JPS6121161A - Composite resin composition - Google Patents

Abstract

PURPOSE:A composition that is obtained by adding a specific amount of an inorganic filler of a specific particle size to a thermoplastic resin, thus being suitable for use in housings such as for refrigerators, because of improved surface gloss and smoothness of moldings and good fabricability such as printing. CONSTITUTION:(A) 80-98wt%, preferably 85-95wt% of a thermoplastic resin such as polyethylene, vinyl chloride-vinyl acetate resin, ABS or nylon 6 are mixed with (B) 20-2wt%, preferably 15-5wt% of an inorganic filler of 0.2- 20 micron particle sizes.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] This invention relates to a composite resin composition as a material from which molded products with excellent smoothness and gloss can be obtained.

[Prior Art] Various plastic molded products obtained by molding resin compositions containing a thermoplastic resin and an inorganic filler have been developed in order to expand their range of application and provide higher added value. Secondary processing such as printing, painting, and metallization is performed on the surface of the molded product. When performing secondary processing such as printing, painting, and metallizing, plastic surfaces generally have poor receptivity to inks, paints, and metal foils, and are chemically inert, so pretreatment is usually necessary. As a result, polishing treatment, surface treatment with solvent, etc. are performed. (The Society of Polymer Science and Technology, Fundamentals of Plastic Processing, first published on March 25, 1982) [Problems to be solved by the invention] However, plastic molded products obtained using conventional composite resin compositions, in particular, Plastic molded products obtained by blow molding thermoplastic resins containing inorganic fillers have poor surface conditions such as surface gloss and smoothness during molding, and if left as is, the surface will be susceptible to secondary processes such as printing, painting, and metallization. Even after processing, the finish was poor. Therefore, in order to improve the adhesion of ink, paint, etc. to the surface of plastic molded products, complicated pretreatment such as polishing is essential.

[Means for Solving the Problems] Based on the above circumstances, the inventors have found that when processed into plastic molded products, the surface gloss of the plastic molded products is extremely good, and at the same time, As a result of intensive research on composite resin compositions that significantly increase the adhesion of ink and paint without treatment, we found that composite resin compositions consisting of a thermoplastic resin and an inorganic filler with a specific particle size are The present invention was achieved by discovering that the surface condition of the plastic molded product can be made extremely good.

That is, in this invention, the thermoplastic resin is 80 to 98% by weight.
and 20 to 2% by weight of an inorganic filler having a particle size of 0.2 to 20 L.

Examples of thermoplastic resins in this invention include general resins such as polyolefin resins, vinyl chloride resins and copolymer resins thereof, vinylidene chloride resins, vinyl acetate resins, polystyrene and copolymer resins thereof, polyamide resins, polyacetals, Examples include engineering plastics such as polycarbonate, thermoplastic polyester resin, polyphenylene oxide and noryl resin, and polysulfone.

Examples of the polyolefin resin include polyethylenes such as ultra-high density polyethylene, high-density polyethylene, medium- and low-density polyethylene, and linear low-density polyethylene;
Examples include polypropylene such as isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene, polybutene, and 4-methylpentene-1 resin. Copolymers with olefins such as ethylene vinyl chloride copolymers, propylene vinyl chloride copolymers, etc. can also be used.

Examples of the vinyl chloride copolymer resin include vinyl chloride vinyl acetate resin, vinyl chloride vinylidene chloride copolymer resin, and vinyl chloride acrylonitrile copolymer resin.

Examples of the vinyl acetate resin include vinyl acetate resin, polyvinyl acetoacetal, polyvinyl butyral, and the like.

As the polystyrene copolymer resin, for example, A
Examples include BS resin, SAN resin, AC5 resin, and the like.

Examples of polyamide resins include nylon 6, nylon 8, nylon 11. Nylon 66, nylon 610
etc.

The polyacetal may be a single polymer (Delrin) or a copolymer (Duracon).

Examples of the polycarbonate include polycarbonate obtained from bisphenol A and phosgene, polycarbonate obtained from bisphenol A and diphenyl carbonate, and the like.

Examples of the thermoplastic polyester resin include polyethylene terephthalate, polypropylene terephthalate, and the like.

Since the composite resin composition according to the present invention is to be subjected to molding, the various thermoplastic resins may be appropriately selected and used as long as the thermoplastic resin has a moldable molecular weight. be able to. The above various thermoplastic resins may be used alone, or two or more types may be mixed and used as a polymer blend. However, among the above various thermoplastic resins, composite resin compositions for blow molding are preferred. Preferred examples include polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyamide, polycarbonate, and polyethylene terephthalate.

The thermoplastic resin is in an amount of 80 to 98% by weight, preferably 85 to 95% by weight, based on the total weight of the thermoplastic resin and the inorganic filler. It is important that it is included in the composite resin composition.

If the content of the thermoplastic resin is less than 80% by weight or more than 98% by weight, the smoothness and gloss of the resulting molded product will be poor.

Examples of the inorganic filler in this invention include carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and magnesium sulfate, sulfites such as calcium sulfite, talc, clay, mica, asbestos, and glass fibers. , glass peas, silicates such as calcium silicate, montmorillonite, and bentonite, metal powders such as iron, zinc, and aluminum, ceramics such as silicon carbide, silicon nitride, and their whiskers, carbon black, graphite, carbon fiber, etc. These inorganic fillers can be used alone or in combination of two or more of the above inorganic fillers.

Among the various inorganic fillers mentioned above, carbonates, sulfates, silicates, and metal powders are preferred, especially calcium carbonate, 't
The calcium carbonate and barium sulfate, preferably irl barium, talc, mica, and zinc powder, not only improve the surface smoothness and gloss of the plastic molded product, but also improve the heat resistance and abrasion resistance of the plastic molded product. can be done.

The inorganic filler may be in the form of particles, plates, or fibers, but in the present invention, it is important that the particle size is within the range of 0.2 to 2 Jt. Even if the particle size of this inorganic filler becomes smaller than 0.21L,
If the effect is small and the particle size is larger than 201L, the dispersion in the resin composition, the glossiness and smoothness of the plastic molded product, and the smoothness after secondary processing will all deteriorate.

The amount of the inorganic filler is within the range of 20 to 2% by weight, preferably 15 to 5% by weight, based on the total weight of the thermoplastic resin and the inorganic filler. , it is important that it be contained in the composite resin composition. If the content of this inorganic filler is less than 2% by weight and more than 20% by weight, the gloss will be poor.

The composite resin composition according to the present invention may contain plasticizers such as phthalate esters, sebacate esters, adipate esters, etc., as long as they do not impair the glossiness, smoothness, and smoothness after secondary processing of the plastic molded product. Antioxidants such as alkylphenols, antistatic agents such as aliphatic sulfonates and higher alcohol sulfates, colorants such as pigments and dyes,
Lubricant agents such as metal stearate and isobutyl stearate, and other appropriate additives may be added.

The composite resin composition according to the present invention is produced by mixing the thermoplastic resin and the inorganic filler with a mixer such as a ribbon blender, tumble mixer, or Henschel mixer. The above-mentioned thermoplastic resin and the inorganic filler can be obtained by a method of simultaneously cross-talking the above-mentioned various crosstalk machines. Further, in the composite resin composition according to the present invention, a mask resin composition is obtained by mixing and/or kneading a part of the thermoplastic resin and the entire amount of the inorganic filler, and then the mask resin composition is It can also be obtained by mixing the remaining amount of the mask resin composition and diluting the mask resin composition.

The heating temperature during mixing or kneading depends on the type of thermoplastic resin used, but is usually in the range of about 150 to 300°C.

The time required for mixing and kneading differs depending on the type of thermoplastic resin used and the type of mixer or mixer, but in the case of an extruder, it usually takes about 1-15 minutes, and when using a Banbury mixer or Henschel mixer. In this case, it will take about 5 to 20 minutes.

The composite resin composition according to the present invention can be molded into various plastic molded products by compression molding, injection molding, extrusion molding, blow molding, or the like.

[Effects of the Invention] The composite resin composition according to the present invention improves the glossiness of the surface appearance of plastic molded products obtained using the composite resin composition as a material,
Moreover, the surface of the plastic molded product is made smooth, and secondary processing such as printing, painting, and metallization can be suitably performed without pretreatment such as polishing. In particular, the surface condition of molded products obtained by blow-molding the composite resin composition according to the present invention is good, the surface is extremely smooth, has good adhesion to ink and paint, and can be easily polished during printing, painting, etc. No pretreatment is required. Therefore, the composite resin composition according to the present invention can be used in refrigerators, washing machines, vacuum cleaners,
It can be widely applied to plastic molded products such as home appliance housings such as lighting equipment, sports and leisure equipment such as windsurfing equipment, ports, and floats, clothing, wooden boxes, storage cases for medicines, etc.

[Examples] Next, examples of the present invention and comparative examples thereof will be shown to further specifically illustrate the present invention.

(Examples 1 to 24) A composite resin composition having the composition shown in Table 1 was pelletized using a 50 mm single-screw extruder (manufactured by Nakatani Kikai), and the pellets were used to use a blow molding machine (manufactured by Japan Steel Works; VE-3), a hollow molded box with a length of 100 mm, a width of 150 mm, and a height of 200 mm was obtained. The temperature of the mold in the blow molding machine was 45° C., and the molding was carried out by blowing an amount of air almost the same as the internal volume of the molded product. The heating temperature in the blow molding machine was 200-220°C for Example 1-18.22.23, 220-240°C for Example 21.24, and 150°C for Example 19.
~170°C, and 210-23 for Example 20
It was 0°C.

In this example, the following thermoplastic resin and inorganic filler were used.

Symbol PE in Table 1: High density polyethylene, 750LB (MI=0
．． 03, d=0.951) PVC manufactured by Idemitsu Petrochemical Co., Ltd.; polyvinyl chloride, JZ-101F FA manufactured by Shin-Etsu Chemical Co., Ltd., polyamide, Leona 120OF, Asahi Kasei (
Co., Ltd. PC; Polycarbonate, N-3000 Idemitsu Petrochemical Co., Ltd. PBdl, 86 parts by weight of PE and 2 parts by weight of high-density polyethylene [210J (MI=5.8, d=0.967), Idemitsu Petrochemical Co., Ltd. PBd2; 20 parts by weight of polypropylene [E l
00G (MI = 0.5, d = 0.900), manufactured by Idemitsu Petrochemical Co., Ltd.] and 70 parts by weight of PE PBd3; 70 parts by weight of PA and 20 parts by weight of polyethylene terephthalate [RT-580 , manufactured by Toyobo Co., Ltd.] Polymer blend Charcoal 1: Calcium carbonate, average particle size 4.5IL Kinpei Mining Coal 2: Light calcium carbonate, average particle size 0.5#L,
Okutama Kogyo Coal Calcium 3; light calcium carbonate, average particle size 1.0, Okutama Kogyo Coal Calcium 4; calcium carbonate, average particle size full, Kinpei Mining Coal Calcium 5; calcium carbonate, average particle size 13μ Kinpei Mining Co., Ltd. Charcoal production Cal 6: Calcium carbonate, average particle size 20L Kinpei Mining Coal production Cal 7: Light calcium carbonate, average particle size 0.3#L,
Okutama Kogyo Co., Ltd. Cal 8: Calcium carbonate, average particle size 30° Kinpei Mining Talc 1: Talc, average particle size 10. , Talc 2 manufactured by Asada Flour Milling; Talc, average particle size 30IL; Mica manufactured by Asada Flour Milling; Mica, average particle size 15p; Ba manufactured by Kuraray; Barium sulfate, average particle size 3μ; Znl manufactured by Barite Industries; Zinc powder, average particle size 1oIL , Sakai Chemical Co., Ltd. Zn2 *Zinc powder, average particle size 30#L, Sakai Chemical Co., Ltd. The surface gloss of the above hollow molded product is JI 5K-71 for the front part (150 x 200 mm) of this hollow molded product.
05, surface glossy needle (Suga Test Instruments, UGV-50
). The measurement results are shown in Table 1.

The smoothness of the hollow molded product is determined according to JIS for the front part.
According to K-7104, the surface is beautiful as a 0 judgment result visually judged (MR-1, MR-2)
0-t', with some (7) unevenness on the surface (MR
-3, MR-4) with Δ mark 1 Items with silver marks or severe unevenness on the surface (MR-5, MR-4)
-6) are shown in Table 1 with an x mark.

The surface smoothness of the hollow molded product after secondary processing is determined by stamping aluminum foil on the front surface of the hollow molded product using a hot stamping machine, and then checking the appearance finish according to JISK-7.
104, the results of the 0 judgment determined visually are shown in Table 1 as 0, Δ, and x marks, similar to the smoothness described above.

(Comparative Examples 1 to 9) A blow molded product was obtained in the same manner as in the above example using a composition having the composition and blending amount shown in Table 1, and for the blow molded product,
Glossiness, surface smoothness, and smoothness after secondary processing were evaluated in the same manner as in the above examples. Note that the heating temperature in the blow molding machine is 210 to 220°C.

(Hereinafter, blank spaces) Continuation of Table 1 (1) Continuation of Table 1 (2) Procedural amendment June 24, 1985 Patent Application No. 142973 filed in 1988 2 Name of the invention Composite resin composition 3 Amendment Relationship with the case of the person who filed the patent application Patent applicant (1) Address: 1-2 Kanda Izumi-cho, Chiyoda-ku, Tokyo
77 Name Calp Industries Co., Ltd. Representative Tsuyoshi Yamato (2) Address 278-14 Choshoji, Notoyo-cho, Kanzaki-gun, Shiga Prefecture Name Cloud Co., Ltd. Representative Usage 4 Agent address 6-3-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. Karakawa Building 2nd floor 6 Number of inventions increased by the amendment 07 Subject of the amendment Column 8 of “Kyocho Φ Reciprocal Honhaiaki” of the specification Contents of the amendment (1) Stated on page 4, line 17 of the specification "Vinyl chloride vinyl acetate resin" is corrected to "vinyl chloride vinyl acetate copolymer resin".

(2) "Windsurfing, port" written on page 11, line 8 of the specification is corrected to "windsurfing port".

(3) “Idemitsu Petrochemical Co., Ltd.” stated in page 12, line 14, page 13, line 1, page 5, line 8, and page 12 of the specification Corrected to "Kagaku Co., Ltd."

(Continuation of Table 1 on page 18 of the specification (1)
Replace with continuation (1) of Table 1 listed in the attached sheet.

Continuation of Table 1 (1)

Claims (2)

[Claims] (1) Thermoplastic resin 80-98% by weight and particle size 0.2
A composite resin composition comprising 20 to 2% by weight of an inorganic filler of ~20μ. (2) The composite resin composition according to claim 1, wherein the composite resin composition is a composite resin composition for blow molding.