JPS6018536A - Weather-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having matting effect without lowering the characteristic features of the base resin, by compounding a non-conjugated diene rubber-reinforced resin with an epoxy group-containing olefin copolymer. CONSTITUTION:(A) A weather-resistant resin composed of (a) 5-100wt% of a polymer obtained by the polymerization of two or more compounds selected from aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl esters in the presence of a non-conjugated diene rubber polymer and (b) 0-95wt% of a copolymer obtained by the polymerization of two or more compounds selected from aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl esters, is compounded with (B) an olefin copolymer containing epoxy group. The non-conjugated diene rubber polymer of the component A is preferably an ethylene-propylene polymer. The amount of the component B is 0.1-40pts.wt. per 100pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to weatherable thermoplastic resin compositions having excellent matte effects.

Non-conjugated diene rubber-reinforced polymers represented by A E S l (acrylonitrile-ethylene/propylene rubber-styrene polymer) have excellent weather resistance, moldability, mechanical properties, etc., and are used in the vehicle field. It is expected to be used in many fields including.

In the vehicle field, particularly for automobile interior parts, matte finish is desired due to the tendency to emphasize safety or harmony with other parts.

As a method to obtain matte parts, thin embossing etc.
Examples include a method of improving the mold surface and a method of modifying the material. When improving the mold surface, the special molding resin is completely adhered to the mold, which causes severe wear on the mold surface, requiring frequent embossing, and the gloss condition is affected by the molding conditions. Ru.

On the other hand, the addition of fillers or rubbery polymers to resins has been proposed as a material modification, but addition of fillers is unfavorable in terms of physical properties and appearance, and addition of rubbery polymers is not suitable for molded products. At present, 70-marks and weld marks on the surface are so severe that good molded products cannot be obtained.

The present inventors have arrived at the present invention as a result of intensive research into a composition that has excellent surface properties (matte) without impairing the excellent properties of non-conjugated diene-based rubber-reinforced resins.

That is, the present invention provides a weather-resistant thermoplastic resin composition having excellent surface properties (matte) characterized by (1) blending an epoxy group-containing olefin copolymer with a non-conjugated diene-based rubber-reinforced resin. be.

The present invention will be explained in detail below.

The non-conjugated diene-based rubbery polymers constituting the weather-resistant resin (A) include ethylene-propylene copolymer, dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, 1,4-cycloheptadiene, 1 , 5-cyclooctadiene and other non-conjugated dienes Gold copolymerized ethylene-
Ethylene-propylene polymers (i) such as propylene-nonconjugated diene copolymers, homopolymers such as methyl acrylate, ethyl acrylate, butyl acrylate, and propyl acrylate, and other copolymers such as styrene and acrylonitrile. Compounds and acrylic acid ester polymers (11) such as Kogyo Hinoki φ1 day needle removal copolymer, chlorinated polyethylene 0
11) and ethylene -Vinyl acetate, and from the combination (V), <one or more policies selected from a group of trigrams are preferably ethylene -zorobirene polymer.

Aromatic vinyl compounds constituting polymers and copolymers include styrene, α-methylstyrene, methyl-α
-Methylstyrene, vinyltoluene St. Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, and the like.

Examples of the unsaturated carboxylic acid alkyl ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like.

When selected from the group consisting of the three types of compounds mentioned above, two or more types of compounds are used in the polymer and copolymerizable compound. Although there are no restrictions, it is preferable that the non-conjugated diene rubbery polymer be 5 to 70% by weight and the compound be 30 to 95% by weight.Also, there are no particular restrictions on the composition ratio of each compound in the compounds constituting such a polymer. However, preferably 50 to 80% by weight of the aromatic vinyl compound and 20 to 50% by weight of the vinyl cyanide compound and/or the unsaturated carboxylic acid alkyl ester compound. Although there is no particular restriction on the composition ratio, it is preferable that the aromatic vinyl compound be 50 to 80% by weight and the cyanide vinyl compound and/or the unsaturated carboxylic acid alkyl ester compound be 20 to 50% by weight.

The copolymer may be produced in the same reactor during polymerization, or may be produced in a separate reactor.

The weather-resistant resin (A) is composed of 5 to 100 weight % of the above-mentioned polymer and 0 to 95 weight % of the copolymer. If the amount of the polymer is less than 5% by weight, the impact resistance of the final composition will be poor, which is not preferable. It is a copolymer consisting of systemically unsaturated compounds. There is no particular restriction on the composition ratio of the epoxy group-containing olefin copolymer, but the unsaturated epoxy compound is 0.
It is preferably 05 to 95% by weight.

The unsaturated epoxy compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule.

For example, unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and P-glycidyl styrenes represented by the following general formulas (1), (1), and (1). .

1 (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond.) (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. XiJ: CH2-0-1R -C-CH2
(1) \ 1 (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. R is hydrogen or a methyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters , butene carboxylic acid esters, allyl glycidyl ether, 2-
Methyl allyl glycidyl ether, styrene-P-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
1-pentene, 3.4-epoxy-3-methylpentene, 5.6-epoxy-1-hexene, vinylcyclohexene monooxy)', P-f lycidylstyrene, and the like.

As olefins, ethylene, propylene, butene
Examples include 1,4 methylpentene-1.

In addition, as ethylenically unsaturated compounds, olefins, vinyl esters containing c2-6 in the saturated carboxylic acid component, acrylic acid and methacrylic esters and maleic esters containing all 01-8 in the saturated alcohol component, halogen Examples include vinyl compounds, vinyl ethers, N-vinyl lactams, and carboxylic acid amides.

When copolymerizing an unsaturated epoxy compound and an olefin, these ethylenically unsaturated compounds are
Is it copolymerized at 0% by weight or less, especially from 0.1 to 45% by weight? Epoxy group-containing olefin copolymers can be made in various ways. For example, in the presence of an unsaturated epoxy compound and an olefin, and in some cases an ethylenically unsaturated compound total radical generator, 50 to 4000 atmospheres, 40 to 300 atmospheres.
Examples include a method of bringing the mixture into contact at .degree. C., and a method of preparing a polymer by mixing an unsaturated epoxy compound with polypropylene and irradiating it with gamma rays under high vacuum.

There is no particular limit to the amount of the epoxy group-containing olefin copolymer, but it is 0.1 to 40 parts by weight per 100 parts by weight of the weather-resistant resin.
Parts by weight are particularly preferred. If it is less than 0.1 parts by weight, there will be problems with dispersibility;
If the amount exceeds 0 parts by weight, layer peeling tends to occur in the molded product.

In addition, when mixing, use known stabilizers, antistatic agents, erasing agents, etc.
Additives such as dyes and pigments may be added as appropriate.

Examples will be described below, but the present invention is not limited thereto.

Example A weather-resistant resin is blended with an epoxy group-containing olefin copolymer or a commonly known matting agent, and a Banbury mixer is used.
After mixing, it was pelletized.

Various test specimens were prepared from the obtained pellets according to conventional methods, and physical properties and surface gloss were measured.

Table 1 shows the composition, physical properties, and surface gloss of each composition.

Note that the weather-resistant resin (AES resin) used in this example
and the epoxy group-containing olefin copolymer are copolymers obtained by the following method.

0 weather-resistant resin ethylene-propylene-ethyritene norbornene (iodine value 8.5, Mooney viscosity 61. Propylene content 4
3% by weight), 55% by weight of styrene, and 25% by weight of acrylonitrile were polymerized by a known solution polymerization method to obtain AES resin-1.

In addition, 30 parts by weight of ethylene-propylene-ethylidenenorbornene, 50% by weight of styrene, and 20% by weight of acrylonitrile were polymerized by a known suspension polymerization method, and a styrene-acrylonitrile copolymer (7o/30) was separately polymerized by suspension polymerization. Mix in beads at a ratio of 1:1 with A.
ES resin-2 was obtained.

Olefin copolymer containing zero engineering poxy group 200 yen for normal autoclave type polyethylene manufacturing equipment
Ethylene monomer compressed to 0 ky/cr/l,
Add glycidyl methacrylate and vinyl acetate together with a catalyst (di-t-butyl peroxide), maintain the temperature at 150-300°C with stirring, and carry out bulk polymerization for several minutes.
The copolymer was separated through a separator and taken out.

*1 Ethylene-glycidyl methacrylate-vinyl acetate copolymer (composition ratio 9O-7-3) *2 Ethylene-glycidyl methacrylate copolymer (composition ratio 9O-10) *3 Merck, Micron White #5000 manufactured by Hayashi Kasei Co., Ltd.
*4 Styrene-butadiene block polymer Toughprene A manufactured by Asahi Kasei *5 Notutina Izotsu impact strength (%#, -30°C) and color difference after irradiation for 1'-1000 hours and color difference patent applicant Sumitomo Naugatuck Co., Ltd.

Claims (1)

[Scope of Claims] 1) Polymerization of two or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds in the presence of a nonconjugated diene-based rubbery polymer. Polymer (a) 5 to io obtained by
Copolymer (b) obtained by polymerizing two or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds. A weather-resistant thermoplastic resin composition comprising ~95% by weight of a weather-resistant resin (8) containing an olefin copolymer containing an epoxy group (2) a non-conjugated diene-based rubbery polymer containing ethylene- The composition according to claim 1, which is one or more polymers selected from the group consisting of propylene polymers, acrylic acid ester polymers, chlorinated polyethylenes, and ethylene-vinyl acetate copolymers. 3) The composition according to claim 1, wherein the epoxy group-containing olefin copolymer (B) is a copolymer consisting of an epoxy group-containing compound and an olefin. 4) Epoxy group-containing olefin copolymer (composition according to claim 1, wherein the rice grains are a copolymer consisting of an epoxy group-containing compound, an olefin, and an ethylenically unsaturated monomer. 5) Weather-resistant resin The composition according to claim 1, wherein 11 to 40 parts by weight of the epoxy group-containing olefin copolymer (B) 'kO is blended per 100 parts by weight of (A).