JPH02369B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a one-component epoxy resin composition that has improved heat resistance, moisture resistance, insulation properties, and adhesive properties, and has fast curing properties and excellent storage stability. A one-component epoxy resin composition is made by blending an epoxy resin with a curing agent, a curing accelerator, various fillers, and the like. Conventionally, when this type of composition is used for electronic parts, electronic equipment, electrical equipment, automobile articles, tools, aircraft equipment, marine equipment, etc., it has poor heat resistance, moisture resistance, insulation, adhesive properties, etc. The problem was that it wasn't enough. The inventor has discovered that in compositions of this type, 3,4-
Dimethyl-6-(2-methyl-1-propenyl)-
A curing agent that is a reaction product of 1,2,3,6-tetrahydrophthalic anhydride and maleic anhydride, at least one curing agent selected from the group consisting of tertiary amines, triazoles, and imidazoles. The present invention has been completed based on the discovery that by blending an accelerator and an inorganic filler, the above-mentioned disadvantages can be improved and a one-component epoxy resin composition having fast curing properties and excellent storage stability can be obtained. That is, the present invention provides: (1) an epoxy resin having two or more epoxy groups in one molecule; (2) 3,4-dimethyl-6-(2-methyl-1-
a curing agent which is a reaction product of (propenyl)-1,2,3,6-tetrahydrophthalic anhydride and maleic anhydride; (3) a curing agent selected from the group consisting of tertiary amines, triazoles and imidazoles; at least 1
The present invention relates to a one-component epoxy resin composition containing a curing accelerator as a seed and (4) an inorganic filler as essential components. The epoxy resin in the present invention is not particularly limited and any known resin can be used, such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, glycidyl ether type epoxy resin. , glycidyl ester type epoxy resins, glycidylamine type epoxy resins, epoxy resins derived by epoxidation of olefin bonds, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, halogenated epoxy resins, etc. Examples include those having two or more epoxy groups in one molecule, and at least one of these is used. In the present invention, 3,4-dimethyl-6-(2-methyl-1-propenyl)-1,
Use a reaction product obtained by reacting 2,3,6-tetrahydrophthalic anhydride and maleic anhydride under heating, usually in equimolar amounts, such as "YH-308" manufactured by Yuka Ciel Epoxy Co., Ltd. is required. The reaction product is a novel curing agent, and the appropriate amount to be used is 20 to 160 parts by weight per 100 parts by weight of the epoxy resin. If it is less than 20 parts by weight, curing will be insufficient and uncured products will be produced. Also,
If it exceeds 160 parts by weight, heat resistance will decrease. Further, in the present invention, a phenol resin may be used in combination as a curing agent. The resin is not particularly limited and a wide variety of known resins can be used, such as phenol novolak resin, tert-
Examples include butylphenol novolac resin, nonylphenol novolac resin, polyparavinylphenol resin, and at least one of these resins is used. The appropriate amount of the phenol resin used is 3 to 50 parts by weight per 100 parts by weight of the epoxy resin. Furthermore, in the present invention, an acid anhydride curing agent may be used in combination as a curing agent. As the acid anhydride curing agent, a wide variety of known ones can be used, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, succinic anhydride, trimellitic anhydride, and anhydride. Pyromellitic acid, 3,3',4,4'-benzophenonetetracarboxylic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, 5
-(2,5-dioxotetrahydrofuryl)-3-
Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic acid dimer, 3,4-dimethyl-6-(2-methyl-1-propenyl)-
3,4,5,6-tetrahydrophthalic anhydride,
Examples include 3,4-dimethyl-6-(2-methyl-1-propenyl)-1,2,3,6-tetrahydrophthalic anhydride, and at least one of these is used. The appropriate amount of the acid anhydride curing agent to be used is 10 to 60 parts by weight per 100 parts by weight of the epoxy resin. As the curing accelerator used in the present invention, a wide variety of known ones selected from tertiary amines, triazoles, and imidazoles can be used, such as benzyldimethylamine, triethanolamine, dimethylaminomethylphenol, tris(dimethylamino methyl)phenol, triethyltetramine, 3,9-bis(3-aminopropyl)-2,4,8-10-tetraoxaspiro(5,
5) Tertiary amines such as undecane, 1, 2, 3
- Triazoles such as benzotriazole and 5-methyltriazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-
Methylimidazole, 2-ethylimidazole,
2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole,
1-vinyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methylimidazole, 2
Examples include imidazoles such as -isopropylimidazole and 1-cyanomethyl-2-methylimidazole, and at least one of these is used. The amount of curing accelerator used is 0.05 to 8 parts by weight per 100 parts by weight of the epoxy resin. If it is less than 0.05 part by weight, the curing accelerating effect will not be sufficient and uncured products will result. Moreover, if it exceeds 8 parts by weight, storage stability will deteriorate. In addition, in the present invention, a wide variety of known inorganic fillers can be used for improving moisture resistance, reducing expansion coefficient, improving thermal conductivity, etc., such as quartz glass, crystalline silica, glass Examples include fiber, talc, alumina, hydrated alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, zirconium silicate, clay, mica, and at least one of these is used. These inorganic fillers are preferably used in powder form. The amount of inorganic filler used is 20 to 450 parts by weight per 100 parts by weight of the epoxy resin. If it is less than 20 parts by weight, no reduction in the expansion coefficient can be expected. Moreover, if it exceeds 450 parts by weight, the melt viscosity becomes extremely high, making it difficult to use. Further, when the one-component epoxy resin composition of the present invention is used for electronic parts, electronic equipment, etc., a flame retardant is further added and used in combination. As the flame retardant, a wide variety of known flame retardants can be used, such as hexabromobenzene,
Examples include antimony trioxide, tetrabromobisphenol A, hexabromobiphenyl, decachlorobiphenyl, red phosphorus, and at least one of these is used. The amount of flame retardant used is 3 to 150 parts by weight per 100 parts by weight of the epoxy resin.
If the amount is less than 3 parts by weight, no flame retardant effect can be expected. Furthermore, in addition to the above-mentioned components, the one-component epoxy resin composition of the present invention may contain additives commonly used in this type of composition, such as colorants such as carbon black and red iron, synthetic wax, and natural wax. A mold release agent such as, methylphenylpolysiloxane, a silicone compound such as methylpolysiloxane, etc. may be added and used in combination. The one-component epoxy resin composition of the present invention has significantly improved heat resistance, moisture resistance, insulation properties, and adhesive properties compared to conventional ones, and is particularly suitable for use in electronic parts, electronic equipment, etc. In addition, electrical equipment, aircraft,
It is also suitable for use in automobiles, building materials, road paving, mechanical tools, housing adhesives, ships, medical equipment, toys, office equipment, stationery, etc. The one-component epoxy resin composition of the present invention also uses 3,4-
Dimethyl-6-(2-methyl-1-propenyl)-
The use of the reaction product of 1,2,3,6-tetrahydrophthalic anhydride and maleic anhydride has the advantage that the gelation rate is fast and curing can be done in a short time. The curing conditions for the one-component epoxy resin composition of the present invention vary depending on the blending amounts of various components.
It is appropriate to carry out post-curing for 16 minutes to 16 hours. Furthermore, the one-component epoxy resin composition of the present invention has excellent storage stability (pot life), and does not deteriorate even when stored for 90 days or more under sealed conditions at 23° C., for example. When the one-component epoxy resin composition of the present invention is used as a molded article, known methods applicable to this type of composition may be used, such as transfer molding, injection molding, hot press molding,
Heat roll molding, pressurized heat molding, heat molding, infrared curing molding, etc. can all be applied depending on the purpose. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Examples 1 to 3 and Comparative Example 1 One-component epoxy resin compositions of the present invention and comparative compositions shown in Table 1 below were prepared by varying the types and blending amounts of various components. Next, all of the components were mixed and stirred at 60° C. using a planetary mixer, taken out, and formed into a sheet using a press. This sheet-like composition was cut into predetermined shapes for various tests and cured for 2 minutes at a pressure of 10 kg/cm ² and a temperature of 170°C.
After further curing for 1 hour, various properties of the cured product were measured.

【table】

[Table] Next, the pot life and gelling time of each composition, as well as the heat distortion temperature (heat resistance), moisture resistance, adhesiveness, insulation, and flame retardance of each cured product obtained above were investigated. Each test method is as follows. Pot life: The time (in days) when the gelation time at 150°C becomes 1/2 of the initial value when stored in a sealed container at a temperature of 23°C and a humidity of 60% RH or less. ) was taken as the pot life. Gelation time: Place 1 g of sample on a hot plate at 150°C and stir with a metal rod. The time until stirring became impossible due to gelation was measured. Heat deformation temperature: carried out according to the method of JIS K-6911. Moisture resistance: A test piece (a disc with a diameter of 50 mm and a thickness of 3 mm) was placed in a constant temperature and humidity chamber at a temperature of 85°C and a humidity of 95% RH, and the water absorption rate was determined after 500 hours.
The judgment criteria are as follows. ○: less than 0.5%, △: 0.5 to 1.0% ×: more than 1.0% Adhesiveness...Method according to JIS K-6850.
The judgment criteria are as follows. ○: 160 Kg/cm ² or more Δ131 to 159 Kg/cm ² ×: 130 Kg/cm ² or less Insulating property (resistivity): Performed according to the method of JIS K-6911. Flame retardancy: Tested according to JIS K-6911 method. The results of each test are shown in Table 2 below.

[Table] Table 2 shows that the composition of the present invention has a longer pot life and shorter gelation time than the comparative example, and that the cured product of the present invention has better heat resistance, moisture resistance, and
It is clear that the adhesive and insulation properties are excellent.

Claims (1)

[Scope of Claims] 1 (1) Epoxy resin having two or more epoxy groups in one molecule, (2) 3,4-dimethyl-6-(2-methyl-1-
a curing agent which is a reaction product of (propenyl)-1,2,3,6-tetrahydrophthalic anhydride and maleic anhydride; (3) a curing agent selected from the group consisting of tertiary amines, triazoles and imidazoles; at least 1
A one-component epoxy resin composition comprising a curing accelerator as a seed and (4) an inorganic filler as essential components.