JPS60245664A - Inorganic filler for epoxy resin and epoxy resin composition containing said inorganic filler - Google Patents

Abstract

PURPOSE:To provide the titled filler which gives an epoxy resin compsn. having improved electrical and mechanical characteristics, by coating the surface of an inorg. filler with a co-hydrolyzate of specified silicon compds. or a hydrolyzate of a co-condensate of said silicon compds. CONSTITUTION:The titled filler is obtd. by coating the surface of an inorg. filler with a co-hydrolyzate of an organo silicon compd. of formula I (wherein R is a 1-18C alkyl, phenyl, vinyl, methacryloylpropyl; X is a hydrolyzable group; m is 1, 2; n is 2, 3; m+n=4), such as methyl-trimethoxysilane, and an organosilicon compd. of formula II [wherein R' is gamma-glycidoxypropyl, beta-(3,4-epoxycyclohexyl)ethyl; X is a hydrolyzable group], such as gamma-glycidoxypropyltrimethoxysilane, or a hydrolyzate of a co-condensate of said compds. Heretofore, blending of a large quantity of an inorg. filler with an epoxy resin has a disadvantage that both electrical and mechanical characteristics are deteriorated. However, this disadvantage can be eliminated by the above treatment.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to inorganic fillers blended into epoxy resins, and casting, insulating materials, festivals, and molding materials for electrical and electronic parts containing the inorganic fillers. The present invention relates to an inorganic filler for epoxy resins with significantly improved electrical properties and mechanical properties used in laminates, etc., and an epoxy resin composition containing the inorganic filler.

(Prior art) Epoxy resin compositions have excellent curability, adhesiveness, chemical resistance, mechanical and electrical properties, processing adaptability, dimensional accuracy, corrosion resistance, abrasion resistance, and heat resistance in high and low temperature ranges. It has well-balanced properties, but in general, inorganic fillers are often added to improve curing shrinkage, thermal conductivity, and thermal expansion properties.

On the other hand, however, as the amount of inorganic filler blended into the epoxy resin increases, the fluidity of the compound is lost, making casting and molding difficult, voids etc. tend to remain in the molded product, and electrical insulation properties are impaired. Furthermore, when an epoxy resin composition containing inorganic fillers is used as a molding material for semiconductor encapsulation, ionic impurities, which have not been considered a problem in the past, may cause the electrical properties of the device to deteriorate. It has been pointed out that it affects the characteristics.

Furthermore, epoxy resin compositions containing a large amount of inorganic filler have poor mechanical properties, especially bending strength, and when used as a resin-sealed package using the molding material for semiconductor encapsulation, equipment may be damaged. It has the fatal drawback of being easy to do.

Conventionally, methods have been used to improve the above-mentioned drawbacks, such as adjusting the particle size distribution of inorganic fillers, or washing with pure water to remove ionic impurities, but these methods have not been shown to be sufficiently effective. It has also been proposed to treat such inorganic fillers with a silane coupling agent, particularly gamma-glycidoxyglobyltrimethoxysilane or gamma-aminopropyltriethoxysilane, but it is possible to combine the epoxy resin and the inorganic filler. However, since these silane coupling agents are hydrophilic, they have poor water resistance. It's hard to say.

Furthermore, if any of the above organosilicon compounds is used but no hydrolysis product is used, the epoxy resin composition in which it is blended contains methoxy groups and epoxy groups, which reduce water resistance, salt water resistance, and rust prevention properties. It is inevitable that a portion of the base will remain and cause considerable deterioration of physical properties after severe tests such as boiling tests and pressure tests.

(Problems to be Solved by the Invention) In view of the above, the present invention aims to improve the electrical properties and mechanical properties that are caused by the above-mentioned conventional drawbacks when an inorganic filler is blended into an epoxy resin composition. As a result of intensive research by the present inventors, it was found that by coating the surface of the inorganic filler with a hydrolysis product of the co-hydrolysis product or co-condensation of the organosilicon compound of the present invention shown below, The inventors have achieved the above object and completed the present invention.

That is, the present invention is based on the general formula % formula % (1) [wherein R is an alkyl group having 1 to 18 carbon atoms, a phenyl group, a vinyl group, or a methacryloxypropyl group,
X is a hydrolyzable group, m is an integer of 1 to 2, n is an integer of 2 to 3, and m+n is 4. ] An organic compound represented by the general formula 1% (2) [In the formula, R' is a gamma glycidoquinpropyl group, i tald heta (3,4-epoxychlorohexyl) ether group, and X is a hydrated It is a degradable group. ] Epoxy resin iC treated with a cohydrolysis product of an organosilicon compound or a hydrolysis product of a cocondensate
The present invention provides an inorganic filler to be blended and an epoxy resin composition containing the inorganic filler that has improved electrical properties and mechanical properties.

Examples of organosilicon compounds having the above general formula +1) include methyltriethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriptoxysilane, dimethyljethoxysilane, octyltriethoxysilane 1, lutriethoxysilane,
Examples include phenyl) IJ ethoxysilane, enyldiethoxysilane, vinyltriethoxysilane, and methacryloxytrimethoxysilane, which may be used alone or in combination.

Organosilicon compounds having the general formula (2), gamma-glycidoxyprobyltrimethoxysilane, gammalycidoxyprobyltriethoxysilane, beta (3
, 4-epoxycyclohexyl) ethertrimethoxysilane, beta(3,4-epoxycyclohexyl) ethertriethoxysilane, etc., and they may be used alone or in combination. ' Note that the cohydrolysis product of the organosilicon compound of general formula (1) and the organosilicon compound of general formula (2) is expressed by the general formula (1).
) can be obtained all at once by hydrolyzing a mixture of the organosilicon compound of general formula (2) and the organosilicon compound of general formula (2). It can be obtained by mixing in the required proportions.

Furthermore, if sufficient water exists on the surface of the inorganic filler to hydrolyze the organosilicon compound of the present invention, a hydrolysis product can also be prepared on the surface.

The same applies to the hydrolysis product of the co-condensate of the organosiliconized product. In any case, there is no problem in adding a hydrolysis catalyst such as an acid such as hydrochloric acid, formic acid, acetic acid, oxalic acid, or phosphoric acid, or an amine, in order to produce a sufficient hydrolysis product.

Since the co-hydrolysis products of such organosilicon compounds or the hydrolysis products of co-condensates progress gradually even in the absence of a catalyst, in the present invention, it is necessary to treat the inorganic filler. It is preferable to leave it in a state without hydrolysis until 0.0 This allows stability to be maintained over a long period of time.

(Function) It is not clear why the epoxy resin composition containing the inorganic filler treated with the organosilicon compound used in the present invention can improve the electrical properties and mechanical properties, but the inorganic This is thought to be because strong adhesion and hydrophobicity were achieved in a well-balanced manner at the interface between the filler and the resin.

This is a mixture of an inorganic filler treated with a hydrolysis product of an organosilicon compound of the general formula +1+ and an inorganic filler treated with a hydrolysis product of an organosilicon compound of the general formula (2). This is well understood from the fact that the epoxy resin composition does not improve the electrical properties or mechanical properties in any way.

Therefore, the ratio of the organosilicon compound of general formula (1) and the organosilicon compound of general formula (2) used in the present invention can be freely selected from 1:9 to 9:l by weight, but the epoxy compound of the present invention From the viewpoint of performance of the resin composition, a ratio of 3 to 7:3 is preferable.

In addition, the inorganic fillers used in the present invention include silica,
Added to epoxy resins such as quartz, alumina, alumina trihydrate, clay, cruzi, asbestos, mica, white carbon, titanium oxide, magnesium oxide, iron oxide, magnesium hydroxide, antimony trioxide, glass fiber or metal powder. It contains most of the inorganic fillers, and there is no problem in using one kind or a mixture of two or more kinds of these inorganic fillers.

As a method for treating such an inorganic filler, inorganic filler 10
0 parts by weight of the organosilicon compound used in the present invention
．． 01 parts by weight to weighted parts, 0°1 parts to 10 parts by weight for good deeds
After adding parts by weight and thoroughly mixing with a high-speed mixer such as a Henschel mixer, the organosilicon compound is heated to 50°C to 150°C to remove the used solvent, water, and by-product alcohols. A common method is to react with an inorganic filler.

When such an inorganic filler is coated with the co-hydrolysis product of the organosilicon compound used in the present invention or the hydrolysis product of the co-condensate, the film thickness is a uniform monomolecular film, but the electrical properties and mechanical properties are It is preferable because of the improvement effect and economically.

- Examples of epoxy resins that are a basic component in the strength wood invention include the reaction product of bisphenol A and epichlorohydrin known as Epicor) 828 (trade name manufactured by Shell), and Araldye) EPN1138 (
Examples include polyfunctional epoxy resins which are epoxy derivatives of novolac known as Ciba Geigy (trade name), etc., and these may be used alone or as a mixture of two or more.

Furthermore, aromatic amines, aliphatic amines, acid anhydrides, phenol/gelac, etc. are used as curing agents in epoxy resin molding materials, but any curing agent can be used in the present invention.

It should be noted that the epoxy resin composition of the present invention may contain various curing accelerators, pigments, flame retardants, etc. as necessary, but the effects of the present invention may be inhibited by blending these. Never.

The present invention will be explained below with reference to examples, but the present invention is not limited to the examples in any way. A mixed solution of 10 parts by weight of ethoxysilane and 10 parts by weight of gamma-glycidoxypropyltrimethoxysilane is gradually added while stirring. 4 parts by weight of the co-hydrolyzed product solution thus prepared were sufficiently mixed with 100 parts by weight of Crystallite VX-S (trade name manufactured by Amamori Co., Ltd.), which is powdered silica, in a high-speed mixer,
It was then dried for 1 hour.

100 parts by weight of the powdered silica thus obtained, epoxy resin Epicor) 828 (trade name manufactured by Shell Co., Ltd.) 1
oO parts by weight are added and then Epicure 12 is added as a hardening agent.
6 (trade name manufactured by Cie. 7) Parts by weight of sO, DMP-30 as a curing accelerator (according to the results in Table 1, manufactured by Tokyo Kasei Co., Ltd., the obtained composition (A) is composition ω), composition Things (C),
It can be seen that the song exhibits higher strength and performance compared to composition (2).

Example 2 5.6 parts by weight of water and a small amount of oxalic acid were added to 100 parts by weight of ethanol, and a mixed solution of 10 parts by weight of dimethyljethoxysilane and gamma glycidoxyglobiltrimethoxysilane was gradually added while stirring. do.

8 parts by weight of the thus prepared co-hydrolysis product solution was taken and alumina A-34 (trade name manufactured by Nippon Light Metal Co., Ltd.) was added.
(200 parts by weight of xy resin Ebico) in a high-speed mixer.
Add 100 parts by weight of 828 (trade name, manufactured by Shell), then 80 parts by weight of Ebicure 126 (trade name, manufactured by Shell) as a curing agent, and 1 part by weight of DMP-30 (trade name, manufactured by Tokyo Kasei Co., Ltd.) as a curing accelerator. In addition, the mixture was degassed and mixed for 1 hour under reduced pressure.

Thereafter, a test piece with a thickness of 3 mm, a width of 1100 tons, and a length of 100 mm was cast and cured at 80° C. for 2 hours and at 140° C. for 30 minutes.

This was designated as composition (2). For comparison, a composition was prepared using untreated alumina according to the above manufacturing method.

Table 2 shows the results of comparing these.

Table 2 According to the results of Table 2, the obtained composition (g) is a composition (goods).
It can be seen that the bending strength and electrical properties are better compared to that of the previous one, and that it exhibits excellent performance.

Patent applicant: Daihachi Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1 General formula RmSiXn (1) [wherein R is an alkyl group having 1 to 18 carbon atoms, a phenyl group, a vinyl group or a methacryloxypquivir group, X is a hydrolyzable group, m is an integer of 1 to 2, n is an integer of 2 to 3, m +
n = 4. ] An organosilicon compound represented by the following, and the general formula R'SiX, ・・・・・・・・・・・・(2)
[In the formula, R' hagamma glycidoxyglobyl group, t;
+'cij beta (3,4-epoxycyclohexyl)
It is an ether group, and X is a hydrolyzable group. ] An inorganic filler blended into an epoxy resin treated with a co-hydrolysis product or a co-condensate hydrolysis product of an organosiliconized compound represented by: 2 General formula RmSiXn・・・・・・・・・・・・(1
) [In the formula, R is an alkyl group having 1 to 1 B carbon atoms, a phenyl group, a vinyl group, or a methacryloxyglobin group, and X is a hydrolyzable group. m is an integer of 1 to 2, n is an integer of 2 to 3, and m 1 n = 4. ] An organosilicon compound represented by the following, and the general formula R' S i XJ・・・・・・・・・・・・
(2) [In the formula, k is a gamma glycidoxyglobin group,
or beta(3,4-epoxycyclohexyl)ethyl group, X is a hydrolyzable group. ] An epoxy resin composition comprising an inorganic filler treated with a co-hydrolysis product of an organosilicon compound or a hydrolysis product of a co-condensate represented by: