JPH0798887B2 - Resin composition having a stone tone - Google Patents

Description

The present invention relates to a resin composition having a stone tone based on a rubber-reinforced styrene resin.

(Prior Art) Rubber-reinforced styrene resin represented by ABS resin (butadiene-based rubber-reinforced acrylonitrile-styrene) has an excellent balance of impact resistance and workability, and is suitable for vehicle parts, office machine parts, sundries, etc. Widely used. At the time of use, the rubber-reinforced styrenic resin is colored by blending dyes and pigments like other resins. Usually, these dyes and pigments are in the form of fine particles and uniformly dispersed in the resin, and they are used as monochromatic molded articles. In some applications, metallic powders are obtained by dispersing metal powder.

However, there is a demand for a more calm appearance, for example, a marble-like molded product, as compared with a conventional single-colored product, especially a colored product or a metallic-like molded product that gives a feeling of plastic, due to a change in lifestyle. Further, the metallic-like molded product containing the metal powder has a drawback that rust is generated during use.

(Problems to be Solved by the Invention) A marble-like molded article is generally obtained by melt-mixing two or more kinds of resins having different melt viscosities and hues. There was a limitation in usage.

(Means for Solving Problems) In view of the above-mentioned problems, the present inventors have earnestly studied a molding material which brings a calm feeling, and as a result, colored fine particles of a fluorine-based resin were changed to a rubber-reinforced styrene-based resin. The compounded composition is such that the colored fine particles are not dissolved in the rubber-reinforced styrene resin at the time of molding as well as at the time of molding, and the coloring agent in the particles is also eluted in the rubber-reinforced styrene resin. However, the present invention has been found to have a stone tone such as sandstone or granite due to being uniformly dispersed in the resin as colored particles, and has arrived at the present invention. Further, the composition of the present invention maintains and retains the original excellent properties of the rubber-reinforced styrene resin.

That is, the present invention provides a rubber-reinforced styrene resin (A) 10
0 to 20 parts by weight of the average particle size containing the pigment is 0.1 to 20
It is intended to provide a resin composition having a stone tone, which is characterized in that 0.1 to 10 parts by weight of fluorine-based resin particles (B) of 0 μ are dispersed.

Hereinafter, the resin composition of the present invention will be described in detail.

The rubber-reinforced styrene resin (A) in the present invention is
A graft copolymer obtained by polymerizing an aromatic vinyl monomer and a monomer copolymerizable therewith in the presence of rubber, or the graft copolymer and an aromatic vinyl monomer. And an aromatic vinyl group polymer obtained by polymerizing a copolymer and a monomer copolymerizable therewith, if necessary.

As the rubber, butadiene rubber (i) such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, etc., binary copolymer (EPR) consisting of ethylene and propylene or butene, ethylene, propylene or butene, and Ethylene-α olefin rubber (i.e., terpolymer (EPDM) composed of non-conjugated dienes)
i), in the presence or absence of a cross-linking agent, an alkyl acrylate having an alkyl group having 1 to 16 carbon atoms (methyl acrylate, ethyl acrylate, butyl acrylate,
Alkyl acrylate rubber (iii) obtained by polymerizing or copolymerizing one or two or more of (2-ethylhexyl acrylate, etc.), and optionally one or more of other copolymerizable monomers. Examples thereof include ethylene-vinyl acetate copolymer (iv), chlorinated polyethylene (v), and the like, and one kind or two or more kinds can be used.

Aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene,
Dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene, etc. are exemplified, and one or more kinds can be used.

As the monomer copolymerizable with the aromatic vinyl monomer,
Vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile,
Unsaturated carboxylic acid alkyl ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, maleimide,
N-phenylmaleimide, N-methylmaleimide, N-
Examples include maleimide-based monomers such as cyclohexylmaleimide and unsaturated amide-based monomers such as acrylamide and methacrylamide, and one or more of them can be used.

Preferred examples of the rubber-reinforced styrene resin include butadiene-based rubber-reinforced acrylonitrile-styrene copolymer (ABS) and butadiene-based rubber-reinforced styrene polymer (HIP
S), butadiene rubber reinforced methyl methacrylate-styrene copolymer (MBS), butadiene rubber reinforced acrylonitrile-methyl methacrylate-styrene copolymer (ABSM), butadiene rubber reinforced acrylonitrile-α
-Methylstyrene-styrene copolymer, butadiene-based rubber-reinforced acrylonitrile-α-methylstyrene-methylmethacrylate, styrene copolymer, butadiene-based rubber-reinforced styrene-N-phenylmaleimide copolymer, butadiene-based rubber-reinforced acrylonitrile-styrene- Examples thereof include N-phenylmaleimide copolymers and butadiene rubber-reinforced styrene-methylmethacrylate-N-phenylmaleimide copolymers. Further, the butadiene rubber (i) in these copolymers is ethylene-α, respectively.
The thing substituted by the olefin type rubber (ii), the alkyl acrylate type rubber (iii), the ethylene-vinyl acetate copolymer (iv), or the chlorinated polyethylene (v) can also be mentioned. These can be used alone or in combination of two or more.

As a method for producing the rubber-reinforced styrene-based resin, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof is used.

The rubber-reinforced styrene resin (A) may be a non-colored product, but it may be colored with a conventionally known dye or pigment. In particular, it is preferable that the colored fluororesin particles have a hue different from that of the fluororesin particles in order to make the dispersion of the fluororesin particles clear and to give a feeling of stone tone.

The form of the rubber-reinforced styrene resin (A) is not particularly limited, and examples thereof include beads, pellets, powder, latex and the like.

In the present invention, the average particle size containing dyes and pigments is 0.
Fluorine resin particles of 1 to 200 μm are dispersed as colored particles in a rubber-reinforced styrene resin.

If the average particle size is less than 0.1 μ, it is difficult to obtain a right-eye tone molded product as a monochromatic product. On the other hand, if it exceeds 200μ, the excellent impact resistance, which is the original feature of rubber-reinforced styrene resin, is reduced. It is preferably 1 to 100 μ.

Examples of dyes and pigments in the colored particles include known dyes and pigments that have been conventionally used in various resins including fluorine-based resins, and there is no limitation on the type, combination, and amount used.

For example, insoluble azo and condensed azo series, anthraquinone series, isoindolinone series, perylene series, perinone series,
Dioxazine type, phthalocyanine type, quinacridone type,
Examples include heterocyclic organic dyes and inorganic pigments such as carbon black, titanium oxide, red iron oxide, iron black, navy blue, and ultramarine. Regarding the amount of dyes and pigments used,
It is preferably 0.01 to 20 parts by weight per 0 parts by weight. 0.0
If it is less than 1 part by weight, it becomes difficult to obtain a granite tone. Also, 2
When it exceeds 0 parts by weight, when it is dispersed in the rubber-reinforced styrene resin, it is in a state of being eluted from the fluorine-based resin particles to the rubber-reinforced styrene resin, and the particle dispersion is unclear, and a good stone-tone molded product is obtained. Tends to be difficult.

As the fluororesin, polytetrafluoroethylene,
Tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer,
Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, fluorine Examples thereof include amine polymers, and one kind or two or more kinds can be used.

These resins can be obtained by known methods such as suspension polymerization, emulsion polymerization, bulk polymerization and solution polymerization.

Since the colored fluorine-based resin particles (B) are homogeneously dispersed in the rubber-reinforced styrene-based resin (A) without being completely melted, a stone tone such as sandstone or granite is exhibited. It is preferable that the colored particles have a melting temperature higher than that of the rubber-reinforced styrene resin.

Further, the dispersion of the colored fluorine-based resin particles (B) in the rubber-reinforced styrene-based resin (A) is performed by the rubber-reinforced styrene-based resin (A).
It is preferable that the temperature is higher than or equal to the melting temperature of and lower than or equal to the melting temperature of the fluororesin.

Examples of the method of incorporating the dye / pigment include melt mixing of the fluororesin and the dye / pigment, addition of the dye / pigment to the polymerization system during the polymerization of the fluororesin.

The colored fluororesin particles (B) are dispersed in the range of 0.1 to 10 parts by weight per 100 parts by weight of the rubber-reinforced styrene resin (A). If it is less than 0.1 parts by weight, it will not have a good stone tone,
If it exceeds 0 parts by weight, the composition is inferior in impact resistance and workability, which is not preferable.

As a method for dispersing the colored fluororesin particles (B) in the rubber-reinforced styrene resin (A), a known compounding device such as a Banbury mixer, a roll or an extruder can be employed.

It should be noted that, at the time of mixing, if necessary, dyes and pigments for coloring the rubber-reinforced styrene resin (A), an antioxidant for the composition, an ultraviolet absorber, an antistatic agent, a lubricant, a plasticizer, a hardener Additives such as a flame retardant and a release agent can be added.
In addition, polyamide, polyacetal, polycarbonate,
A thermoplastic resin such as polybutylene terephthalate, polyphenylene oxide, polymethylmethacrylate, or polyvinyl chloride can also be appropriately blended.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The numbers of parts and percentages are shown on a weight basis.

Examples and Comparative Examples Commercially available rubber-reinforced styrene-based resin and pre-colored resin particles are melt-mixed, pelletized and then injection-molded by injection molding to obtain a test piece for measuring Izod impact strength and a flat plate for appearance evaluation (70 mm
X 120 mm x 3 mm) was created.

The composition ratio and the evaluation results are shown in Table 1.

Rubber-reinforced styrene resin (A) A-1 (HIPS): White impact-resistant polystyrene pellets with rubber content of about 5% A-2 (ABS): Gray ABS resin powder A-3 (heat-resistant ABS) with rubber content of about 15% ): White heat resistance of rubber containing about 15% rubber compounded with α-methylstyrene-acrylonitrile copolymer
ABS resin pellets A-4 (heat resistant AES): Gray AES resin pellets with a rubber content of about 15% Fluorine-based resin particles (B) B-1: Melted and mixed with 99% polytetrafluoroethylene and 1% carbon black Black particles.

(Average particle size: 50 μ) B-2: Polytetrafluoroethylene 98%, titanium oxide 1.
Gray particles made by melt mixing 6% and 0.4% carbon black.

(Average particle size: 15μ) B-3: ethylene-tetrafluoroethylene copolymer 99.7
% And Pelogen Red 0.3% red particles.

(Average particle diameter: 70μ) Styrenic resin particles (b) b-1: Styrene-acrylonitrile resin (acrylonitrile content of about 28%) Black particles obtained by melting and mixing 99% and carbon black 1%.

(Average particle diameter: 50 μm) b-2: Black particles obtained by melting and mixing 99% polystyrene and 1% carbon black.

(Average particle size: 50μ) <Effects of the Invention> The composition of the present invention provides a molded product having a stone tone such as sand stone and granite and excellent physical properties (impact resistance, etc.).

Further, such a molded product does not have the problem of corrosion (rust) in the conventional metallic-like molded product.

Claims (1)

[Claims] 1. A fluorinated resin particle (B) having an average particle diameter of 0.1 to 200 μm and containing 0.1 to 10 parts by weight of 100 parts by weight of a rubber-reinforced styrene resin (A) and having a mean particle diameter of 0.1 to 200 μm dispersed therein A resin composition having a stone tone characterized by: