JPH09169871A - Surface-treated filler and resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a filler which gives a resin compsn. excellent in strengths and durability and which improves esp. the mechanical characteristics of a resin compsn. by treating a filter with a specific imidazolesilane. SOLUTION: A filler (except glass fibers) is treated with an imidazolesilane represented by formula I, II, or III (wherein R<1> is H, vinyl, or a 1-5C alkyl; R<2> is H or a 1-20C alkyl; R<3> and R<4> are each a 1-3C alkylene; and (n) is 1-3) or a mixture of these imidazolesilanes. Usually the amt. of the imidazolesilane attached to the filler is 0.001-10wt.% of the filler. The treatment is performed e.g. by an aq. soln. method wherein the imidazolesilane is hydrolyzed in water having a certain pH and then reacted with the filler, by an org. solvent method wherein the imidazolesilane is dissolved in an org. solvent contg. a small amt. of water and then reacted, or by a spray method wherein an aq. or org.-solvent soln. of the imidazolesilane is sprayed to a filler under vigorous stirring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition used for electric / electronic parts, adhesives, paints, composite materials and the like, and particularly a filler for improving mechanical properties and a resin composition using the same. It is about things.

[0002]

2. Description of the Related Art Conventionally, fillers have been reduced in cost and weight,
Non-reactive substances have been added for the purpose of improving mechanical strength. However, since such an inert filler has no durability, an active filler is used for the purpose of improving durability. As a method for chemically activating the surface, a method using a silane-based or titanium-based compound having a functional group such as an amino group, an epoxy group, and a mercapto group is generally used.

[0003]

However, the filler treated with the conventionally known coupling agent improves the strength and durability of the resin, but its effect is not sufficient.

An object of the present invention is to provide a functional filler for a resin composition having excellent resin strength and durability.

[0005]

The present invention provides a filler obtained by modifying the surface with an imidazolesilane having a structure represented by the following general formula (1), (2) or (3) or a mixture thereof. It was found that a resin composition excellent in strength and durability can be obtained by using it, and the present invention has been completed.

That is, the present invention provides the following general formula (1):
The present invention provides a filler obtained by treating the imidazole silane represented by (2) or (3) or a mixture thereof, and a resin composition using the filler.

[0007]

Embedded image

The amount of the filler used in the present invention is not particularly limited, but is usually 10 to 5 relative to 100 parts by weight of the resin.
The amount is 00 parts by weight, preferably 50 to 300 parts by weight. 1
If the amount is less than 0 parts by weight, the desired strength will not be exhibited, and 5
If it exceeds 100 parts by weight, the resin strength will decrease.

The resin used in the present invention is not particularly limited,
Any organic material such as thermosetting resin or thermoplastic resin can be used.

As the thermosetting resin, phenol resin,
Examples thereof include amine resin, furan resin, epoxy resin, silicon resin, acrylic resin and polyimide resin.

Examples of the phenol resin include novolac type, resol type and poly-p-vinylphenol resins.

Examples of the amine resin include urea resin, melamine resin and guanamine resin.

Furan resins include furfuryl alcohol resins, furfuryl alcohol / furfural co-condensation resins, furfural / phenol co-condensation resins, furfural / ketone co-condensation resins and the like.

As the epoxy resin, bisphenol A
Examples thereof include diglycidyl ether, bisphenol F diglycidyl ether, polyalkylene oxide diglycidyl ether, and those whose side chain or main chain is modified with a flexible resin such as rubber, urethane, polyether, polyester, etc., alone or 2 A mixture of more than one type can be used.

Examples of the thermoplastic resin include nylon, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyurethane ABS and acrylic resin.

These resins can be used alone or in admixture of two or more.

Further, a curing agent, a polymerization initiator and an accelerator are required depending on the type of resin. In addition, if necessary flame retardant,
A low stress agent and an antioxidant can be added.

Examples of the curing agent include amine type, acid anhydride type and phenol resin type curing agents.

Examples of the polymerization initiator include diazo type and peroxide type thermal polymerization initiators, and acetophenone type and benzoin type photopolymerization initiators.

As the accelerator, a tertiary amine, an organic metal salt,
Examples include aromatic phosphines and phenols.

As the flame retardant, an organic flame retardant such as phosphorus,
Examples thereof include halogen-based and boron-based inorganic flame retardants.

Examples of the antioxidant include phenol type, phosphorus type and sulfur type.

The shape of the filler used in the present invention may be spherical, needle-like or plate-like. There is no limit to the type of filler, and silica, diatomaceous earth, alumina, zinc oxide,
Oxides such as iron oxide, magnesium oxide, tin oxide and titanium oxide, hydroxides such as magnesium hydroxide, aluminum hydroxide and basic magnesium carbonate, carbonates such as calcium carbonate, zinc carbonate, hydrotalcite and magnesium carbonate. , Barium sulfate, sulfate such as gypsum, calcium silicate, talc, glass beads, sericite activated clay, silicate such as bentonite, aluminum nitride, nitride such as silicon nitride,
Carbons such as graphite, charcoal powder, carbon black, and various metals can be mentioned.

In the present invention, glass fiber is not included in the filler.

As the treating agent used in the present invention, imidazole silane represented by the following general formula (1), (2) or (3) or a mixture thereof is used.

[0026]

Embedded image

(However, R ¹ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, and R ² is hydrogen or 1 carbon atom.
To 20 alkyl groups, R ³ and R ⁴ are alkyl groups having 1 to 3 carbon atoms, and n is 1 to 3) R ^{1 to} R ⁴ in the above formulas (1) to (3) are as specified. However, R ¹ is preferably hydrogen, methyl, ethyl, undecyl or heptadecyl, R ² is preferably hydrogen, methyl or vinyl, and R ³ or R ⁴ is preferably methyl or ethyl in view of ease of synthesis. .

Regarding the synthesis method of these, Japanese Patent Laid-Open No. 5-18
No. 6479. Even when it is obtained as a mixture of the imidazole silanes represented by the above formulas (1) to (3) by this synthetic method, it is advantageous to use it in the form of a mixture without any need for separation.

The treatment amount (coating amount) of the imidazole silane of the present invention is not particularly limited, but is usually 0.001 to 10 parts by weight, preferably 0.00, based on 100 parts by weight of the filler.
2 to 5 parts by weight. If it is less than 0.001 part by weight, the expected effect is not exhibited, and if it exceeds 10 parts by weight, the cured resin becomes brittle and the water absorbency increases, and the durability decreases. It is important that the surface of the filler of the present invention is treated with the above-mentioned imidazole silane, but other fillers treated with a surface treating agent can be used together. Examples of other surface treatment agents include silane coupling agents, titanate coupling agents, aluminate coupling agents, and the like.

As the method for treating the imidazole silane with the filler, an aqueous solution method of injecting and dissolving in a water-solvent having a constant pH, hydrolyzing and then reacting with the filler, and dissolving and reacting in an organic solvent containing a small amount of water are reacted. An organic solvent method and a spray method in which an aqueous solution or an organic solution of imidazole silane is sprayed on a vigorously stirred filler are included.

The general method for preparing the resin composition of the present invention as a molding material is to add the above-mentioned resin, a filler treated with imidazolesilane, and optionally other components such as a curing agent, and mix thoroughly with a mixer or the like. After mixing evenly,
Further, it can be melt-mixed under heating with a kneader or the like, and cooled to obtain a molding material.

As a general method of molding, casting,
Transfer molding, injection molding, compression molding and the like are known. Curing by heating is preferably performed by heating to 150 ° C. or higher.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples, but the present invention is not limited to the Examples. The "parts" and "%" in the examples mean "parts by weight" and "% by weight".

Production Example 1 2 parts of imidazolesilane (Note 1) was added to 100 parts of a 1: 1 mixture of water and ethanol, and hydrochloric acid was added to make it acidic (pH about 5) in order to enhance the reactivity with the filler.
After making the alkoxysilyl group of the coupling agent a hydroxysilyl group, 100 parts of a filler (Note 2) was added. 1
The mixture was stirred for 24 hours, filtered with a solvent, washed with ethanol several times, and dried under reduced pressure at 100 ° C. for 1 hour to obtain an imidazolesilane-treated filler (IS-1).

(Note 1) R ¹ = R ^{2 in the} general formulas (1) to (3)
= H; R ³ = CH ₃ ; n = 3 imidazole silane (mixed composition ratio of each formula (1) :( 2) :( 3) = 45: 2
2:33 mixture) (Note 2) Silica (product name: ST-7; average particle size: 30 μ)
m; manufactured by Tatsumori Co., Ltd. Production Example 2 100 parts of the filler (ST-7) used in Production Example 1, 0.2 part of the same imidazole silane and 100 parts of ethanol were mixed, and after stirring at 60 ° C. for 1 hour. The volatile components were distilled off. Subsequently, it was dried at 100 ° C. under reduced pressure for 1 hour to obtain an imidazolesilane-treated filler (IS-2).

Production Example 3 An epoxysilane-treated filler (ES-1) was obtained in the same manner as in Production Example 1 except that epoxysilane (Note 3) was used in place of imidazolesilane.

(Note 3) γ-glycidoxypropyltrimethoxysilane (KBM403; manufactured by Shin-Etsu Chemical Co., Ltd.) Production Example 4 In Production Example 2, epoxy silane (Note 3) was used instead of imidazole silane. Was treated in the same manner as in Production Example 2 to obtain an epoxysilane-treated filler (ES-2).

Examples 1 to 4 and Comparative Examples 1 to 7 100 parts of the epoxy resin (Note 4) was used by mixing the components shown in Table 1 in the ratios shown in Table 1 so as to be uniform.
This mixture is 10 cm long * 3 cm wide * 0.4 cm thick
It was poured into a mold of (1) and the primary curing was performed at 100 ° C. for 1 hour and the secondary curing was performed at 150 ° C. for 1 hour to prepare a molded body.

(Note 4) Bisphenol A type epoxy resin (Product name: Epicoat 828; Yuka Shell) Epoxy Co., Ltd., epoxy equivalent: 190)

[0040]

[Table 1]

1) Dicyandiamide (Product name: AH-15
4; Ajinomoto Co., Inc. 2) Phenolic resin (Product name: EK-170; OH group equivalent: 361 g / eq; Yuka Shell Epoxy Co., Ltd.) 3) Diaminodiphenylmethane (Kanto Chemical Co., Inc.) 4) Isophorone diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 5) 2 ethyl 4 methyl imidazole (Product name: 2E4M
Z; Shikoku Kasei Co., Ltd. 6) Methyltetrahydrophthalic anhydride (Product name: HN-2)
200; manufactured by Hitachi Chemical Co., Ltd.) 7) After processing into a size having a length of 80 mm, a thickness of 4 mm and a width of 10 mm, the bending strength was measured according to JIS K 6911.

8) The obtained test piece was immersed in water heated to 90 ° C. for 17 hours, and then measured according to JIS K6911.

[0043]

As described above, when the filler treated with the imidazole silane of the present invention is used, the imidazole group present on the filler surface acts as a curing catalyst and a reaction starting point, and thus, compared with the epoxy group, Due to the fact that a chemical bond is easily formed with the organic matrix and the physical adsorption including the inducing effect by the relatively high polar group, not only the initial characteristics are improved, but also the durability is improved and the imidazolesilane is improved. Worked effectively and showed high bending strength.

Therefore, it is useful as an adhesive, a sealing material, a coating material, a laminated material, a molding material and the like which require close adhesion.

Claims (2)

[Claims] 1. A filler treated with an imidazole silane represented by the following general formula (1), (2) or (3) or a mixture thereof (excluding glass fiber). Embedded image (However, R ¹ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ³ and R ⁴ are alkyl groups having 1 to 3 carbon atoms. Group, n is 1 to 3) 2. A resin composition containing the filler treated in claim 1.