JPS6137836A - Matte thermoplastic resin composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent matte effect, impact resistance, and processability, made by incorporating a polyolefin modified with an acid and/or an olefin copolymer containing epoxy groups into a methacrylic resin. CONSTITUTION:100pts.wt. methacrylic resin (A) (e.g. a polymethyl methacrylate) is kneaded together with 0.1-100pts.wt. (graft) copolymer (B) of 50-99.5wt% olefin with an unsaturated carboxylic acid (derivative) [e.g. ethyl (meth)acrylate] and/or copolymer (C) which contains epoxy groups and consists of either an unsaturated epoxy compound [e.g. glycidyl (meth)acrylate] in an amount of 0.05-95wt% and an olefin or these with an ethylenically unsaturated compound.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention The present invention relates to a high hardness impact resistant thermoplastic resin composition having an excellent matting effect.

Methacrylic resin has the best transparency of all plastics, and has excellent impact resistance and weather resistance, and is easily colored, so it is used as interior and exterior materials for airplanes, automobiles, signboards, displays, etc. It is used in a wide range of fields such as lighting materials. Note that in the fields in which the resin molded product is used, it is often desirable to have a matte surface, and especially in the case of automobile interior parts, a matte finish is desired for safety or decorative purposes.

Conventionally, there are two ways to obtain matte resin molded products: one is to apply a matte finish to the molded product surface from the mold surface, such as by using a mold with a matte finish on the surface, and the other is to apply fillers or other polymers to the resin. An example of this method is to add it and make it matte from the viewpoint of the material. .

However, the method of matting from the mold surface has drawbacks such as severe abrasion of the mold surface because the molding resin is completely adhered to the mold, and the surface of molded products with complex shapes cannot be matted. be.

On the other hand, in the method of matting from the material side, non-uniform matting occurs due to poor dispersion of additives.

Furthermore, adding fillers impedes transparency, and adding other polymers reduces hardness or moldability, which is undesirable.

The present inventors have arrived at the present invention as a result of intensive research into resins that have a matting effect without impairing the excellent physical properties inherent to methacrylic resins.

That is, the present invention provides a matte thermoplastic resin composition in which a methacrylic resin is acid-modified.

■ Structure of the invention The present invention will be explained in more detail below.

The methacrylic resin in the present invention is a homopolymer of an alkyl methacrylate ester and a copolymer mainly composed of an alkyl methacrylate ester. As the methacrylic acid alkyl ester, methyl methacrylate,
It is a methacrylic acid alkyl ester having a C1-4 alkyl group such as ethyl methacrylate. In addition, examples of compounds copolymerized with methacrylic acid alkyl esters include ethyl acrylate, butyl acrylate, etc.
Examples include acrylic esters having 5 alkyl groups, aromatic vinyls such as styrene and α-methylstyrene, and vinyl cyanides such as acrylonitrile and methacrylonitrile. Preferred are polymethyl methacrylate and methyl methacrylate)'jz50 copolymers with saturated carboxylic acids or derivatives thereof, and polymers in which unsaturated carboxylic acids or derivatives thereof are grafted onto polyolefins. The composition ratio of the acid-modified polyolefin is not particularly limited, but it is preferably 50 to 99.5% by weight of the olefin. In addition, it also includes those in which part of the olefin is replaced with other ethylenically unsaturated monomers.

As olefins, ethylene, fluoropylene, butene
Examples include 1,4-methylpentene-1, with ethylene and propylene being particularly preferred.

Examples of unsaturated carboxylic acids or derivatives thereof include monocarboxylic acids such as acrylic acid and methacrylic acid; monocarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride; Examples include carboxylic acid alkyl esters such as methyl meth)acrylate and ethyl (meth)acrylate.

In addition, as ethylenically unsaturated compounds, olefins, vinyl esters containing saturated carboxylic acid components KC2 to 6, acrylic acid and methacrylic esters containing C1 to 8 as saturated alcohol components, maleic esters,
Examples include vinyl halides, vinyl ethers, N-vinyl lactams, -carboxylic acid amides, and the like.

Furthermore, the epoxy group-containing olefin copolymer used in the present invention is a copolymer consisting of an unsaturated epoxy compound and an olefin, or these and an ethylenically unsaturated compound. The composition ratio of the epoxy group-containing olefin copolymer is not limited to %, but the unsaturated epoxy compound is 0.
Preferably, the weight is 0.05-95.

The unsaturated epoxy compound is a compound having an epoxy group and an unsaturated group copolymerized 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 (]), (If), and (1). .

(R is a 02-18 hydrocarbon group having an ethylenically unsaturated bond.) (R is a 02-18 hydrocarbon group having an ethylenically unsaturated bond (
This is Psakuryon. Xke-CH9-0-- (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-
Examples include 1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and P-glycidylstyrene.

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

Examples of ethylenically unsaturated compounds include olefins, vinyl esters containing C2-6 in the saturated carboxylic acid component, acrylic and methacrylic esters and maleic esters containing 01-8 in the saturated alcohol component, halogen Examples include vinyl compounds, vinyl ethers, N-vinyl lactams, and carboxylic acid amides.

In particular, vinyl esters represented by vinyl acetate are preferred.

When copolymerizing an unsaturated epoxy compound and an olefin, these ethylenically unsaturated compounds are
Copolymerization is carried out below zero weight, especially from 0.1 to 45% by weight.

Epoxy group-containing olefin copolymers can be made in various ways. For example, an unsaturated epoxy compound and an olefin, or depending on the situation, an ethylenically unsaturated compound, in the presence of a radical generator at 50 to 4000 atm and 40 to 30'
There is no particular restriction on the amount of the 7-group-containing olefin copolymer blended by mixing polypropylene with an unsaturated epoxy compound and irradiating it with gamma rays under high vacuum. It is particularly preferable that the amount is 0.1 to 100 parts by weight. If it is less than 0.1 part by weight, a sufficient matting effect cannot be obtained on the resin surface, and if it exceeds 100 parts by weight, transparency and impact resistance may deteriorate. descend.

The method of mixing the methacrylic resin and the acid-modified polyolefin polymer and/or the epoxy group-containing olefin copolymer in the present invention includes a Banbury mixer, a single-screw extruder, and a cross-wire block. A known mixing method using a twin-screw extruder or the like can be mentioned.

In addition, known stabilizers, antistatic agents, lubricants,
Additives such as dyes and pigments may be added as appropriate.

Examples will be described below, but the present invention is not limited to these in any way.

Example: Water-maleic acid-modified polyethylene), epoxy group-containing olefin copolymer (ethylene-glycidyl methacrylate copolymer), and acrylic rubber were kneaded at the compounding ratios (parts by weight) shown in Table IK, and various compositions were prepared. Obtained.

Various test pieces were prepared from the obtained composition and their properties were evaluated. The evaluation results are shown in Table-1.

Remaining days *1 Sumipex B manufactured by Sumikata Chemical Co. *2 Sumipex HT-01 manufactured by Sumikata Chemical Co. *3 Manufactured by Daicel Corporation
Cevian MASIO”*4 0.5 parts by weight of maleic anhydride is added to 100 parts by weight of polyethylene powder, and after mixing 20 parts by weight
The mixture was kneaded for about 3 minutes using two rolls heated to 0°C to obtain maleic anhydride-modified polyethylene sheets.

After cooling, it was ground into a 3-square die.

*5 Ethylene monomer and glycidyl methacrylate compressed to 2000 #/ca were added together with a catalyst (di-t-butyl peroxide) to a normal autoclave type polyethylene manufacturing equipment, and the mixture was heated to 150 ~
Bulk polymerization was carried out at 300° C. for several minutes, and the copolymer was separated through a separator and taken out.

*6 "Acryloid KF-700" manufactured by Rohm &'Hass *7 High molecular weight polymethyl with an average molecular weight of 1 million ■ Effects of the invention Acid-modified polyolefin polymer and/or epoxy group-containing olefin copolymer is placed on methacrylic resin The composition has an excellent matting effect. Furthermore, the composition of the present invention has superior impact resistance and processability compared to compositions using conventional matting agents.

Claims (1)

[Scope of Claims] 1) A matte thermoplastic resin composition comprising a methacrylic resin blended with an acid-modified polyolefin polymer and/or an epoxy group-containing olefin copolymer. 2) The composition according to claim 1, wherein the amount of the acid-modified polyolefin polymer and/or the epoxy group-containing olefin copolymer is 0.1 to 100 parts by weight per 100 parts by weight of the methacrylic resin.