JPS59219367A - Composite resin composition - Google Patents

Abstract

PURPOSE:To provide a composite resin compsn. which gives moldings having excellent thermal, electrical and mechanical properties, by mixing a synthetic resin, glass having a low softening point and a silane coupling agent and/or a modified polyolefin. CONSTITUTION:5-90pts.wt. synthetic resin (A) such as a thermoplastic resin, e.g. polypropylene, or a thermosetting resin, e.g. epoxy resin, 95-10pts.wt. low- softening glass (B) having a softening point of 400 deg.C or below, e.g. silicate or phosphate glass, and 1-10pts.wt. (per 100pts.wt. of the combined quantity of components A and B) silane coupling agent, e.g. vinyltrichlorosilane or gamma-methacryloxypropyltrimethoxysilane, and/or modified polyolefin, e.g. terminal hydroxylated polybutadiene-modified polypropylene (C) are mixed together to obtain the desired composite resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite resin composition, and more particularly to a composite resin composition from which a molded article with excellent thermal, electrical and mechanical properties can 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 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 material in the resin, and becomes a stress concentration point for external stress, causing a reduction in various properties such as mechanical properties. Ta.

The present invention solves the above-mentioned conventional drawbacks by selecting a low softening point glass as a filler and using either or both of a specific coupling agent and modified polyolefin.

The object of the present invention is to provide a composite resin composition with improved electrical and mechanical properties.

That is, the present invention uses synthetic resin and low softening point glass.

A composite resin composition comprising a silane coupling agent and/or a modified polyolefin is provided.

The synthetic resin used in the present invention may be either a thermoplastic resin or a thermosetting resin, and is not particularly limited. Examples of the thermoplastic resin include polyethylene, polypropylene, acrylonitrile-butadiene-styrene resin (ABS resin) , nylon-6 and nylon-6,
Examples include polyamide resins such as No. 6, polystyrene, polyether, polyesters such as polybutylene terephthalate and polybutylene terephthalate, polycarbonate, polyvinyl chloride, and polyether sulfone. Examples of thermosetting resins include melamine resins, area resins, phenol resins, silicone resins, epoxy resins, alkyd resins, unsaturated polyester resins, and urethane resins. Among these, polypropylene, polyethylene, etc. are preferred.

Next, as the glass to be mixed in the synthetic resin, a low softening point glass is used, and a glass having a softening point of 400° C. or lower is particularly preferable. Examples of such low softening point glasses include silicate glasses, phosphate glasses, borate glasses, and soda-lime glasses.

Examples include lead glass and barium glass.

The blending amount of the above synthetic resin and low softening point glass is 5% of the synthetic resin.
-90 parts by weight, preferably 10-80 parts by weight, and 95-10 parts by weight, preferably 90-20 parts by weight of glass. If the amount of the synthetic resin exceeds 90 parts by weight, molding shrinkage will deteriorate, which is not preferable. Further, if it is less than 5 parts by weight, moldability deteriorates, which is not preferable. If the blending amount of the low softening point glass exceeds 95 parts by weight, moldability deteriorates, which is not preferable. Moreover, if it is less than 10 parts by weight, mold shrinkage properties will deteriorate, which is not preferable.

Furthermore, in the present invention, a silane coupling agent and/or a modified polyolefin are used.

Various silane-based coupling agents are used, and there are no particular limitations, such as γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyl tris(β- methoxyethoxy)silane, γ-methacryloxyglobyltrimethoxysilane, methacryloxypropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltritoxysilane.

γ-Glycidoxyprobyltrimethoxysilane.

Mercaftoglobil trimethoxysilane, γ-mercapdobuH pyrutrimethoxysilane, N-()rimethoxysilylprobyl)-ethylenediamine.

Amino functional silanes, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(polyethyleneamino)propyltrimethoxysilane.

N-β-(aminoethyl)-r-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-oxypropylmethyldialkoxysilane.

Examples include γ-ureidoglobil triethoxysilane, γ-amidinothioglobil trihydroxysilane N/-vinylhen-)ruN-)rimethoxysilylprobylethylenediamine salt, and the like. Among these, γ-methacryloxyglobyltrimethoxysilane is particularly preferred.

The blending amount of this silane coupling agent is 1 part by weight per 100 parts by weight of the above synthetic resin and low softening point glass.
~10 parts by weight, preferably 2 to 7 parts by weight. If the amount of the silane coupling agent exceeds 10 parts by weight, processability will deteriorate. Also, if it is less than 11 Keibu,
The molded appearance deteriorates.

Next, as the modified yj-'lyolefin, polyolefins chemically modified with liquid rubber and/or unsaturated carboxylic acids (including anhydrides) or derivatives thereof are preferably used. Here, terminal hydroxylated polybutadiene is suitable as the liquid rubber. In producing this chemically modified polyolefin, a polyolefin such as polypropylene, a liquid rubber, and an unsaturated carboxylic acid or its m-conductor are mixed in a solvent such as xylene, toluene, heptane, or monochlorobenzene, and a radical generator such as benzoyl peroxide is added. What is necessary is just to make it react using it. For details of the manufacturing method of this chemically modified polyolefin, please refer to Japanese Patent Application Laid-Open No. 1983-1999. It is disclosed in the publication No.-124049.

The blending amount of this modified polyolefin is 1 to 10 parts by weight per 100 parts by weight of the above synthetic resin and low softening point glass.
parts by weight, preferably 2 to 7 parts by weight. If the amount of the modified polyolefin exceeds 10 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.

Either the silane coupling agent or the modified polyolefin may be used alone, or both may be used in combination. When both are used together (1-), the rigidity is further improved and the molding shrinkage is improved.

In addition, in the present invention, various additives such as lubricants, inorganic/organic fillers, antistatic agents, colorants, flame retardants, antioxidants, ultraviolet absorbers, and plasticizers may be added as necessary. can be added. 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 A-esters of fatty acids, aliphatic alcohols, and polyglycols. Examples include alcohol-based lubricants such as, metal soaps such as calcium stearate and barium stearate, silicone such as silicone oil, and modified silicone. Calcium carbonate as a filler,
Inorganic fillers such as barium sulfate, talc, silica, mica, clay, and metal powder; Wood flour such as pine, fir, hemlock, and poplar; Wooden products; Grain flour from fruits such as walnut and palm; Organic materials such as waste and paper Examples include fillers. Various surfactants are used as the antistatic agent. In addition, colorants include poorly soluble azo dyes, red colorants, and 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.

Furthermore, examples of plasticizers include phthalic acid diesters, butanol diesters, phosphoric esters, and the like.

The composite resin composition of the present invention can be obtained by kneading the above components. Each component is kneaded using the usual method.
. For example, this is carried out using a kneading machine such as a Banbury mixer and a single-screw extruder, but it is particularly preferable to carry out the kneading at a temperature of +10"C or more above the softening point of the low softening point glass. There are no particular restrictions on the kneading time. Hana (・ga Banbury mixer)
When using , it usually takes about 15 to 20 minutes. Also,
When kneading, it is preferable to preheat the mixture in advance.

Next, the composite resin composition thus obtained is formed into a pellet, and the pellet is further molded into an appropriate shape by a molding means such as injection molding or extrusion molding 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. Both the molding temperature and the above-mentioned kneading temperature should be +10"C or higher than the softening point of the low softening point glass. It is possible to melt the glass in the resin and create strong physical and chemical bonds under cold conditions.

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;
It has an excellent heat insulating effect and a high fat charge rate.

Therefore, the composite resin composition of the present invention can be effectively used as a material for building materials such as office equipment housings and bathtubs, precision equipment parts, audio parts, and automobile parts.

Next, the present invention will be explained in detail using examples.

Production Example Production of Modified Polyolefin Polypropylene (melt index (MI)
) s 9/1o min, density 0.919/cm”.

Product name: , y7ooc+, manufactured by Idemitsu Petrochemical @) 1.
Terminal hydroxylated 1,4-polybutadiene (number average molecular weight 3000. Trade name: I'OIY)
bd R45HT, made by AROOChem, formerly ■)
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 heated to 120°C under stirring for 1 hour. react for an hour, then at 140°C.
The reaction was continued for 3 hours. After the reaction was completed, it was cooled, precipitated in a large excess of acetone, filtered with suction, and further dried (79%).
The powder was then placed in a Soxhlet extractor and extracted with acetone for 16 hours to remove unreacted polybutadiene and maleic anhydride, resulting in a chemically modified polyolefin. I got it.

Examples 1 to 19 50% of a blend containing a predetermined amount of synthetic resin, low softening point glass, silane coupling agent, and modified polyolefin
A composition was prepared by kneading using a φ-screw extruder under the mixing conditions shown in Table 1, and then formed into pellets. Using this pellet, injection molding machine (manufactured by Toshiba Machine @, 10 oz)
Test pieces were prepared 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: A plate with a positive molding shrinkage rate of 140 x 140 x 3.2 was molded and its dimensional change rate was evaluated.

26 Flexural modulus Conforms to ASTM D-790.

3. Thermal conductivity Conforms to ASTM C-1,77.

4. Induction rate Conforms to ASTM D-150.

5. Moldability ■Melt flow index (M, F, I,) JIS
Compliant with K-7210.

■Appearance The appearance of the grate used to measure the molding shrinkage rate was visually judged.

Examples 20 to 35 Evaluations were carried out under the same conditions as Examples 1 to 19, except that the crosstalk conditions and molding temperature were as shown in Table 1, and the blending ratio was as shown in Table 2. I did this. The evaluation results are shown in Table 2.

Table 1 *l Polypropylene (Idemitsu Petrochemical @), J-2
000G) *2 Acrylonitrile-butadiene-styrene resin (manufactured by Ube Cycon Co., Ltd., EX-15) 3rd
Polyethylene (manufactured by Idemitsu Petrochemical Co., Ltd., ll0J)
*4 Manufactured by Ube Industries, Ltd., P-10111i'*5
Polyethylene terephthalate (Nippon Unipet Co., Ltd.)
Made.

RT-580) *6 Manufactured by Sumitomo Bakelite@), PM-9300J Hot'7 Imperial Chemical Industries
Limited, VICTREX 300P *8 Borosilicate glass (Na2O-0aO-B2O
3-8i02) *9 γ-methacryloxyglopyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-
503) *10 Use of the product obtained in the above manufacturing example Patent applicant Calp Industries Co., Ltd. Procedural amendment (spontaneous) December 20, 1980 Commissioner of the Patent Office Kazuo Wakasugi Tono 1, Case indication patent application 1982- 94066 2 Name of the invention Composite resin composition 5 Relationship to the case of the person making the amendment Patent applicant Calb Industries Co., Ltd. 4, Agent 1-1-10-5, Kyobashi, Chuo-ku, Tokyo 104 104 of the specification subject to the amendment Column for Detailed Description of the Invention & Contents of Amendment (1) In the second line from the bottom of page 6 of the specification, between “Polyethersulfone” and “1 etc.”, “Polymethyl methacrylate, polyoxymethylene, polysal 7” On, add polyphenylene oxide r synthesis-rm'.

(2) Add ``Plastic softening at a temperature below the decomposition temperature of synthetic resins'' between ``As a glass'' and ``Low softening point'' on page 4, lines 6-7.

(3) In the 11th line of page 4, "Barium glass, etc. may be mentioned." Examples include salt glass, molybdate glass, sulfate glass, halide glass, chalcogenide glass, hydrated glass, and water-soluble glass, and these can be used alone or in combination. ” is corrected.

(4) Page 17, line 11 [borosilicate glass (
Na2O-OaO-B, 03-slo,
℃)”.

(＞Two people

Claims (1)

[Scope of Claims] 1. A composite resin composition comprising a synthetic resin, a low softening point glass, a silane coupling agent and/or a modified polyolefin. 2. The composite resin composition according to claim 1, wherein the softening point of the glass is 400°C or less. 3. Synthetic resin 5-90 parts by weight and low softening point glass 95
The composite resin composition according to claim 1, wherein 1 to 10 parts by weight of a silane coupling agent and/or 1 to 10 parts by weight of a modified polyolefin are blended to 100 parts by weight of the total amount of ~10 parts by weight. thing. 4. 10 to 80 parts by weight of synthetic resin and low softening point glass 9
The composite resin according to claim 1, which is formed by blending 2 to 7 parts by weight of a silane coupling agent and/or 2 to 7 parts by weight of a modified polyolefin to a total amount of 0 to 20 parts by weight, ioo parts by weight. Composition.