JPH0243234A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve impact resistance, heat resistance, processability, chem. resistance and resistance to moisture absorption by compounding a polyphenylene ether resin, a polyolefin resin, a specified A-B-A' type block copolymer elastomer and an unsatd. compd. together. CONSTITUTION:100 pts.wt. compsn. consisting of 20-95wt.% polyphenylene ether resin (A) of the formula (wherein R1-4 are each H, a halogen, a (hydroxy) hydrocarbon or a (hydroxy)halohydrocarbon; a is the total number of monomer units and 20 or larger) and 80-5wt.% polyolefin resin (e.g., polyethylene) are compounded with 1-30 pts. A-B-A' type block copolymer elastomer (A and A' are each a polymerized unit of an arom. hydrocarbon compd; B is a polymerized unit of a conjugated diene or a hydrogenated compd. thereof) and 0.01-20 pts.wt. unsatd. compd. having a C-C double bond and one or more functional groups selected from carboxylate, acid anhydride, amide, imide, epoxy, amino and hydroxyl groups (e.g., maleic acid).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides impact resistance represented by Izodili strength,
The present invention relates to a thermoplastic resin composition that is excellent in both heat resistance as represented by heat distortion temperature and moldability as represented by melt flow index.

[Conventional technology]

Polyphenylene ether resin is a resin with excellent mechanical properties and heat resistance, but it is generally not used alone because it has a high melt viscosity and requires high temperatures during molding, causing discoloration or oxidative deterioration. For the purpose of improving properties, resin compositions of polyphenylene ether resin and polystyrene or rubber-modified polystyrene are used. However, although this resin composition improved the moldability of polyphenylene ether resin, the heat distortion temperature was significantly lowered, and the impact resistance and chemical resistance were also not fully satisfactory. Further, JP-A-54-88960 discloses a composition comprising a polyphenylene ether resin, a polyolefin resin, and an A-B-A' type block copolymer elastomer. Although this composition has fairly good impact resistance, it has problems with chemical resistance.
Furthermore, when molded products are made, there are problems such as poor appearance and layer cracking.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a resin composition for engineering plastics that is based on polyphenylene ether resin and has excellent heat resistance, impact resistance, processability, chemical resistance, and moisture absorption resistance.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors found that polyphenylene ether resin, polyolefin resin,
The present invention was achieved by discovering that a resin composition comprising an A-B-A' type block copolymer elastomer and a compound having a specific functional group can achieve the above object.

That is, the present invention relates to (a) a group consisting of the general formula (wherein R1, R, , Ih and R4 are each independently hydrogen, halogen, hydrocarbon, halohydrocarbon, hydrocarbonoxy and halohydrocarbonoxy); (where n represents the total number of monomer units and is an integer of 20 or more)
~95% by weight of a polyolefin resin (b) and 80 to 5% by weight of a polyolefin resin (b), an A-B-A' type block copolymer elastomer (where A, A' are B is a unit polymerized from a vinyl aromatic hydrocarbon compound, and B is a unit polymerized from a conjugated diene or a hydrogenated polymerized conjugated diene unit.)
1 to 30 parts by weight and a carbon-carbon double bond as component (d), and as a functional group, a carboxylic acid group, an acid anhydride group, an amide group, an imide group, a carboxylic acid ester group, an epoxy group, an amino This is a thermoplastic resin composition comprising 0.01 to 20 parts by weight of an unsaturated compound having one or more of groups and hydroxyl groups.

The polyphenylene ether resin as the component (a) constituting the thermoplastic resin composition of the present invention has a repeating unit represented by the above general formula, and -M is manufactured using phenols as a raw material, and is manufactured using a U.S. patent It can be produced by the method described in No. 3306874, No. 3306875, No. 3257357, and No. 3257358. Phenols used as raw materials include 2.6-dimethylphenol, 2.6-dinitylphenol, 2.6-sibutylphenol, 2.6-dilaurylphenol,
．． 6-dipropylphenol, 2.6-diphenylphenol, 2-methyl-6-nitylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6-
Medoxyphenol, 2-methyl-6-butylphenol, 2.6-simethoxyphenol, 2,3.6-1-
Examples include, but are not limited to, trimethylphenol, 2,3,5.6-titramethylphenol, and 2,6-dinitoxyphenol.

In the present invention, a particularly preferred polyphenylene ether resin is poly(2,6-cymethyl-1,4-phenylene).
It is manufactured using ether as a raw material.

Examples of the polyolefin resin as component (b) constituting the thermoplastic resin composition of the present invention include polypropylene, polyethylene, propylene-ethylene copolymer, polybutene, polymethylpentene, and the like. These are commercially available and may be manufactured by methods well known to those skilled in the art.

A of component (c) constituting the thermoplastic resin composition of the present invention
-B-A' type block copolymer elastomer is composed of vinyl aromatic hydrocarbon polymer A, block conjugated diene polymer B, and examples of the vinyl aromatic hydrocarbon compound include styrene, α - methylstyrene,
Examples include vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. A and Ao may be the same or different,
Further, examples of conjugated dienes include 1,3-butadiene, 2.
Mention may be made of 3-dimethylbutadiene, isoprene and 1,3-pentadiene and mixtures thereof.

Further, a hydrogenated conjugated diene polymer B block can be suitably used in the present invention.A-B-A' type block copolymer elastomer used in the present invention is commercially available. , for example styrene/butadiene/
For hydrogenated products of styrene block copolymers, Shell Chemical ■
There is a styrene/butadiene/styrene block copolymer (trade name: Kraton C-1650) manufactured by
Manufactured by Shell Chemical Co., Ltd. [Product name: Cauliflex TR-110]
1), which can be easily produced by methods well known to those skilled in the art.

Component (d) constituting the thermoplastic resin composition of the present invention has a carbon-carbon double bond and has a functional group such as a carboxylic acid group, an acid anhydride group, an amide group, an imide group, or a carboxylic acid group. An unsaturated compound having one or more of an ester group, an epoxy group, an amino group, and a hydroxyl group (hereinafter referred to as a compound having a specific functional group), such as α,β-ethylenically unsaturated dibasic acid or Its anhydrides, amides, imides, and esters. Specifically, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N-diethylamide, maleic acid- N-motuptilamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide,
fumaric acid diamide, fumaric acid-N-monoethylamide,
fumaric acid-N,N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N,N-dibutylamide,
Maleimide, N-butylmaleimide, N-phenylmaleimide, bismaleimide, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid di-
Examples include n-butyl ester. In addition, epoxidized natural oils and fats such as epoxidized soybean oil, allyl alcohol,
Methyl vinyl carbinol, allyl carbinol, 4-
Examples include unsaturated alcohols such as penten-1-ol and propargyl alcohol, and unsaturated amines in which the OH group of such unsaturated alcohols is replaced with an NHz group.

In the thermoplastic resin composition of the present invention, the blending ratio of (a) polyphenylene ether resin and (b) polyolefin resin is 20 to 95% by weight, preferably 40 to 9% by weight.
0% by weight, (b) is 80-5% by weight, preferably 60-5% by weight
It is necessary that the amount is in the range of 10% by weight, and (a) is 2% by weight.
If it is less than 0% by weight, heat resistance and rigidity will be poor, and if (a) exceeds 95% by weight, impact resistance and chemical resistance will decrease, which is undesirable, and (C) A-B-A' type block copolymer. The amount of the combined elastomer and (d) compound having a specific functional group is (a) + (b) based on 100 parts by weight of the total.
c) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, (
d) is 0.01 to 20 parts by weight, preferably 0.5 to 10 parts by weight.
Use within the range of parts by weight. Outside the above range, for example, if (c) is less than 3 parts by weight, the impact resistance will be poor, and if it is 30 parts by weight or more, the rigidity will be reduced. Furthermore, if (d) is less than 0.01 parts by weight, molding processability is reduced, and if it is more than 20 parts by weight, heat resistance and impact resistance are reduced, which is not preferable.

There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and generally known methods can be employed.

That is, (a) polyphenylene ether resin, (b) polyolefin resin, (c) A-B-A' type block copolymer elastomer, and (d) a compound having a specific functional group were uniformly mixed using a high-speed stirrer or the like. After that, a method of melt-kneading using a single-screw or multi-screw extruder with sufficient kneading capacity can be adopted.

The thermoplastic resin composition of the present invention may optionally contain polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer (ABS),
It is also possible to modify it into a desired material by appropriately mixing thermoplastic resins such as styrene-maleic anhydride copolymer, rubber-modified polystyrene, and α-methylstyrene-acrylonitrile copolymer. Depending on the purpose, reinforcing materials such as pigments, dyes, glass fibers, metal fibers, and carbon fibers, fillers such as talc and calcium carbonate, antioxidants, ultraviolet absorbers, lubricants, flame retardants, and antistatic agents may also be added. Can be added.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

The characteristics of the polymers and molded articles described in Examples and Comparative Examples were evaluated according to the following method.

(1) Izod impact strength J[S- based on 7110.

(2) Heat distortion temperature Compliant with JIS-7207.

Bending stress 18.56Kg/c+J (3) Melt flow index (formability) JIS
- Compliant with 7210.

Load 2.16Kg, temperature 300'C Examples 1 to 3 Polyphenylene ether resin (manufactured by GEM Polymer ■)
, polypropylene-ethylene block copolymer as polyolefin resin [manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: BJH]
-C;), hydrogenated product of styrene/butadiene/styrene block copolymer as A-B-A' type block copolymer elastomer [manufactured by Shell Chemical Company, trade name: Kraton G]
-1650) and N-phenylmaleimide as a compound having a specific functional group were blended in the proportions shown in Table 1, and the mixture was kneaded and pelletized at a temperature of 270 to 300°C.

Injection molded test pieces were made from these pellets, and the above physical properties were measured. The results are shown in Table 1.
It has excellent workability and appearance and has sufficient practical value.

Examples 4 to 6 In Examples 1 to 3, the A-B-A' type block copolymer elastomer was a styrene/butadiene/styrene block copolymer [manufactured by Shell Chemical Co., Ltd., trade name: Califlex TR-1101], The same procedures as Examples 1 to 3 were carried out except that maleic anhydride was blended as a compound having a specific functional group in the proportion shown in Table 1. All of them have excellent impact resistance, heat resistance, workability, and appearance, and have sufficient practical value.

Comparative Examples 1 to 4 The polyphenylene ether resin, propylene-ethylene block copolymer, hydrogenated product of styrene/butadiene/styrene block copolymer and N-phenylmaleimide used in Examples 1 to 3 were added in the proportions shown in Table 1. The same procedure as in Examples 1 to 3 was carried out except that the ingredients were blended.

If the composition ratio specified in the present invention is deviated from, any of the impact resistance, heat resistance, moldability, and appearance will be significantly reduced, and the product will not have sufficient practical value.

Comparative Example 5 Example 6 was carried out in the same manner as in Example 4, except that a styrene-butadiene random copolymer (manufactured by JSR ■, trade name JSR-1500) was used instead of the styrene/butadiene/styrene block copolymer. However, the impact resistance was poor.

〔Effect of the invention〕

The thermoplastic resin composition of the present invention has excellent impact resistance, heat resistance, and moldability, and is suitably used for automobile parts, industrial parts, electrical materials, and the like.

Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1, R_2, R_3 and R_4 each independently represent hydrogen, halogen, hydrocarbon, halohydrocarbon, hydrocarbon 20 to 95% by weight of a polyphenylene ether resin selected from the group consisting of hydrogen oxy and halohydrocarbon oxy, where n represents the total number of monomer units and is an integer of 20 or more; (b) polyolefin resin 80
~5% by weight of a composition consisting of 100 parts by weight of an A-B-A' type block copolymer elastomer (where A and A' are polymerized from a vinyl aromatic hydrocarbon compound) as component (c). B is a unit polymerized from a conjugated diene or a hydrogenated polymerized conjugated diene unit.) 1 to 30 parts by weight and carbon-carbon 2 as the component (d).
Having a heavy bond and as a functional group, a carboxylic acid group, an acid anhydride group, an amide group, an imide group, a carboxylic acid ester group,
A thermoplastic resin composition comprising 0.01 to 20 parts by weight of an unsaturated compound having one or more of epoxy groups, amino groups, and hydroxyl groups.