JPS6264864A - Composite resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. providing a molding having excellent mechanical properties, appearence, color tone and fabricability, by blending a blend of a specific glass fiber and a thermoplastic resin with a maleic anhydride-modified PP. CONSTITUTION:A glass fiber (a) (e.g., non-alkali glass fiber) is surface coated with an org. silane compd. (b) [e.g. N-beta-(aminoethyl)-gamma-amino propyltrimethoxysilane] to obtain a 4-8mu diameter, 3-5mm long glass-fiber coated with 0.1-0.2wt% compd. (b) Separately, a PP (c), a liquid rubber (d) (e.g. hydroxyl-terminated polybutadiene) and maleic anhydride (e) are reacted in the presence of a radical generator in a solvent to obtain a maleic anhydride- modified PP (C). 100pts.wt. blend of 18-75wt% component (A) and 82-25wt% thermoplastic resin (B) selected from among PE, PP, ABS resin, polyurethane, polyamide and polyacetal is blended with 1-4pts.wt. component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite resin composition, and more specifically, it is possible to obtain a molded product having excellent mechanical strength, good appearance, excellent secondary processability, and good color tone. The present invention relates to a composite resin composition that can be produced.

Conventionally, in glass fiber blended thermoplastic resins, the glass fibers blended generally have a fiber length of 3 to 5 sue.

Those having a fiber diameter of 15 to 25 Jj are used. In addition, in order to improve the adhesion between glass fibers and thermoplastic resins, glass fibers are subjected to appropriate chemical treatments, and in such cases the amount of treatment agent attached to the glass fibers is usually 0. It is said to be .25 to 0.30% by weight.

For this reason, when the glass fibers are blended into the thermoplastic resin, the glass fibers break due to shearing, resulting in a length of 200 to 300 mm, resulting in a problem that the mechanical strength, particularly the tensile strength, 9 bending strength, and the impact strength are reduced.

Therefore, in order to obtain the target physical properties, it is necessary to increase the amount of glass fiber blended, but when a large amount of glass fiber is blended, new problems arise. In other words, if a large amount of glass fiber is blended, (1) the glass fibers cause wire crosstalk and abrasion of the molding machine, (2) the glass fibers stand out on the surface of the molded product, resulting in poor appearance and poor secondary processability. Problems such as (1) resulting in the use of a large amount of processing agent resulting in yellowing of the molded product and (2) increased specific gravity occurred.

The inventors of the present invention have made extensive studies in order to eliminate the above-mentioned conventional drawbacks. As a result, the fiber diameter of the glass fiber was reduced to 4 to 8 mm, which is 172 to 1/3 of that of conventional products, and the surface of the glass fiber was treated with an organic silane compound to prevent the organic silane compound from adhering to the glass fiber. The amount is 0.1-0.2% by weight.
The present inventors have discovered that the above-mentioned conventional drawbacks can be overcome by doing so, and have completed the present invention.

That is, in the present invention, (A) the fiber #I diameter is 4 to 8 μ;
and the amount of organic silane compound attached to the glass fiber is 0.
Glass fibers whose surface has been treated with an organic silane compound to a concentration of 1 to 0.2% by weight! i18-75% by weight, (B) 82-25% by weight of one type of thermoplastic resin selected from the group consisting of polyethylene, polypropylene, ABS resin, polycarbonate, polyamide and polyacetal (C) for a total of 100 parts by weight The present invention provides a composite resin composition containing 1 to 4 parts by weight of maleic anhydride-modified polypropylene.

The glass fiber used as component (A) in the present invention is
The tag diameter is 4 to 8μ. If the fiber diameter is outside this range, the mechanical strength will decrease, which is not preferable. Further, the fiber length is not particularly limited, but a fiber length of 3 to 5 mm is usually used. Furthermore, this glass fiber is surface-treated with an organic silane compound, and the amount of the organic silane compound attached to the glass fiber is 0.1 to 0.2.
% by weight. If the adhesion amount is less than 0.1% by weight, the mechanical strength will decrease, while if it exceeds 0.2% by weight, the molded product will yellow, which is not preferable.

The glass fibers are not particularly limited, but examples thereof include non-alkali glass m fibers, low alkali glass 5iII, and the like. Various organic silane compounds are used, and there are no particular limitations, such as γ-chloropropyltrimethoxysilane, vinyltrichlorosilane,
Vinyltriacetoxysilane, vinyltriethoxysilane, vinyl tris(β-methoxyethoxy)silane,
γ-methacryloxypropyltrimethoxysilane.

Methacryloxypropyltrialkoxysilane.

β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, γ-
Mercaptopropyltrimethoxysilane, N-()rimethoxysilylprobyl)-ethylenediamine, aminofunctional silane, γ-aminopropyltriethoxysilane,
N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(polyethyleneamino)propyltrimethoxysilane, N-β-(aminoethyl)-γ
-Aminopropyltrimethoxysilane.

Examples include N-β-(aminoethyl)-γ-oxydipropylmethyldialkoxysilane, γ-ureidopropyltriethoxysilane, and γ-amidinothiopropyltrihydroxysilane.

Among these, those containing amino groups, especially N-β-
(Aminoethyl)-γ-aminopropyltrimethoxysilane is preferred.

In order to obtain glass m-fibers surface-treated with the above-mentioned organosilane-based compound, glass m-fibers are usually treated with the above-mentioned organosilane-based compound,
Preferably, contact treatment may be performed with an amine group-containing organic silane compound. At this time, it is not necessary to use a solvent, but preferably a mixed solvent of lower alcohol and water is used.

Next, examples of the thermoplastic resin used as component CB) of the present invention include polypropylene, ABS resin, polycarbonate, polyamide, polyacetal, polyethylene and the like.

Moreover, liquid rubber can be used when producing the maleic anhydride-modified polypropylene of component (C). Here, terminal hydroxylated polybutadiene is suitable as the liquid rubber. In producing this chemically modified polypropylene, polypropylene, liquid rubber, and maleic anhydride may be reacted in a solvent such as xylene, toluene, heptane, or monochlorobenzene using a radical generator such as benzoyl peroxide. For details on the manufacturing method of this chemically modified polypropylene, please refer to JP-A-54-1
It is disclosed in Japanese Patent No. 24048.

The blending ratio of the above components (A), (B) and (G) is usually 18 to 75% by weight of component (A) and 82% by weight of component (B).
25% by weight, more preferably 1 to 4 parts by weight of component (C) per 100 parts by weight of the total of 20 to 60% by weight of component (A) and 80 to 40% by weight of component (B).

In addition, in the present invention, in addition to the above-mentioned components (A), (B), and (C), inorganic fillers other than glass fibers may be blended if necessary. The inorganic filler is not particularly limited, and examples thereof include talc, mica, calcium carbonate, wood flour, and the like.

Furthermore, in the present invention, crosslinking agents, lubricants,
Antistatic agent 2 Colorants, flame retardants, antioxidants, ultraviolet absorbers, plasticizers, etc. can be added.

The composite resin composition of the present invention can be obtained by kneading the above components. Mixing of each component is done in the usual way,
For example, a kneader such as a Banbury mixer is used.

Further, it is preferable to premix the ingredients beforehand during kneading. Next, the composite resin composition thus obtained can be manufactured using a single screw extruder.

According to the present invention, it is possible to obtain a molded article that is superior in mechanical strength, especially tensile strength, 9 bending strength, and impact strength, as compared to conventional products. Moreover, according to the present invention, it is possible to obtain a molded product that does not have glass fibers oozing out on the surface of the molded product, has a good appearance, and has excellent secondary processability such as paintability.

Further, according to the present invention, molded products are less likely to yellow due to the processing agent, and molded products with good color tone can be obtained.

Therefore, the composite resin composition of the present invention can be effectively used as a material for various molded products, particularly precision mechanical parts, office machines, audio component housings, automobile parts, electric tools, home appliance housings, and the like.

Next, the present invention will be explained in detail with reference to examples.

Preparation Example Preparation of glass fiber whose surface has been treated with an organic silane compound ■N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (10% by weight) is added to a mixed solvent of 80% by volume of vinyl acetate and 10% by volume of water. % dissolved. Then, the above solution was mixed with glass am (fiber length 3-5 m+s).

m#l diameter 6g) into a super mixer, stirred at low speed for 2 minutes at room temperature, and then lowered the temperature to 150~20℃.
The temperature was raised to 0° C. and the mixture was stirred for 10 minutes to remove volatile components, thereby preparing glass fibers surface-treated with an organic silane compound.

The amount of treatment agent adhered to glass m#l was 0.17% by weight.

■Concentrations of N-β-(aminoethyl)-γ-7minoprobyltrimethoxysilane were added to a mixed solvent of vinyl acetate θO volume% and water 10% by volume at 5°8 and 10.20%, respectively.
．． The solution adjusted to 30% by weight was then dissolved into a super mixer together with various glass fibers with a fiber diameter of 2 to 14 μm and II (fiber length of 3 to 5 layers), and the following steps were carried out in the same manner as in (1) above. Glass fibers surface-treated with organic silane compounds were prepared with varying amounts of treatment agent adhering to the glass fibers. The relationship between the concentration of the organic silane compound and the amount of the treatment agent attached to the glass fibers is shown below.

Production Example Production of Modified Polypropylene Polypropylene (melt index (XI)
) 8g/10min, density 0.91g/c+l13. Product name: J700G, manufactured by Idemitsu Petrochemical ■) Terminal hydroxylated 1,4-polybutadiene (number average molecular weight 3000, product name: Poly bd) per 100 parts by weight
R45HT, ARCOChe layer, manufactured by Div) 5
parts by weight, 20 parts by weight of maleic anhydride, 1.72 parts by weight of dicumyl peroxide, and 600 parts by weight of xylene, heated in an oil bath using an immersion heater, and reacted at 120°C for 1 hour with stirring. The reaction was then continued at 140°C for 3 hours. After the reaction was completed, the mixture was cooled, precipitated in a large excess of acetone, filtered with suction, and dried (at 70° C. for 50 hours) to obtain a white powder. Subsequently, this powder was placed in a Soxhlet extractor and extracted with acetone for 16 hours to remove unreacted polybutadiene and maleic anhydride to obtain chemically modified polypropylene.

Examples 1 to 23 and Comparative Examples 1 to 11 The glass fibers surface-treated with the organosilane compound obtained in the above Preparation Example, the thermoplastic resin, and the modified polypropylene obtained in the above Production Example in the proportions shown in Table 1. Mix it with
- Extrude using a shaft extruder (manufactured by Nakatani Machinery, NVG-50) at a temperature of 210 to 230°C and a discharge rate of 30 kg/hr to obtain a strand with a diameter of 21 fat, and use a pelletizer to form a strand of 2 m diameter x 3 layers. A pellet of size was obtained.

Using this pellet, the physical properties were evaluated according to the following method. The results are shown in Table 1.

Evaluation method 1.Tensile test Compliant with ASTM 0-838 2. Bending test Compliant with ASTM D-790 3.Izotsu impact test Compliant with ASTM D-258 4. Yellowing degree Yellow index value (Y, I value) It is preferably 10 or less.

5. Appearance A plate measuring 100 mm long x 100 mm wide x 3II11 thick was molded using an injection molding machine, and its surface was visually evaluated.

O...Beautiful Rei Δ... Some glass fibers appeared on the surface.

×...Glass fibers oozed out over the entire surface.

12, Standard 1 Polypropylene (manufactured by Idemitsu Petrochemical ■, Idemitsu Polypropylene J-3050H, melt index: 30 g
710 minutes) 2nd ABS resin (manufactured by Ube Saikon Co., Ltd., EX-15
1) No. 3 Polycarbonate (manufactured by Idemitsu Petrochemical Co., Ltd., Idemitsu Polycarbonate) A-2700) 46-nylon (manufactured by Ube Industries, Ltd., 6-nylon P-1)
011F) *5 Polyacetal (manufactured by Asahi Kasei ■, Tenacuo 6, manufactured by Asada Seifun ■, 1 particle size 2-3, final zero 7, manufactured by Asada Seifun ■, particle size 5-6μ, attack 8, manufactured by Kaneko Mining ■, KS-1300, particle size 1- 3 #L Zero 〇 Particle size: 80 mesh wood powder pulverized product 1 10 Glass TA fiber was easily broken.

Claims (1)

[Claims] 1. (A) The fiber diameter is 4 to 8μ, and the amount of organic silane compound attached to the glass fiber is 0.1 to 0.2% by weight
18 to 75% by weight of glass fiber whose surface has been treated with an organic silane compound so that A composite resin composition comprising 1 to 4 parts by weight of (C) maleic anhydride-modified polypropylene per 100 parts by weight of 25% by weight in total.