JPH0455459A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in clearness and resistance to heat, impact and chemicals, comprising rubber-reinforced styrene-based resin, saturated polyester resin and two kinds of each specific copolymer. CONSTITUTION:The objective composition can be obtained by incorporating 100 pts. wt. of a composition comprising (A) 10 - 85 wt.% of a rubber-reinforced styrene-based resin prepared by graft polymerization of an aromatic vinyl compound, vinyl cyanide etc. in the presence of a rubbery polymer, (B) 5 - 50 wt.% of a saturated polyester resin and (C) 10 - 70 wt.% of an alpha-methylstyrene-based copolymer prepared from alpha-methylstyrene, vinyl cyanide compound and, where needed, an aromatic vinyl compound and/or unsaturated carboxylic alkyl ester compound with (D) 0.2 - 50 pts. wt. of an epoxy group-contg. olefinic copolymer prepared from an olefinic and epoxy group-contg. unsaturated compound etc. The content of said rubbery polymer in the components A, B, C plus D should be 5 - 25 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermoplastic resin composition that has excellent image clarity, heat resistance, chemical resistance, and impact resistance.

<Prior art> Polystyrene, styrene-acrylonitrile copolymer,
Styrenic resins such as ABS resin, AES resin using EPDM rubber or acrylic rubber as a rubber component, and AAS resin have an excellent balance of physical properties and dimensional stability, and are used in a wide range of fields. Among them, there are many applications in the automobile field, but in this case, chemical resistance such as gasoline resistance and brake oil resistance is always an issue, and improvement in this aspect has been an important issue. On the other hand, saturated polyester resin is already known as a polymer with excellent chemical resistance, but since it has poor impact resistance, it has been proposed to blend ABS resin with saturated polyester resin (Japanese Patent Publication No. 47-80421. -25261).

<Problems to be Solved by the Invention> However, compositions made of ABS resin and saturated polyester resin have problems such as insufficient impact resistance and poor heat resistance.

Furthermore, although these compositions are painted for the purpose of decoration or improving weather resistance, there is a problem in that the sharpness of the painted surface is also poor.

Means for Solving Problems〉 As a result of intensive study on improving the above-mentioned quality problems of a composition consisting of a rubber-reinforced styrenic resin and a saturated polyester resin, the present inventor has developed a rubber-reinforced styrenic resin and a saturated polyester resin. The inventors have discovered that a composition composed of a saturated polyester resin and two specific copolymers has excellent image clarity, as well as excellent heat resistance, impact resistance, and chemical resistance, and has thus arrived at the present invention.

That is, the present invention provides a rubber-reinforced styrene obtained by graft polymerizing an aromatic vinyl compound (ii) and a vinyl cyanide compound and/or another vinyl compound (iii) in the presence of a rubbery polymer (i). 10 to 85% by weight of system resin, (b) 5 to 50% by weight of saturated polyester resin, and 0 a-methylstyrene (i), vinyl cyanide compound (i), and aromatic vinyl compound (α-methyl Containing 0 olefin (i) and epoxy group It is characterized in that it contains 0.2 to 50 parts by weight of an unsaturated olefin copolymer, and the rubbery polymer content in the composition (A10B10+D) is 5 to 25% by weight. The present invention provides a thermoplastic resin composition.

0 Rubber-reinforced styrenic resin Rubber-reinforced styrenic resin is a resin obtained by grafting an aromatic vinyl compound (ii) with a vinyl cyanide compound and/or another vinyl compound (ii) in the presence of a rubbery polymer (i). It is a resin obtained by polymerization.

Rubbery polymer (i) in rubber-reinforced styrenic resin,
There is no particular restriction on the composition ratio of aromatic vinyl compound (h) and compound (1ii), but rubbery polymer 10
-70% by weight, preferably 15-70% by weight of aromatic vinyl compounds and 5-50% by weight of compounds.

Examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, acrylic ester copolymer, chlorinated polyethylene, etc.
They can be used alone or in combination of two or more. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and the like. There are no particular restrictions on the particle size and gel content of the rubbery polymer when produced by emulsion polymerization, but it is desirable that the average particle size is 0.1 to 1 μm and the gel content is 0 to 95%.

Examples of aromatic vinyl compounds include styrene, a-methylstyrene, 0-methylstyrene, m-methylstyrene, and p-methylstyrene.
-Methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene,
Examples include vinylnaphthalene, which can be used alone or in combination of two or more. Particularly preferred are styrene and a-methylstyrene.

Other vinyl compounds that constitute rubber-reinforced styrenic resins together with rubbery polymers and aromatic vinyl compounds include unsaturated nitrile compounds such as acryloniatrile, methacrylonitrile, and fumaronitrile, methyl (meth)acrylate, and ethyl (meth)acrylate. ) acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and other unsaturated carboxylic acid alkyl ester compounds, each of which can be used alone or in combination of two or more. Particularly preferred are unsaturated nitrile compounds.

There is no limit to the grafting rate of the graft polymer, but it is preferably 25 to 150%. As a polymerization method for the graft polymer and copolymer, known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination thereof are used.

0 Saturated polyester resin (B) Examples of the saturated polyester resin used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyester-ether brosoxypolymer having a polyester hard segment and a polyether soft segment, etc. It is synthesized from 4-butanediol and terephthalic acid or dimethyl terephthalate and ethylene glycol. Note that these can be used alone or in a mixture of two or more. Particularly preferred is polybutylene terephthalate.

(C) α-Methylstyrene copolymer ◎α-methylstyrene copolymer refers to α-methylstyrene (i), vinyl cyanide compound (ii) and, if necessary, an aromatic vinyl compound (α- (excluding methylstyrene) and/or an unsaturated carboxylic acid alkyl ester compound (ili).

Suitable for composition of α-methylstyrene copolymer.

Further, the intrinsic viscosity (dimethylformamide solution, 30° C.) of the α-methylstyrene copolymer is preferably 0.3 to 1.0.

As for each compound constituting the α-methylstyrene copolymer, the same compounds as those described in the section of rubber-reinforced styrene resin (2) can be mentioned.

Examples of methods for producing the α-methylstyrene copolymer include emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

Olefin copolymer containing 0-functional epoxy group ◎ The olefin copolymer containing epoxy group is a copolymer consisting of olefin (i) and an epoxy group-containing compound or an epoxy group-containing compound and an ethylenically unsaturated compound (ii) .

The composition of the epoxy group-containing olefin copolymer is not particularly limited, but preferably 99.95 to 5% by weight of olefin, 0.05 to 95% by weight of epoxy group-containing compound, and θ to 40% by weight of ethylenically unsaturated compound. , especially olefins 99-50% by weight, epoxy group-containing compounds 1-50%
% by weight and ethylenically unsaturated compounds from 0 to 80% by weight.

As olefins, ethylene, propylene, butene
Examples include 1,4 methylpentene-1, used alone or with 2
More than one species can be used.

Particularly preferred is ethylene.

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

Examples thereof include unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated clyridyl ethers, epoxy alkenes, and P-glycidyl styrenes represented by the following general formulas (I), (2), and (2).

(R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond.) (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. X is -CH2-0-(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, allylcricidyl ether, 2-
Methyl allyl glycidyl ether, styrene-P-glycidyl ether, 3,4-epoxybutene, 8,4-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, which can be used alone or in combination of two or more. Glycidyl (meth)acrylate is particularly preferred.

In addition, examples of ethylenically unsaturated compounds include vinyl esters containing C2 to 6 in the saturated carboxylic acid component, acrylic and methacrylic esters and maleic esters containing C+ to 8 in the saturated alcohol component, and vinyl halides. , vinyl ethers, N-vinyl lactams,
Examples include carboxylic acid amides. In particular, vinyl esters represented by vinyl acetate are preferred.

Epoxy group-containing olefin copolymers can be made in various ways. For example, an unsaturated epoxy compound and an olefin, in some cases an ethylenically unsaturated compound, are mixed in the presence of a radical generator at 50 to 4000 atm and 40 to 300 atm.
Examples include a method of contacting at °C, and a method of mixing an unsaturated epoxy compound with polypropylene and irradiating it with gamma rays under high vacuum to prepare a polymer.

0 Thermoplastic Resin Composition The composition of the present invention comprises the above-mentioned rubber reinforced styrenic resin (A
)10-85% by weight, saturated polyester resin @5-50
Weight % and α-methylstyrene copolymer C) 10~
2 to 50 parts by weight of an epoxy group-containing olefin copolymer (D) is blended per 100 parts by weight of a composition consisting of 70% by weight, and the composition (A+B 10+D) contains a rubber-like polymer. The amount of the composition is between 5 and 25% by weight.

Outside this range, a composition with excellent image clarity, heat resistance, impact resistance, and chemical resistance cannot be obtained. From the level of heat resistance, impact resistance, and chemical resistance, as well as the balance of these physical properties, (A) 20 to 70% by weight, @10
~40% by weight and (C) 20-50% by weight, 01-2
0 parts by weight (100 parts by weight of A+B+C) and a rubbery polymer content of 10 to 20% by weight.

There are no restrictions on the mixing order and state of the rubber-reinforced styrene resin (A), saturated polyester resin (A), α-methylstyrene copolymer q, and epoxy group-containing olefin copolymer 0, and pellets, Examples include simultaneous mixing of the four components (8), (c), 0, and 0 in the form of beads, powder, etc., and a method of premixing specific components and then mixing other components. As a mixing method, a known method such as a Banbury mixer roll or an extruder can be employed.

In addition, antioxidants, ultraviolet absorbers,
Additives such as light stabilizers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers, metal flakes, reinforcing materials, and fillers can be added. In addition, polyacetal, polycarbonate, polyamide,
Thermoplastic resins such as polyphenylene oxide, polymethyl methacrylate, and polyvinyl chloride may also be appropriately blended.

Next, the present invention will be specifically explained using reference examples, working examples, and comparative examples, but the present invention is not limited by these in any way. Note that the number of copies and percentages are both shown based on important criteria.

Reference example-1 Rubber reinforced styrene resin prisoner Various resins were obtained based on the compositions shown in Table-1.

Reference Example-2 Polyester resin B: Polybutylene terephthalate (PBT) Viscosity average molecular weight 80.000 Reference Example-3 α-methylstyrene copolymer 0 Various copolymers were obtained based on the compositions shown in Table-2. Ta.

Reference example-4 Epoxy group-containing olefin copolymer 0 Various copolymers were obtained based on the compositions shown in Table 3.

Table-1 *1. Polybutadiene with an average particle size of 0.45μ and 88% gel*2. Cross-linked polybutyl acrylate with an average particle size of 0.8μ *8. Iodine number 21, Mooney viscosity 75, propylene content 50% ethylene-propylene-ethylidene norbornene exogenous styrene-free 57xO nitrile Table-2 Table-8 *1 *2 *3 *4 α-Methylstyrene acrylonitrile methyl methacrylate 30 °C1 dimethylformamide solution *1 *2 *8 *4 Ethylene glycidyl methacrylate vinyl acetate melt flow index JIS K-6760 (190°C) To each obtained in Example Reference Examples 1 to 4 ~ ◎ Ingredients are shown in Table 4 Various compositions were obtained by collectively kneading the compositions shown.

Table 4 shows the physical properties of the obtained composition.

The test method is as follows.

1) Impact strength ASTM D-256, 1/4 inch, notched Izot 2) Heat resistance ASTM D-648, 1/4 inch, 18.6 kg/
- Load 3) Chemical resistance A test piece of 150 + w x 20 m x 8 m was molded, and dioctyl phthalate was applied to the test piece under 1.5% strain. After 48 hours in an 80°C oven, the presence or absence of cracks was determined. I judged it.

4) Sharpness: A flat plate of 90 m x 150 m x am was formed using an injection molding machine, and a urethane paint made by Nihon Yushi Corporation - Hiureta: 15100' was applied onto the flat plate using a spray gun to a coating film thickness of 80 μm. did.

The painted molded product was baked in a 65°C oven for 30 minutes, and was then evaluated for image clarity.

■ The image clarity of the painted surface was measured at an incident angle of 60 degrees using an image clarity measuring device "ICM-ID" manufactured by Suga Test Instruments.

■ A metal bar on a straight line was held stationary in a space of LOW above the painted surface, and the sharpness of the metal bar reflected on the painted surface was visually judged.

O: The metal bar is clearly reflected in a straight line on the painted surface, and is good. Moreover, it has an excellent balance of physical properties among impact resistance, heat resistance, and chemical resistance, and is very useful industrially.

Claims (1)

[Scope of Claims] (A) A rubber obtained by graft polymerizing an aromatic vinyl compound (ii) with a vinyl cyanide compound and/or another vinyl compound (iii) in the presence of a rubbery polymer (i). 10 to 85% by weight of reinforced styrenic resin, (B) 5 to 50% by weight of saturated polyester resin, and (C) α-methylstyrene (i), vinyl cyanide compound (ii) and aromatic vinyl compound as necessary. (α−
Composition 10 consisting of 10 to 70% by weight of an α-methylstyrene copolymer consisting of (excluding methylstyrene) and/or an unsaturated carboxylic acid alkyl ester compound (iii)
(D) 0.2 to 50 parts by weight of an epoxy group-containing olefin copolymer consisting of an olefin (i) and an epoxy group-containing unsaturated compound or an epoxy group-containing unsaturated compound and an ethylenically unsaturated compound (ii) parts by weight, and the composition (
A thermoplastic resin composition characterized in that the rubbery polymer content in A+B+C+D) is 5 to 25% by weight.