagaku Co., Ltd.), etc.

(3) Epicoat 828,834,827,1001,1002,1004,1007,1009 (produced by Yuka Shell Co., Ltd.), Dow Epoxy DER331,332,662,663U, 662U (produced by Dow Chemical Co.), Araldite 60717071,7072 as bisphenol A type epoxy resin. (Manufactured by Ciba Geigy), Epicron 840,850,855,860,1050,3050,
4050, 7050 (manufactured by Dainippon Ink and Chemicals, Inc.), etc.

Urethane-modified bisphenol A type epoxy resin such as ADEKA RESIN EPV-6, EPV-9, EPV-15 (manufactured by Asahi Denka Co., Ltd.).

Araldite 8011 (manufactured by Ciba Geigy) as brominated bisphenol A type epoxy resin, Dow epoxy resin DER5
11 (manufactured by Dow Chemical Co.), etc.

(4) Araldite CY-179 as alicyclic epoxy resin,
CY-178, CY-182, CY-183 (manufactured by Ciba Geigy) and the like.

(5) Others: Bisphenol F type, resorcin type, tetrahydroxyphenylethane type, polyalcohol, polyglycol type, glycerin triether type, polyolefin type, epoxidized soybean oil, ester type epoxy resin, etc. may also be used. it can.

Regarding these epoxy resins, those that are liquid at room temperature can be used as they are, but those that are solid at room temperature are
It may be melted by heating above its melting point or liquefied by using a liquid epoxy resin together.

The silicone resin (a) of the formulas [I], [I '] and [II "] according to the present invention is, for example, a terminal silanol polydimethylsiloxane, a terminal silanol diphenyl siloxane, a terminal silanol polydimethyl-diph- ane manufactured by Chitso Corporation. Erylosiloxane and polytetramethyl-p-sylphenylene siloxane are commercially available.
It is selected in the range of 5 to 200 parts, preferably 5 to 50 parts per 100 parts. If it is less than 5 parts, the modifying effect cannot be obtained, and if it exceeds 200 parts, the entire resin is in a gel state.

Structural formulas and compound names of specific examples of the aminosilane compound (b) of the formulas [II] and [III] in the present invention are listed below.

Aminosilane compound of formula [II] H ₂ NC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ γ-aminopropyltriethoxysilane H ₂ NC ₂ H ₄ Si (OCH ₃ ) ₃ β-aminoethyltrimethoxysilane γ-Aminopropyldiethoxymethylsilane CH ₂ ＝ CHCH ₂ NHC ₃ H ₆ Si (OCH ₃ ) ₃ γ-allylaminopropyltrimethoxysilane β- (β-aminoethylthioethyl) diethoxymethylsilane H ₂ NC ₂ H ₄ SC ₂ H ₄ Si (OC ₂ H ₅ ) ₃ β- (β-aminoethylthioethyl) triethoxysilane β-phenylaminopropyltrimethoxysilane γ-Cyclohexylaminopropyltrimethoxysilane γ-benzylaminopropyltrimethoxysilane γ- (Vinylbenzylaminopropyl) triethoxysilane Aminosilane compound of formula [III] H ₂ NC ₂ H ₄ NHC ₃ H ₆ Si (OCH ₃ ) ₃ N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane H ₂ NC ₂ H ₄ NHCH ₂ Si (OCH ₃ ) ₃ β-aminoethylaminomethyltrimethoxysilane H ₂ NC ₂ H ₄ NHC ₂ H ₄ NHC ₃ H ₆ Si (OCH ₃ ) ₃ γ- [β- (β-aminoethylaminoethylamino) propyl] trimethoxysilane N- (3-Triethoxysilylpropyl) urea Structural formulas and compound names of the specific examples of the mercaptosilane compound (c) of the formula [IV] in the present invention are listed below.

3-Mercaptopropylmethyldimethoxysilane HS-CH ₂ CH ₂ CH ₂ -SiOC ₂ H ₅ ) ₃ 3-Mercaptopropyltriethoxysilane HS-CH ₂ -SiOCH ₃ ) ₃ Mercaptomethyltrimethoxysilane HS-CH ₂ CH ₂ CH _2- SiOCH ₃ ) ₃ 3-Mercaptopropyltrimethoxysilane With respect to specific examples of the epoxysilane compound (d) of the formulas [V] and [V ′] in the present invention, the structural formulas and compound names are listed below.

β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane [2- (3,4-epoxy-4-methylcyclohexyl) propyl] methyldiethoxysilane (3-glycidoxypropyl) methyldiethoxysilane 3-Glycidoxypropyltrimethoxysilane Structural formulas and compound names are listed below as specific examples of the isocyanate silane compound (e) of the formula [VI] in the present invention.

OCN-CH ₂ CH ₂ CH ₂ -SiOC ₂ H ₅ ) ₃ γ-isocyanatopropyltriethoxysilane OCN-CH ₂ CH ₂ CH ₂ CH ₂ -SiOCH ₃ ) ₃ γ-isocyanatopropyltrimethoxysilane These organosilane compounds (b) ~ (E) are all
The organic silane compounds (b) to (e) functioning as a dispersion stabilizer and a curing agent, and the formula [VI] exemplified below.
One kind or a mixture of two or more kinds may be selected and used from the group of the organosilane compounds (f) and (g) of [I] and [VIII]. The amount used (the total amount in the case of a mixture of two or more kinds) is generally the molar ratio of the hydroxyl group and the alkoxy group to the silicone resin (a): [OR ₆ and / or OR ₁₂ ] / [OH ] Is 0.1 to 15. If this ratio is less than 0.1, the dispersion stabilizing effect will not be exhibited, and if it exceeds 15, the viscosity stability of the epoxy resin composition obtained by dispersing the silicone resin particles will be poor.
In the present invention, the adhesiveness between the epoxy resin and the silicone resin particle interface is also taken into consideration, and the alkoxy group may be used in a considerably excessive molar ratio with respect to the hydroxyl group (silanol group).

The organosilane compound (f) or (g) can be crosslinked only with the silicone resin to form particles without crosslinking the epoxy resin. Specific examples (structural formulas and compound names) of the organosilane compound (f) or (g) are listed below.

(C ₂ H ₅ O ₄ Si tetraethoxysilane CH ₂ ═CHCH ₂ Si (OC ₂ H ₅ ) ₃ allyltriethoxysilane CH ₂ ═CHCH ₂ Si (OCH ₃ ) ₃ allyltrimethoxysilane C ₅ H ₁₁ Si (OC ₂ H ₅ ) ₃ Amyltriethoxysilane Benzyl triethoxysilane _{C 4 H 9 Si (OCH 3} ) 3 n- butyl trimethoxysilane _{C 2 H 5 Si (OC 2} H 5) 3 ethyltriethoxysilane _{C 2 H 5 Si (OCH 3} ) 3 ethyltrimethoxysilane CH ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ n-hexyltrimethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ Methyltriethoxysilane CH ₃ Si (OCH ₃ ) ₃ Methyltrimethoxysilane CH ₃ (CH ₂ ) ₁₇ Si (OC ₂ H ₅ ) ₃ n-octadecyltriethoxysilane Phenyltriethoxysilane Phenylalanine trimethoxysilane _{CH 3 (CH 2) 2 Si} (OCH 3) 3 n- propyltrimethoxysilane (CH ₃ O) ₄ Si tetramethoxysilane _{CH 2 = CHSi (OC 2 H} 5) 3 vinyltriethoxysilane CH ₂ = CHSi (OCH ₃ ) ₃ Vinyltrimethoxysilane NC (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ Cyanoethyltriethoxysilane 3- (3-Cyanopropylthio) propyldimethoxymethylsilane C ₈ F ₁₇ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ (Heptadecafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane C ₆ F ₁₃ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ (tridecafluoro-1,1,2,2-tetrahydrooctyl)
Triethoxysilane (3,3,3-Trifluoropropyl) methyldimethoxysilane CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (3,3,3-trifluoropropyl) trimethoxysilane 3-trifluoroacetoxypropyltrimethoxysilane CF ₃ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ (3,3,3-trifluoropropyl) triethoxysilane The epoxy resin composition according to the present invention has the following method. Can be manufactured in.

(1) One kind or two or more kinds of the above-mentioned epoxy resin, silicone resin (a), and organic silane compounds (b) to (g) are mixed at a predetermined ratio, and these are mixed by stirring.

(2) After reacting any of the organosilane compounds (b) to (g) to the extent that gelation does not occur in the silicone resin (a), this is added to the epoxy resin, and the silicone resin is further added while stirring and mixing. Any of the organosilane compounds (b) to (g) necessary for crosslinking the resin (a) is added.

(3) Organosilane compound (b) on epoxy resin,
After reacting either (c) or (e), the silicone resin (a) is added, and if necessary, any of the organosilane compounds (b) to (g) is added and mixed with stirring.

The cross-linking reaction by stirring may be carried out at room temperature, but if necessary, it may be heated to an appropriate temperature, or a reaction catalyst (t-butyltin oxide, lead octylate, tin octylate, a tertiary amino compound, water. Etc.) can be added to accelerate the reaction and the reaction time can be shortened. Also, stirring is
It is preferable to make the whole uniform by high-speed rotation, and the particle size changes depending on the stirring efficiency.

The formed silicone resin particles can be stably dispersed in the epoxy resin matrix by the stirring action,
A liquid or solid composition according to the invention is obtained.

The composition of the present invention is characterized by having specific silicone resin particles uniformly dispersed, whereby the flexibility is improved without lowering the strength of the epoxy resin at the time of heating, and the desired crack resistance and toughness are improved. Granted. The composition of the present invention cures in the presence of a usual epoxy resin curing agent and the like. Applications include, for example, IC encapsulants due to their low dielectric constant, various coating materials, paints, adhesives, prepregs, etc. because of their excellent water repellency, high impact resistance, and high flexibility. To be

Next, the present invention will be described more specifically with reference to examples.

Example 1 0.5 part of t-butyltin oxide was added to 100 parts of a bisphenol A type epoxy resin (Epicote 828, manufactured by Yuka Shell Co., Ltd.), and terminal silanol polydimethylsiloxane [I] (was added thereto while stirring at 80 ° C. _{p = 350~380, R 1 = CH} 3) 50
Parts and 1 part of γ-aminopropyltriethoxysilane are added, and heating and stirring are continued for another 6 hours. The reaction mixture becomes a milky white liquid, and after completion of the reaction, it is left to stand at room temperature and cooled to obtain an epoxy resin composition in which silicone resin particles are uniformly dispersed in the epoxy resin. Viscosity measured by B-type viscometer at 25 ° C 26000 cps. As a result of observation under an optical microscope, the particle size of the silicone resin was 0.5 to 3 µ.

Next, when a modified resin group polyamine was added to this epoxy resin composition and cured, the elastic modulus of the cured product (20 ° C)
Was 8.5 × 10 ⁹ (dyne / cm ² ). On the other hand, the elastic modulus of “Epicote 828” alone is 1.1 × 10 ¹⁰ (dyne / c
m ² ).

Example 2 As in Example 1, 100 parts of bisphenol F type epoxy resin (Epicote 807, manufactured by Shell Chemical Co., Ltd.) and 0.5 part of t-butyltin oxide were stirred at 80 ° C., and the same liquid silicone as in Example 1 was added thereto. 130 parts of resin and 8 parts of γ-aminopropyltriethoxysilane are added, and the mixture is heated and stirred for 6 hours, then left standing and cooled to obtain a milky white liquid epoxy resin composition. Viscosity 180,000 cps, particle size 1-10μ. Elastic modulus of the cured product of modified aliphatic polyamine 3.6 × 10 ⁹ (dyne / cm ² ).

Example 3 As in Example 1, 90 parts of a bisphenol A type epoxy resin (manufactured by Yuka Shell Co., Epicoat 1001), 10 parts of an ester type epoxy resin (manufactured by Shell Chemical Co., Epicoat 871) and t-butyltin oxide. 0.5 part was stirred at 90 ° C., to which 15 parts of the same liquid silicone resin as in Example 1 and N-β-
0.8 part of (aminoethyl) -γ-aminopropyltrimethoxysilane was added, and the mixture was heated and stirred for 3 hours, then left standing and cooled to obtain a semi-solid epoxy resin composition. Particle size 1-3
μ.

Example 4 "Epicoat 80" which is a bisphenol F type epoxy resin
Liquid silicone resin [I] (R ₁ = CH) having 0.5 parts of t-butyltin oxide and an average molecular weight of 1700 (n≈20) per 100 parts of 7 "
₃ ) Add 5 parts, 0.5 parts of N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and 0.5 parts of tetraethoxysilane and stir mix at room temperature for 6 hours to obtain a milky white liquid epoxy resin composition . Viscosity 4000cps, particle size
0.5-2μ.

Example 5 "Epicoat 154" 100 which is a novolak type epoxy resin
0.5 part of t-butyltin oxide was added to 50 parts of the same and stirred at 80 ° C., and 50 parts of the same liquid silicone resin as in Example 1 and γ-aminopropyltriethoxysilane 1 were added thereto.
And the mixture is stirred and mixed at 80 ° C. for 3 hours to obtain a milky white highly viscous liquid epoxy resin composition. Viscosity in B type viscometer at 80 ° C. is 50,000 cps, particle size is 2 to 12 μ.

Example 6 To 100 parts of a bisphenol A type epoxy resin (manufactured by Yuka Shell Co., Epicoat 1001), 10 parts of a silanol-terminated polytetramethyl-p-sylphenylene siloxane having a molecular weight of 150000 was added, and the mixture was stirred at 150 ° C. t-butyltin oxide
0.5 part and γ-aminopropyltriethoxysilane 0.5
Parts and continue heating and stirring for 3 hours. The resulting epoxy resin composition was a pale yellow solid at room temperature. Particle size 2
~ 5μ.

Example 7 0.5 part of t-butyltin oxide was added to 100 parts of a bisphenol A type epoxy resin (Epicote 828, manufactured by Yuka Shell Co., Ltd.), and silanol polydimethyl-terminated terminal silanol was added at 80 ° C. with stirring.
50 parts of diphenylsiloxane [I ′] (p = 28, q = 1), 1 part of γ-aminopropyltriethoxysilane and 7 parts of phenyltrimethoxysilane are added, and the mixture is further heated and stirred for 6 hours. The obtained epoxy resin composition was a milky white liquid. The viscosity of the B type viscometer at 25 ℃ is
42000 cps. As a result of observation under an optical microscope, the particle size of the silicone resin was 0.5 to 2 µ.

Example 8 Bisphenol A type epoxy resin (produced by Yuka Shell Co., Ltd., 10
01) 0.5 part of t-butyltin oxide was added to 100 parts, 4 parts of γ-isocyanatopropyltrimethoxysilane was added with stirring at 100 ° C. under N ₂ atmosphere, and the mixture was heated and stirred for 5 hours, and then the isocyanate group was detected by IR. It was confirmed that there was no absorption. Then, 30 parts of the same liquid silicone resin as in Example 1 is added, and the mixture is heated and stirred in air for another 6 hours. The obtained epoxy resin composition was solid. Particle size 2
5μ.

Example 9 0.5 part of t-butyltin oxide was added to 100 parts of a bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Co., Ltd.), and the mixture was heated and stirred at 80 ° C. to obtain the same liquid silicone resin as in Example 1. Part, 3-mercaptopropyltrimethoxysilane (2 parts) and water (0.5 part) are added, and the mixture is heated and stirred. The obtained epoxy resin composition was a milky white liquid. Viscosity measured by B-type viscometer at 25 ℃ is 20000pcs. Particle size 0.5-2μ.

Example 10 0.5 part of t-butyltin oxide was added to 100 parts of bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Co., Ltd.) and stirred at 80 ° C., and 30 parts of the same liquid silicone resin as in Example 1 was added. And 1 part of 3-glycidoxypropyltrimethoxysilane are added, and heating and stirring are continued for 6 hours. The obtained epoxy resin composition was a milky white liquid. Viscosity at 25 ° C in B-type viscometer is 32000 cps. Particle size 3-8
μ.

Example 11 Terminal silanol polydimethylsiloxane [I] (p =
7) To 10 parts, 2.5 parts of (3,3,3-trifluoropropyl) methyldimethoxysilane and 0.5 part of t-butyltin oxide are added, and a condensation reaction is carried out at 50 ° C. for 24 hours in a nitrogen atmosphere. The reaction was confirmed by disappearance of IR absorption of the methoxy group. Thereafter, 100 parts of a bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Co., Ltd.) and 1.0 part of γ-aminopropyltriethoxysilane are added, and the mixture is heated and stirred in air at 80 ° C. for 6 hours. The obtained epoxy resin composition was a milky white liquid. Viscosity measured by B-type viscometer at 25 ℃ is 24,000 cps. Particle size 0.5-2μ.

Claims (1)

[Claims] 1. A formula (a) for 100 parts by weight of an epoxy resin: [Wherein R ₁ is methyl or phenyl, R ₂ is phenyl, p
Is 9 to 500, and q is 0 or 6% or less of p]. 5 to 200 parts by weight of a mixture of one or two or more types of the terminal silanol organopolysiloxane which is liquid at room temperature and is represented by the following compound group: Formula (b): Wherein, R ₃ is hydrogen, phenyl, benzyl, cyclohexyl, vinyl benzyl or allyl, R ₄ is _{-C 2 H 4 -, - C} 3
H ₆ - or _{-C 2 H 4 SC 2 H 4} -, methyl or ethyl and R ₅ and R ₆ are identical or different and, R ₇ is _{-C 2 H 4 -, - C} 2 H 4 SC
₂ H ₄ −, −C ₂ H ₄ NHC ₂ H ₄ − or R ₈ is —C ₂ H ₄ — or —C ₃ H ₆ —, and m is 0 or 1.] (c) Formula: [Wherein R ₅ , R ₆ and m are as defined above, and R ₉ is -C
₃ H ₆ — or —CH ₂ —], (d) Formula: [Wherein R ₅ , R ₆ and m are as defined above, and R ₁₀ is An epoxysilane compound represented by the formula (e): [Wherein R ₅ , R ₆ and m have the same meanings as described above, and R ₁₁ represents-
A- or -Q-NHCOX-A- (where A is an alkylene group, Q is a diisocyanate residue, and X is -NH-,
-O- or -S-)], an isocyanate silane compound represented by the formula (f): [Wherein R ₅ is as defined above, R ₁₂ is methyl or ethyl, R ₁₃ is —CH ₂ —, —C ₂ H ₄ — or —C ₃ H ₆ —, and Y is CH _{2
= CH-, C 6 H 5,} CnF 2 n +1 (n = 1~10), NC- or NC (CH _{2) 3} S-, and r is 0, 1 or 2, m organosilane compound is represented by a 0 or 1 when r is 2] and (g) formula: [Wherein R ₅ and R ₁₂ are as defined above, and R ₁₄ is C _{n ′} H
_{2n '+ 1 (n' =} 1~20), CH 2 = CH- or C ₆ H _5, and r is 0 or 1 when 0, 1 or 2, m is r is 2
And a mixture of one or more kinds selected from the group of the organic silane compounds represented by the formula [1], the molar ratio of the hydroxyl group and the alkoxy group of them is [OR ₆ and / or OR ₁₂ ] / [OH] is 0.1. Blended in a ratio of 15 to 15 and, if necessary, mixed by stirring under heating, so that the silicone resin particles, which are the cross-linking reaction product of the silanol organopolysiloxane having both terminals and the organic silane compound, are uniformly dispersed in the epoxy resin matrix. An epoxy resin composition characterized by being stably dispersed and present.