JPH064765B2 - Resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing aluminum borate whiskers. In general, whiskers have no defects in their structure, and therefore their strength and elastic modulus are extremely high. Therefore, by adding it to the resin,
The elastic modulus is expected to increase significantly, and it can be used as a filler for composite materials. Moreover, since the shape of the whisker is extremely small, it is possible to reinforce a product having a small shape, and it is possible to obtain a molded product in which the filler is not exposed on the surface of the product.

Conventional technology Since resin materials are lightweight and easy to mold, they are used in a wide range of applications such as household appliances, electrical products, automobile parts, and building material parts.

In recent years, the properties required for these resin materials (in particular, mechanical properties such as strength and elastic modulus, heat resistance, etc.) have become severe. Generally, a resin composition is often mixed with an inorganic filler for the purpose of increasing strength and elastic modulus and improving heat resistance.

In particular, as shown in the examples of fiber reinforced plastics (FRP, FRTP), the position occupied by the fibrous filler in the resin-based structural composite material is extremely important. For example, glass fiber / alumina fiber is a reinforcing filler. Has been developed and applied as. Whiskers such as potassium titanate having a short fiber length are also used as a reinforcing filler.

Also, the strength of these resin-based structural composites, such as fiber-reinforced plastics, is dependent on the presence of bonds between the filler fibers and the matrix-forming plastic. The surface of the filler is chemically treated to make a strong bond. The treating material used at this time is a coupling agent, which is a silicon-based, titanium-based, aluminum-based, zirconium-based, zirco-aluminum-based material. , Chromium-based, boron-based, phosphorus-based, amino acid-based, etc. are used.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Generally, when a resin is used for applications requiring high strength and high elastic modulus, a method of adding a powder filler at a high filling ratio and a relatively high strength and elasticity of glass fiber or the like are generally used. There is a method of using a fibrous filler having

However, the former method of adding powder filler at a high filling rate not only deteriorates workability due to an increase in viscosity of the resin composition before curing or during melting, but also lowers impact resistance, increases specific gravity, and increases water resistance. There is an adverse effect such as deterioration of sex. Conventionally used powder fillers such as silica, alumina, calcium carbonate, aluminum hydroxide, and talc have such drawbacks.

In the latter method using glass fiber, etc., since the size of glass fiber is larger than other fillers, it is not possible to reinforce products with a small shape, and it is exposed on the surface of the product after molding and resistant. There is also a problem of abrasion, and it is not preferable in terms of appearance.

Means for Solving the Problems In view of such circumstances, the present inventors have conducted extensive studies, and as a result, by compounding aluminum borate whiskers with a resin as a filler, the strength of the resin is higher than that of the base resin. The inventors have invented a resin composition having a high elastic modulus, capable of reinforcing a product having a small shape, and obtaining a molded product in which the filler is not exposed on the surface of the product.

Suitable resins for carrying out the present invention include so-called thermoplastic resins such as polyethylene, polypropylene, polystyrene, ABS resin, polyamide, thermoplastic polyester,
Polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyether imide, polyether ether ketone, etc. are considered. As the so-called thermosetting resin, epoxy resin, unsaturated polyester, vinyl ester, phenol resin, alkyd resin, silicone resin, diallyl phthalate homopolymer, polyamide, urea and melamine-containing resin, polyurethane and the like are considered. These resins may be used alone or in combination of two or more. Further, as a so-called polymer alloy, it is possible to use a composite of several kinds of different resins such as polycarbonate and polyethylene, polycarbonate and ABS resin, polyphenylene ether and polystyrene in advance.

Typical of aluminum borate whiskers used in the practice of the present invention are 2Al ₂ O ₃ · B ₂ O ₃ or 9Al ₂
O ₃ · 2B ₂ O ₃ having a composition represented by, for example, 2
Aluminum borate whiskers having a composition represented by Al ₂ O ₃ · B ₂ O ₃ are at least one aluminum supply component selected from aluminum hydroxide and aluminum inorganic salts, boron oxide, and oxygen. An acid and at least one boron supplying component selected from the alkali metal salts thereof, and at least one melting agent selected from alkali metal chlorides, alkali metal sulfur salts and alkali metal carbonates. It can be obtained by reacting and growing by heating to a temperature of 600 to 1000 ° C in the presence.

Further, aluminum borate whiskers having a composition represented by 9Al ₂ O ₃ · 2B ₂ O ₃ are at least one aluminum supplying component selected from aluminum hydroxide and aluminum inorganic salts, and an oxide of boron. , Oxygen acid, and at least one boron-supplying component selected from alkali metal salts thereof, and at least one melt selected from alkali metal chlorides, alkali metal sulfates, and alkali metal carbonates. It is obtained by heating to a temperature of 900 to 1200 ° C in the presence of an agent to cause reaction and growth.

Aluminum borate whiskers obtained by these methods have a fiber diameter of 0.05 to 5 μm and a fiber length of 2 to 100 μm, and are significantly smaller than glass fibers, so they can be reinforced for products with small shapes, and the surface of the product The filler is not exposed.

In order to further enhance the reinforcing effect on these aluminum borate whiskers, it is effective to improve the wettability and bondability between the aluminum borate whiskers and the matrix resin by surface treatment with a coupling agent. . The coupling agents used at this time are silicon-based, titanium-based, aluminum-based, zirconium-based,
Zirco aluminum type, chromium type, boron type, phosphorus type,
It is a known amino acid type.

Specifically, the surface treatment of aluminum borate whiskers using the above-mentioned known coupling agents of silicon type, titanium type, aluminum type, zirconium type, zirco aluminum type, chromium type, boron type, phosphorus type, amino acid type, etc. Any method can be adopted as a method for carrying out, but generally, a method of charging aluminum borate whiskers into a blender equipped with a spray device and spraying a coupling agent while operating the blender, water or an organic solvent. A method of dissolving the coupling agent in a solvent and dipping the aluminum borate whiskers in this solution and then removing the solvent to dry, the coupling agent and the aluminum borate whiskers in a dry state within the range of room temperature to 250 ° C. There are methods such as mixing. The amount of these coupling agents used is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of aluminum borate whiskers. It should be noted that these coupling agents may be blended and mixed when the resin is mixed with the aluminum borate whiskers and other additives to prepare the resin composition.

The treatment of these coupling agents is appropriately determined depending on the compatibility with the resin serving as the matrix, but is not particularly limited, and a plurality of treatments can be combined.

The amount of the aluminum borate whiskers relative to the resin as the main component in the composition of the present invention can be appropriately changed depending on the application of the resin composition of the present invention.

However, generally, the addition amount of aluminum borate whiskers is less than 5 parts by weight with respect to the resin, there is a possibility that the reinforcing effect by the whiskers may not be sufficiently expressed, and the addition amount of the whiskers to the resin is 100. When it exceeds the weight part, the dispersibility of the reinforcing material deteriorates and it becomes difficult to obtain a uniform molding composition.
It should be used in the range of 5 to 100 parts by weight, preferably 10 to 80 parts by weight.

In carrying out the present invention, if necessary, a colorant, a dispersant, a plasticizer, an antioxidant, an antiaging agent, an ultraviolet absorber, a flame retardant, a crosslinking agent, a curing agent, a curing accelerator, a thixotropy imparting agent, Reinforcing fillers including reactive diluents, leveling agents, lubricants, thickeners, anti-settling agents, antifoaming agents, adhesion promoters, wetting agents, rust inhibitors, corrosion inhibitors, glass fibers, etc.,
You may use together various additives normally used, such as a non-reinforcing filler.

In order to prepare a resin composition containing the resin, aluminum borate whiskers and other additives, a blender, a kneader, a roll, etc. are appropriately mixed in a conventional manner within the above-mentioned mixing ratio range. Done by. Further, the resin composition thus prepared,
In the case of a thermoplastic resin, a desired product is molded by ordinary extrusion molding or injection molding, and in the case of a thermosetting resin, it is cured under appropriate curing conditions.

EXAMPLES The present invention will be described in detail with reference to Examples and Comparative Examples below.

The glass transition temperature in these tests is measured by ASTM
D-696, flexural strength, flexural modulus according to JIS K-7203, heat distortion temperature according to JIS K-7207, and tensile shear adhesive strength according to JI
The measurement was performed using a steel plate that had been degreased after polishing with SK-6850. The tensile strength is measured according to JIS K-7113, the flexural modulus is according to JIS K-7203, and the Izod impact test is performed.
It was measured according to JIS K-7110.

Example 1 To 100 parts by weight of a diglycidyl ether type liquid epoxy resin of bisphenol A (trade name Epicoat # 828, manufactured by Yuka Shell Epoxy), methyl-Δ ⁴ -tetrahydro which is a cyclic aliphatic acid anhydride as a curing agent. Phthalic anhydride (Brand name Epicron B-570 manufactured by Dainippon Ink and Chemicals)
86.4 parts by weight, and 0.2 parts by weight of 2-ethyl-4-methylimidazole (trade name Cureazole 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator are added, and uniformly mixed with a stirrer. This is the base resin (1), and this base resin (1) 100
Prepared by adding 10 parts by weight and 20 parts by weight of aluminum borate whiskers having a composition of 9Al ₂ O ₃ · 2B ₂ O ₃ to 1 part by weight, and kneading them uniformly with a three-roll mill. And These blends were heated at 80 ° C. for 2 hours, further heated and cured at 150 ° C. for 4 hours, and the physical properties were measured. The results are shown in Table 1.

Example 2 With respect to 100 parts by weight of the same epoxy resin as in Example 1, 2,4-diamino-6- {2'-methylimidazolyl was used as a curing agent.
(1) '} Ethyl-s-triazine / isocyanuric acid adduct (trade name: Cureazole 2MA-OK, manufactured by Shikoku Chemicals Co., Ltd.) is added in an amount of 5 parts by weight, and uniformly mixed with a stirrer. This was used as the base resin (2), and 9 Al was added to 100 parts by weight of this base resin (2).
Aluminum borate whiskers having a composition of ₂ O ₃ · 2B ₂ O ₃ were added at a ratio of 10 parts by weight and 20 parts by weight, respectively, to prepare a composition in the same manner as in Example 1, and after curing, Was measured. The results are shown in Table 1.

Example 3 .gamma.-aminopropyltriethoxysilane in methanol 2 (trade name KBE-903, produced by Shin-Etsu Silicone) After stirring added 10g was added whiskers 500g having the composition _{9Al 2 O 3 · 2B 2 O} 3 , Stirred at room temperature for another 15 minutes, filtered and made whiskers with coupling treatment on the surface.
After drying at 0 ° C. for 3 hours, the same base resin as in Example 1
(1) Add 10 parts by weight and 20 parts by weight to 100 parts by weight,
A formulation was prepared and cured in the same manner as in Example 1, and the physical properties of each were measured. The results are shown in Table 1.

The place of the whiskers having the composition _{9Al 2 O 3 · 2B 2 O} 3 in the present example whiskers having the composition _{2Al 2 O 3 · B 2 O} 3, epoxy resin composition obtained by repeating the same processing Is
It had almost the same performance as in Table 1.

Comparative Example 1 In Example 1, 10 parts by weight of alumina (trade name A-12 Showa Denko) was used instead of aluminum borate whiskers.
20 parts by weight were added to each, and a mixture was prepared and cured in the same manner, and the physical properties of each were measured. The results are shown in Table 2.

Comparative Example 2 In Example 1, 10 parts by weight and 20 parts by weight of fused silica (trade name F-44 Denki Kagaku Kogyo) were added in place of the aluminum borate whiskers to prepare a mixture and cure. After that, each physical property was measured. The results are shown in Table 2.

As shown in Table 1 and Table 2, the composition containing the aluminum borate whiskers of the present invention was compared with the base resin alone, the alumina compounding composition, and the fused silica compounding composition.
The flexural strength, flexural modulus, and tensile shear adhesive strength are significantly improved, which indicates that aluminum borate whiskers have an excellent reinforcing effect. It was also found that the reinforcing effect on the epoxy resin is further improved by subjecting the surface of the whisker to the usual treatment with a silicon-based coupling agent.

Example 4 25 parts by weight and 50 parts by weight of aluminum borate whiskers having a composition of 2Al ₂ O ₃ · B ₂ O ₃ with respect to 100 parts by weight of a polyamide resin (nylon 6 manufactured by A-1030SR Unitika). Add each of them, put them in a mixer and mix them uniformly, and then use a twin-screw extruder to pelletize the compound, and after drying, injection temperature 240 ℃, mold temperature 80 ℃, injection pressure 770Kg.
Injection molding was performed under the condition of / cm ² and the physical properties were measured. The results are shown in Table 3.

Comparative Example 3 In Example 4, 500 parts by weight of talc (trade name LMS-100 manufactured by Fuji Talc Industry Co., Ltd.) was added to 100 parts by weight of the polyamide resin instead of the aluminum borate whiskers, and a molded product was prepared in the same manner. After that, each physical property was measured. The results are shown in Table 3.

The composition containing the aluminum borate whiskers of the present invention has significantly improved tensile strength, tensile modulus, flexural strength and flexural modulus as compared with the polyamide resin alone and the talc filled composition. No improvement in impact strength was observed.

Example 5 10 g of γ-aminopropyltriethoxysilane (trade name KBE-903, manufactured by Shin-Etsu Silicone) was added to methanol 2 and stirred, and then a whisker having a composition of 2Al ₂ O ₃ · B ₂ O ₃ was added.
Add 500 g, stir at room temperature for another 15 minutes, filter to make whiskers with coupling treatment on the surface.
Polyamide resin similar to that of Example 4 after drying at 0 ° C. for 3 hours
25 parts by weight and 50 parts by weight were added to 100 parts by weight, respectively, and a molded product was prepared in the same manner as in Example 4, and then the physical properties thereof were measured. The results are shown in Table 3, and by applying the coupling agent treatment to the aluminum borate whiskers, the wettability with respect to the polyamide resin was improved, the reinforcing effect was further improved, and the impact resistance was also improved.

Also, in this example, a whisker having a composition of 2Al ₂ O ₃ · B ₂ O ₃
Instead of whisker having a composition of _{9Al 2 O 3 · 2B 2 O} 3, wherein the polyamide resin composition E by repeating the same process was one having substantially the same performance as in Table 3.

25 parts by weight of aluminum borate whiskers having a composition of _{9Al 2 O 3 · 2B 2 O} 3 with respect to Example 6 Polycarbonate resin (trade name Yupiron S-2000 from Mitsubishi Gas Chemical), prepared plus 50 parts by weight And stir and mix with a stirrer. 240 ° C
Was uniformly kneaded with a hot roll to pelletize. After drying the pellets, injection molding was performed under the conditions of an injection temperature of 300 ° C., a mold temperature of 80 ° C. and an injection pressure of 1100 Kg / cm ² , and the physical properties were measured under the same conditions as in Example 4. The results are shown in Table 4.

After stirring was added 10g of in Example 7 Methanol 2 .gamma.-aminopropyltriethoxysilane (trade name KBE-903 by Shin-Etsu Silicone), aluminum borate having a composition of _{9Al 2 O 3 · 2B 2 O} 3 whisker 500g Was added. After stirring at room temperature for further 15 minutes, filtration was performed to obtain a surface-treated whisker. The filtered whiskers were dried at 110 ° C. for 3 hours, and then the same polycarbonate resin as in Example 6 was used, to which 25 parts by weight and 50 parts by weight were added. Thereafter, a molded product was prepared in the same manner as in Example 6 and the physical properties thereof were measured. The results are shown in Table 4.

In the polycarbonate resin composition containing the aluminum borate whiskers of the present invention, the tensile strength, the tensile elastic modulus, the bending strength and the bending elastic modulus were significantly improved as compared with the resin alone. In addition, the reduction of impact strength was improved by blending the whisker treated with a coupling agent with the resin.

The place of the whiskers having the composition _{9Al 2 O 3 · 2B 2 O} 3 in the present example whiskers having the composition _{2Al 2 O 3 · B 2 O} 3, wherein the polycarbonate resin composition obtained by repeating the same process Had almost the same performance as in Table 4.

Example 8 Using a pellet containing 50 parts by weight of the same aluminum borate whiskers as in Example 6, injection molding was carried out under the same conditions as in Example 6 to make a very small gear (diameter 2.0 mm, thickness 0.5 mm). . A polycarbonate resin (trade name: Iupilon GS-2030M manufactured by Mitsubishi Gas Chemical Co., Ltd.) containing 43 parts by weight of glass fiber was also injection-molded in the same manner. Molded products containing aluminum borate whiskers are dense and no exposure of whiskers is visible on the surface of the molded product, whereas molded products containing glass fibers leave bubbles and glass fibers are exposed on the surface of the molded product. The shape of the gear was damaged.

Example 9 PBT resin (trade name: Kanebo PBT720, manufactured by Kanebo)
Prepare 25 parts by weight and 50 parts by weight of aluminum borate whiskers having a composition of 2Al ₂ O ₃ · B ₂ O ₃ , and stir and mix with a stirrer. This was uniformly kneaded with a hot roll at 230 ° C. and pelletized. After drying the pellets, injection molding was performed under the conditions of an injection temperature of 250 ° C., a mold temperature of 80 ° C., and an injection pressure of 840 kg / cm ² , and the physical properties were measured under the same conditions as in Example 4.
The results are shown in Table 5.

Example 10 10 g of γ-aminopropyltriethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Silicone) was added to methanol 2 and stirred, and then 500 g of aluminum borate whiskers having a composition of 2Al ₂ O ₃ · B ₂ O ₃ was added. Was added. After stirring at room temperature for further 15 minutes, filtration was performed to obtain a surface-treated whisker. After drying the filtered whiskers at 110 ° C for 3 hours,
The same PBT resin as in Example 9 was added with 25 parts by weight and 50 parts by weight. Thereafter, a molded product was prepared in the same manner as in Example 9 and the physical properties thereof were measured. The results are shown in Table 5.

PB containing aluminum borate whiskers of the present invention
The T resin composition was significantly improved in tensile strength, tensile elastic modulus, bending strength, and bending elastic modulus as compared with the resin alone. Further, the impact strength was greatly improved by blending the whiskers treated with the coupling agent with the resin.

The _{2Al 2 O 3 · B 2 O} 3 of a whisker having a composition in place of whiskers having a composition of _{9Al 2 O 3 · 2B 2 O} 3, a polyamide resin composition E by repeating the same processing in this example It had almost the same performance as in Table 5.

Example 11 Using a pellet containing 50 parts by weight of the same aluminum borate whiskers as in Example 9, a very small gear (diameter 2.0 mm,
A thickness of 0.5 mm) was injection-molded under the same conditions as in Example 9.
A PBT resin (trade name: Kanebo PBT719G30 Kanebo) containing 43 parts by weight of glass fiber was also injection-molded in the same manner. Molded products containing aluminum borate whiskers are dense and no exposure of whiskers is visible on the surface of the molded product, whereas molded products containing glass fibers leave bubbles and glass fibers are exposed on the surface of the molded product. The shape of the gear was damaged.

Claims (4)

[Claims] 1. A resin composition comprising a resin and aluminum borate whiskers. (However, excluding polyvinyl chloride resin composition) 2. The resin composition according to claim 1, wherein the aluminum borate whiskers are surface-treated with a coupling agent. 3. Aluminum borate whiskers are 9Al ₂ O ₃ ·.
A composition represented by 2B ₂ O ₃
The resin composition according to (1) or (2). 4. An aluminum borate whisker comprising 2Al ₂ O ₃
A composition comprising B ₂ O ₃
The resin composition according to (1) or (2).