JPH0359098B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composite resin composition, and more particularly to a composite resin composition that allows molded articles with excellent thermal, electrical, and mechanical properties to be obtained. Until now, it has been known to blend relatively large amounts of inorganic and/or organic fillers into synthetic resins, especially thermoplastic resins, for the purpose of improving various properties such as thermal properties and electrical properties, and increasing the amount. However, I have not yet obtained anything satisfactory. Furthermore, in order to compensate for the mechanical strength, attempts have been made to include a coupling agent in the hope of creating a physical or chemical bond between the resin and the filler. However, even in such cases,
The filler exists only as a solid foreign substance in the resin, and serves as a stress concentration point for external stress, causing deterioration of various properties such as mechanical properties. The present invention solves the above-mentioned conventional drawbacks by selecting a low softening point glass as a filler and using both a specific coupling agent and a modified polyolefin, and improves thermal, electrical and mechanical properties. The object is to provide an improved composite resin composition. That is, the present invention provides 10 to 60 parts by weight of a synthetic resin selected from the group consisting of polypropylene, polyethylene, acrylonitrile-butadiene-styrene resin, polyamide resin, polyester, polyether sulfone, and phenol resin, phosphate glass, and boric acid salt. 1 to 10 parts by weight of a silane coupling agent and modified polyolefin to a total of 100 parts by weight of 90 to 40 parts by weight of a low softening point glass selected from the group consisting of glass, lead glass, and barium glass with a softening point of 400°C or less. Blending 1 to 7 parts by weight,
The present invention provides a composite resin composition which is kneaded at a temperature of +10° C. or higher than the softening point of the low softening point glass. In the present invention, the synthetic resins used include polypropylene; polyethylene; acrylonitrile-butadiene-styrene resin (ABS resin); polyamide resins such as nylon-6 and nylon-6.6; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyether sulfone and phenol resins. Use one selected from the group consisting of: Next, as the glass to be added to the synthetic resin, a low softening point glass having a softening point of 400° C. or lower is used. As such a low softening point glass, one selected from the group consisting of phosphate glass, borate glass, lead glass, and barium glass is used. The blending amounts of the synthetic resin and low softening point glass are 10 to 60 parts by weight of the synthetic resin, preferably 15 to 55 parts by weight, and 90 to 40 parts by weight of the glass, preferably 85 to 45 parts by weight. If the amount of the synthetic resin exceeds 60 parts by weight, mold shrinkage will deteriorate, which is not preferable.
Further, if it is less than 10 parts by weight, moldability deteriorates, which is not preferable. If the amount of low softening point glass exceeds 90 parts by weight, moldability will deteriorate, which is not preferable. Moreover, if it is less than 40 parts by weight, molding shrinkage properties will deteriorate, which is not preferable. Furthermore, in the present invention, a silane coupling agent and/or a modified polyolefin is used. Various silane-based coupling agents are used, and although there are no particular limitations, examples include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, and vinyl tris(β-methoxysilane). ethoxy)silane, γ-methacryloxypropyltrimethoxysilane, methacryloxypropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane,
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-(trimethoxysilylpropyl)-ethylenediamine,
Amino functional silane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(polyethyleneamino)propyltrimethoxysilane, N-β-(aminoethyl)- γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)
-γ-oxypropylmethyldialkoxysilane, γ-ureidopropyltriethoxysilane,
Examples include γ-amidinothiopropyltrihydroxysilane, N'-vinylbenzyl-N-trimethoxysilylpropylethylenediamine salt, and the like. Among these, γ-methacryloxypropyltrimethoxysilane is particularly preferred. The amount of the silane coupling agent to be blended is 1 to 10 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the total amount of the synthetic resin and low softening point glass. If the amount of the silane coupling agent exceeds 10 parts by weight, processability will deteriorate. Moreover, if it is less than 1 part by weight, the molded appearance will deteriorate. Next, as the modified polyolefin, polyolefins chemically modified with liquid rubber and/or unsaturated carboxylic acids (including anhydrides) or derivatives thereof are preferably used. As the liquid rubber, terminal hydroxylated polybutadiene is suitable. In producing this chemically modified polyolefin, radicals such as benzoyl peroxide are generated by heating a polyolefin such as polypropylene, liquid rubber, and an unsaturated carboxylic acid or its derivative in a solvent such as xylene, toluene, heptane, or monochlorobenzene. The reaction may be carried out using an agent. Details of the method for producing this chemically modified polyolefin are disclosed in JP-A-54-124049. The amount of this modified polyolefin blended is 1 to 7 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the total amount of the synthetic resin and low softening point glass. If the amount of the modified polyolefin exceeds 7 parts by weight, moldability and molded appearance will deteriorate. Moreover, if it is less than 1 part by weight, the rigidity of the molded product will decrease. The above-mentioned silane coupling agent and modified polyolefin are both used in combination. When both are used together, the rigidity is further improved and the molding shrinkage is improved. In addition, in the present invention, various additives such as lubricants, organic/organic fillers, antistatic agents, colorants, flame retardants, antioxidants, ultraviolet absorbers, and plasticizers can be added as appropriate. . Examples of lubricants include hydrocarbon lubricants such as liquid paraffin, natural paraffin, and wax, fatty acid lubricants such as higher fatty acids and oxyfatty acids, ester lubricants such as lower alcohol esters of fatty acids, alcohols such as aliphatic alcohols, and polyglycols. lubricant,
Examples include metal soaps such as calcium stearate and barium stearate, silicone such as silicone oil, and modified silicone. Fillers include inorganic fillers such as calcium carbonate, barium sulfate, talc, silica, mica, clay, and metal powder.
Examples include wood flour such as pine, fir, hemlock, and poplar; wooden frame products; fruit shell powder such as walnut and coconut; and organic fillers such as waste paper. Various surfactants are used as the antistatic agent. In addition, colorants include poorly soluble azo dyes, red colorants, cadmium yellow,
Examples include chrome yellow and titanium white. Examples of flame retardants include inorganic antimony oxide and zircon oxide, and organic phosphoric acid esters and tricresyl phosphate. As the antioxidant, a phenol type is used, and as the ultraviolet absorber, a triazole type, salicylic acid type, or acrylonitrile type is used. moreover,
Examples of plasticizers include phthalic acid diesters, butanol diesters, and phosphoric esters. The composite resin composition of the present invention can be obtained by kneading the above components. The components are kneaded by a conventional method, for example, using a kneader such as a Banbury mixer or a single-screw extruder, but in particular at a temperature of +10° C. or more above the softening point of the low softening point glass. The kneading time is not particularly limited, but when a Banbury mixer is used, it is usually about 15 to 20 minutes. Further, it is preferable to premix the ingredients beforehand during kneading. Next, the composite resin composition thus obtained is pelletized, and the pellets are further molded into appropriate shapes by injection molding, extrusion molding, or other molding means to produce various molded products. Here, the molding temperature is preferably +10° C. or higher than the softening point of the low softening point glass. By setting both the molding temperature and the above-mentioned kneading temperature to +10°C or higher than the softening point of the low softening point glass, the glass in the resin is melted and a strong physical and chemical bond is created under cold conditions. I can do it. Therefore, according to the composite resin composition of the present invention, a molded article having excellent mechanical properties, especially rigidity, can be obtained. Moreover, the composite resin composition of the present invention has extremely low molding shrinkage during molding, has excellent moldability, and has a good molded appearance. Furthermore, the molded product obtained by molding the composite resin composition of the present invention has a low thermal conductivity, an excellent heat insulating effect, and a high dielectric constant. Therefore, the composite resin composition of the present invention can be effectively used as a material for office equipment housings, building materials such as bathtubs, precision equipment parts, audio parts, automobile parts, and the like. Next, the present invention will be explained in detail using examples. Production example Production of modified polyolefin Polypropylene (melt index (MI) 8 g/10 minutes, density 0.91 g/cm ³ ,
Product name: J700G, manufactured by Idemitsu Petrochemical Co., Ltd.) 1,4-terminal hydroxylated 1,4-polybutadiene (number average molecular weight 3000, product name: Poly bd)
R45HT, manufactured by ARCO Chem.Div.) 5 parts by weight, maleic anhydride 20 parts by weight, dicumyl peroxide
Charge 1.72 parts by weight and 600 parts by weight of xylene,
The mixture was heated in an oil bath using an immersion heater, and reacted with stirring at 120°C for 1 hour, and 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 under 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 a chemically modified polyolefin. Examples 1 to 16 and Comparative Examples 1 to 3 A compound containing a predetermined amount of synthetic resin, low softening point glass, silane coupling agent, and modified polyolefin was kneaded using a 50 mmφ single screw extruder under the kneading conditions shown in Table 1. A composition was prepared and pelletized. Using this pellet, test pieces were prepared using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., 10 oz.) at the molding temperatures shown in Table 1, and evaluated. The blending ratios and evaluation results are shown in Table 2.
In addition, the evaluation was performed by the following method. Evaluation method 1 Molding shrinkage rate A plate of 140 x 140 x 3.2 mm was molded and the rate of dimensional change was measured. 2 Flexural modulus Based on ASTM D-790. 3 Thermal conductivity Compliant with ASTM C-177. 4 Inductivity Compliant with ASTM D-150. 5. Formability Melt flow index (MFI) Compliant with JIS K-7210.

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[Table] Molding appearance The appearance of the plate used for measuring the molding shrinkage rate was visually judged. ○...Good △...Slight flow marks occurred ×...Surface is not smooth and filler is present as solid foreign matter Comparative Examples 4 to 15 and Reference Examples 1 to 2 The kneading conditions and molding temperature were as shown in Table 1. Evaluations were conducted under the same conditions as Examples 1 to 16 and Comparative Examples 1 to 3, except that the blending ratios were as shown in Table 2. The evaluation results are shown in Table 2.

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Claims (1)

[Claims] 1 10 to 60 parts by weight of a synthetic resin selected from the group consisting of polypropylene, polyethylene, acrylonitrile-butadiene-styrene resin, polyamide resin, polyester, polyethersulfone, and phenolic resin, phosphate glass, borate glass, lead glass Low softening point glass 90 with a softening point of 400℃ or less selected from the group consisting of
1 to 10 parts by weight of a silane coupling agent and 1 to 7 parts by weight of a modified polyolefin are blended to 100 parts by weight of the total amount of ~40 parts by weight, and kneaded at a temperature of +10°C or higher than the softening point of the low softening point glass. A composite resin composition made of