JPH08157638A - Resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin composition containing a resin, a filler, colloidal silica and a fibrous filler, having low viscosity, high thixotropic property and excellent workability and useful e.g. as an adhesive suitable e.g. for bonding the glass bulb such as an electric light bulb to the base. CONSTITUTION: This resin composition contains (A) a resin (e.g. epoxy resin, urethane resin, acrylic resin or unsaturated polyester resin), (B) a filler (e.g. silicon oxide, aluminum oxide or calcium carbonate containing >=50wt.% of a fraction having particle diameter of 40-500μm), (C) colloidal silica and (D) a fibrous filler (e.g. asbestos, sepiolite or whisker having fiber diameter of 0.1-0.3μm and fiber length of 5-50μm).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which contains a filler in a high concentration and has a low viscosity, thixotropic properties and excellent workability.

[0002]

2. Description of the Related Art Epoxy resin, urethane resin,
Acrylic resins and unsaturated polyester resins are used as adhesives, sealants, molding resins and the like. It is expected that the filler will be added at a high concentration with the goal of improving the performance of the resin and reducing the price, but if the filler with a small particle size is filled at a high concentration, the viscosity of the resin will become extremely high, and the target content will be Is known not to reach. On the other hand, in order to add the filler at a high concentration, a filler having a coarse particle size may be used, but in this case, the filler having a low viscosity and thixotropic property (sol-gel transition property) is used. There was a problem such as sedimentation and the need to stir before work. It is known to add colloidal silica in JP-B-46-38914 in order to suppress sedimentation, but addition of a small amount has no effect of suppressing sedimentation, and conversely when the amount is large, the viscosity becomes high and the filler There were various problems such as a decrease in the addition amount of.

[0003]

Therefore, an object of the present invention is to provide a resin composition in which a filler is added at a high concentration in a resin and the workability is improved without the filler settling. .

[0004]

That is, the object of the present invention is achieved by a resin composition containing a resin (A), a filler (B), a colloidal silica (C) and a fibrous filler (D). .

The constitution of the present invention will be specifically described below. The resin (A) in the present invention is preferably a resin selected from one kind or two or more kinds of epoxy resin, urethane resin, acrylic resin and unsaturated polyester resin. Here, the epoxy resin has an average of two or more epoxy groups per molecule, and includes, for example, bisphenol A, halogenated bisphenol A, aliphatic glycol,
Polyglycidyl ethers obtained by reacting polyhydric phenols such as catechol, resorcinol, etc. or polyhydric alcohols such as glycerin with epichlorohydrin, or polyglycidyl esters, epoxy obtained by condensing novolac type phenolic resin with epichlorohydrin Examples include novolac, epoxidized polybutadiene epoxidized by the peroxide method, dicyclopentadiene oxide, and epoxidized vegetable oil. Examples of the curing agent include a one-component latent curing agent and a two-component amine curing agent.

The urethane resin is a synthetic polymer having a urethane bond --NHCOO-- in its main chain, and various polyisocyanate compounds and polyethers, or polyesters and auxiliaries and catalysts such as amines, metal salts and silicone oils. Is used. Polyether refers to polyhydric alcohols such as polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Examples of the polyisocyanate compound include tolylene diisocyanate, 4.4'-diphenylmethane diisocyanate, 1.5-naphthalene diisocyanate, tolidine diisocyanate, xylene diisocyanate, hexamethylene diisocyanate and modified products thereof, dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like.

Acrylic resins are monomers derived from acrylic acid or methacrylic acid and their ester compounds, or polymers derived from these monomers and other copolymerizable monomers.

The acrylic copolymer is mainly composed of the components obtained from the above-mentioned monomers, but may further contain 30 mol% or less of a monomer copolymerizable therewith.
Examples of copolymerizable monomers are styrene, α-methylstyrene, vinyltoluene, vinyl chloride, (meth) acrylamide, vinyl acetate, acrylonitrile, maleic anhydride, monomers or diesters of maleic acid or fumaric acid, allyl alcohol, Itaconic acid etc. These copolymers can be prepared by various widely known polymerization methods so far, but most commonly, they are obtained by polymerization in a solution with a radical initiator such as an organic oxide and an azo compound, and have a suitable polymerization method. Often provided as a solution in a solvent.

Further, the acrylic resin includes acrylic oligomers having one or more (meth) acrylic groups at the terminals such as oligoester acrylate, oligourethane acrylate and oligoepoxy acrylate. Although such an acrylic oligomer can be used alone, two or more kinds of oligomers can be used in combination.

The unsaturated polyester resin is polycondensed with unsaturated dibasic acids such as maleic anhydride and fumaric acid and saturated dibasic acids such as phthalic anhydride and glycols such as ethylene glycol and propylene glycol. To produce an unsaturated alkyd. It is a liquid resin dissolved in a polymerizable vinyl monomer such as styrene, combined with a peroxide such as benzoyl peroxide and an accelerator such as dimethylaniline and cobalt naphthenate, and then cured by heating and at room temperature. is there. In addition, adipic acid, sebacic acid, etc. as flexibility modifiers, tetrachlorophthalic anhydride, hexachloroendomethylenetetrahydrophthalic acid anhydride, etc., which are self-extinguishing, should also be added to these formulations depending on the purpose. You can

The filler (B) in the present invention includes inorganic fillers such as silicon oxide, aluminum oxide, calcium carbonate, talc, mica and magnesium oxide.
It is preferable that 50% or more of the particles have a particle size in the range of 40 to 500 μm. The colloidal silica (C) in the present invention is a fine powder of SiO ₂ and has a function of giving basic thixotropic properties.

The fibrous filler (D) in the present invention has a fiber diameter of 0.1 to 0.3 µ and a fiber length of 5 to 50 µ, and examples thereof include asbestos, sepiolite and whiskers.

In the present invention, when only the colloidal silica (C) is contained in the resin (A), the effect of giving thixotropic property is great, but hydrogen bond occurs between SiO ₂ and the alcoholic OH, so that it can be changed over time. It is difficult to obtain a desired viscosity because the viscosity increases rapidly. Further, it is known that the fibrous filler (D) suppresses the sedimentation of the filler due to the entanglement of the fibers in the resin and gives the thixotropic property, but the thixotropic property occurs only with the fibrous filler. However, sedimentation of the filler cannot be suppressed. Therefore, by combining this colloidal silica and a fibrous filler, both properties of thixotropic properties and suppression of the sedimentation of the filler can be exhibited, and the resin properties have satisfactory workability. It becomes.

If necessary, a coupling agent such as a silane coupling agent, a titanate compound, and various additives such as a leveling agent, a flame retardant, and a fluidity adjusting agent are added to the resin composition of the present invention. be able to. [Measurement Method] The particle diameter of the filler (B), the fiber diameter and the fiber length of the fibrous filler (D) in the present invention are measured by the following methods. Particle size of filler (B): 10 g of a sample is put into a JIS standard screen, and the screen is divided into screens. . Fiber diameter and fiber length of fibrous filler (D): Using an optical microscope, the fibrous filler is dispersed on a slide glass for close-up photography. The fiber length and fiber diameter are measured in advance using a close-up scale under the same conditions.

[Examples] Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 Carbonic acid containing 75% by weight or more of 100 parts by weight of an epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) having a particle size distribution in the range of 10 to 500 μ and having a particle size of 40 μ or more. Calcium (P-200, Shiraishi Industry Co., Ltd.)
Made of latent latent curing agent dicyandiamide 10 to 200 parts by weight
Parts by weight, colloidal silica (# 200, manufactured by Nippon Aerosil Co., Ltd.) 1 part by weight, fibrous filler (Milcon P, manufactured by Showa Mining Co., Ltd.) 1 part by weight, isopropyl alcohol 1
0 parts by weight and 10 parts by weight of methyl ethyl ketone are blended and mixed in a planetary mixer.

The thixotropic property is measured by dropping 0.5 g of the composition on a slide glass, marking a line at the dropping position and standing vertically after 10 minutes, and then measuring the difference from immediately after the dropping. The smaller the difference, the better the thixotropic property. The viscosity was measured by using a B-type rotary viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with a helical stand, with a spindle attached, at 30 ° C. for 3 minutes. As for the sedimentation property, the presence or absence of sedimentation of the filler after 30 days under the standing condition of 30 ° C. was confirmed. Table 1 shows the results. Example 2 Acrylic copolymer "Cotax LH601" (manufactured by Toray Industries, Inc., 50% solid content, solvent: ethyl acetate, butyl acetate) 140 parts by weight, oligoester acrylate M53
00 (manufactured by Toagosei Co., Ltd.) 10 parts by weight, oligoepoxy acrylate SP1506 (manufactured by Showa Polymer Co., Ltd.) 20
The procedure of Example 1 was repeated, except that parts by weight of AIBN was used as a radical initiator to prepare the composition of Table 1. Table 1 shows the results.

Example 3 50 parts by weight of unsaturated polyester resin Rigolac 380 (manufactured by Showa Polymer Co., Ltd.) and 50 parts by weight of styrene, and 2 parts by weight of a curing agent Niper BO (benzoyl peroxide, manufactured by NOF CORPORATION). The same procedure as in Example 1 was carried out except that the composition shown in Table 1 was used. Table 1 shows the results.

Example 4 Example 1 was carried out in the same manner as in Example 1 except that calcium carbonate was changed to silicon oxide to obtain the composition shown in Table 1. Table 1 shows the results.

Example 5 Example 5 was carried out in the same manner as in Example 1 except that the composition shown in Table 1 was used. Table 1 shows the results. Comparative Example 1 In the composition of Example 1, except that calcium carbonate was changed from P-200 to P-10 (Shiraishi Industry Co., Ltd.) having a particle size of 99% or more and 10 μ or less, the composition shown in Table 1 was used. The same procedure as in Example 1 was performed. Table 1 shows the results. Comparative Example 2 The procedure of Example 1 was repeated, except that the fibrous filler was omitted from the composition of Example 1 to obtain the composition shown in Table 1. Table 1 shows the results.

Comparative Example 3 Example 2 was carried out in the same manner as in Example 1 except that the fibrous filler was removed and the calcium carbonate was changed from P-200 to P-10 to obtain the composition shown in Table 1. The results are shown in Table 1.
Shown in

Comparative Example 4 Example 1 was carried out in the same manner as in Example 1 except that the colloidal silica was omitted from the composition. Table 1 shows the results.

[0023]

The resin composition of the present invention has a high thixotropic property, an appropriate viscosity, and excellent workability. Also,
The resin composition is used for general adhesives, cast products, etc., but in particular, the adhesion of a glass tube to a base in a tube such as a straight tube fluorescent lamp, an incandescent lamp, a compact fluorescent lamp, that is, an electric lamp. Most suitable as an adhesive for tube caps.

[0024]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 63/00 NLD 67/06 MSE 75/04 NFY 101/00 H01K 1/46 X 9508-2G

Claims (5)

[Claims] 1. A resin composition comprising a resin (A), a filler (B), a colloidal silica (C) and a fibrous filler (D). 2. The resin composition according to claim 1, wherein the resin (A) is a resin selected from one kind or two or more kinds of an epoxy resin, a urethane resin, an acrylic resin and an unsaturated polyester resin. 3. The filler (B) contains 50% by weight or more of particles having a particle size of 40 to 500 μ, and the content of the filler (B) in the resin (A) is 50% by weight or more. Item 3. The resin composition according to Item 1 or 2. 4. The fibrous filler (D) has a fiber diameter of 0.1 to 10.
The resin composition according to claim 1, 2 or 3 having a fiber length of 0.3 µ and a fiber length of 5 to 50 µ. 5. An adhesive for a bulb base of an electric lamp, which comprises the resin composition according to any one of claims 1 to 4.