JPH0312450A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent impact resistance and molding and processing properties by blending a polyphenylene ether resin and an aromatic polycarbonate resin with an elastomer of A-B-A' type block copolymer and a core-shell type elastomer. CONSTITUTION:100 pst.wt. resin composition consisting of (A) 10-90wt.% polyphenylene ether resin and (B) 90-10wt.% aromatic polycarbonate resin is blended with <=40 pts.wt. total amounts of (C) 5-35 pst.wt. elastomer of A-B-A' type block copolymer (A and A' are vinyl-based aromatic hydrocarbon polymer; B is conjugated diene polymer or a hydrogenated substance thereof) and (D) 5-35 pst.wt. core-shell type elastomer such as elastomer having a core phase comprising acrylic rubber and a rigid thermoplastic shell phase and optionally (E) 0.5-20 pts.wt. acid imide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a thermoplastic resin composition, in particular mechanical properties represented by Izod impact strength, moldability represented by melt flow index, The present invention relates to a thermoplastic resin composition that has excellent heat resistance as typified by heat distortion temperature.

[Conventional technology]

A resin composition consisting of a polyphenylene ether resin and an aromatic polycarbonate resin is known from US Pat. No. 3,221,080. However, although the resin mixture of the patent has good solvent resistance, it has poor mechanical strength and poor thermal stability during molding.
No. 42456 discloses a block copolymer of a polyphenylene ether resin and a carbonate-containing polymer, but the Ui% resistance! In JP-A No. 61-62555, poly(methylhydrogen) siloxane and a specific impact modifier were added to a mixture of polyphenylene ether and aromatic polycarbonate. In addition to the stability of the product, the mechanical strength can be improved.U.S. Pat. has been disclosed, however, the improvement in IIWl strength is not sufficient and the heat resistance is significantly reduced.In such a composition containing a polyphenylene ether resin and an aromatic polycarbonate resin, el
No material with excellent mechanical strength, moldability, and heat resistance has been obtained.

[Problem to be solved by the invention]

An object of the present invention is to provide an engineering plastic that improves the compatibility between polyphenylene ether resin and aromatic polycarbonate resin, has excellent mechanical properties and moldability, and exhibits less deterioration in heat resistance.

[Means to solve the problem]

The present inventors have solved the above-mentioned problem (as a result of intensive studies, we have developed an A-B-A' type block copolymer elastomer and a core-shell type The present invention was achieved by discovering that a thermoplastic resin composition obtained by combining an elastomer and blending and melt-kneading an acid imide compound in a specific ratio can achieve the above object.

That is, the present invention includes (c) A -B -A' in 100 parts by weight of a resin composition consisting of (a) 10 to 90% by weight of a polyphenylene ether resin and (b) 90 to 10% by weight of an aromatic polycarbonate resin. type block copolymer elastomer [where A and A' are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block or a hydrogenated polymerized conjugated diene block] 5 to 35 parts by weight, and (d) 5 to 35 parts by weight of a core-shell elastomer, and (c)
and (d) in a total amount not exceeding 40 parts by weight.

The present invention improves mechanical properties, heat resistance and molding process by using an A-B-A' type block copolymer elastomer and a core-shell type elastomer in combination with a composition of a polyphenylene ether resin and an aromatic polycarbonate resin. The thermoplastic resin composition may further contain an acid imide compound (the acid imide compound may include -a with NH3 or a primary amine compound). It is a cyclic imide derived from the acyl group of a dibasic acid.

The polyphenylene ether resin as the component (a) constituting the thermoplastic resin composition of the present invention is preferably a homopolymer or copolymer containing one or more units represented by -Fukudai [■] (in the formula, RRl, R3 , and R1 are each independently hydrogen.

selected from the group consisting of halogen, hydrocarbon, halohydrocarbon, hydrocarbonoxy and halohydrocarbonoxy;
n represents the total number of monomer units, and the method for producing polyphenylene ether resin is not particularly limited, but □U.S. Patent No. 33
No. 06874, No. 3306875, No. 32573
It can be produced by the reaction of phenols according to the method described in No. 57 and No. 3,257,358. These phenols include 2,6-ramethylphenol, 26-dinitylphenol, 2.6-sibutylphenol, 2.
6-dilaurylphenol, 2,6-dipropylphenol, 2,6-diphenylphenol, 2-methyl-6
-Nitylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6-medoxyphenol, 2
-Methyl-6-butylphenol, 2.6-simethoxyphenol, 2.36-drimethylphenol, 2.3
．． These include, but are not limited to, 5,6-teI-ramethylphenol and 2,6-ethoxyphenol. A preferred polyphenylene ether resin in the present invention is poly(2,6-ramethyl-1,4-phenylene) ether.

Further, the polyphenylene ether resin (a) used in the present invention may contain polystyrene + h fat, such as OF polystyrene, high impact polystyrene, styrene/butadiene copolymer, styrene/maleic anhydride copolymer, Styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer,
Examples include styrene/methyl methacrylate copolymer.

Furthermore, the polyphenylene ether resin (a) in the present invention includes those in which a styrene polymer or other polymer is grafted onto the above-mentioned polyphenylene ether. The manufacturing method for these is described in Japanese Patent Publication No. 47-. 471
362, Special Publication No. 12197, Special Publication No. 48-12197, Special Publication No. 49-5
623, Special Publication No. 52-38596, Special Publication No. 52-3
0991, in which styrene monomer and/or other polymerizable monomers are graft-polymerized with organic peroxide in the presence of polyphenylene ether, or JP-A-52-142799, Examples include a method of melt-kneading the above-mentioned polyphenylene ether, a polystyrene polymer, and a radical generator as shown.

The aromatic polycarbonate resin used as component (b) of the present invention is a compound known per se.

Generally, these are prepared by reacting dihydric phenols with carbonate precursors, such as phosgene, halogenformates, or carbonate esters. The dihydric phenols used in the production of aromatic polycarbonate resins may contain one or more aromatic nuclei. These phenols contain few (two) hydroxy groups directly bonded to the carbon atoms of the aromatic nucleus. Suitable dihedral phenols include 2,2-bis=(4-hydroxyphenyl)propane [bisphenol A], hydroquinone, 2
．． 2-bis-(4-hydroxyphenyl)pentane, 2
．． 4'-(dihydroxydiphenyl)methane, bis-(
2-hydroxyphenyl)methane bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-5-
nitrophenyl)methane, 1.1-bis(4-hydroxyphenyl)ethane, 3.3-bis(4-hydroxyphenyl)pentane, 2.2-dihydroxydiphenyl, 2
, 6-hydroxynaphthalene, bis-(4-hydroxyphenyl)sulfone, bis-(3,5-diethyl-4
-hydroxyphenyl)sulfone, 2,2-bis(3,
Examples include 5-dimethyl-4-hydroxyphenyl)propane.

In the present invention, homopolymers derived from bisphenol A are preferably used.

A of component (c) constituting the thermoplastic resin composition of the present invention
-B-A' type block copolymer elastomer,
Examples of vinyl aromatic hydrocarbons include elastomers consisting of vinyl aromatic hydrocarbon polymers A and A' brocs and conjugated diene polymers B brocs; examples of vinyl aromatic hydrocarbons include styrene, α
-methylstyrene, vinyltoluene, vinylxylene,
Examples include ethylvinylxylene, vinylnaphthalene and mixtures thereof. A and A' may be the same or different; examples of conjugated dienes include 1.
Examples include 3-butadiene, isoprene 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, It can be manufactured by methods well known to those skilled in the art.

The core-shell type elastomer of component (d) is a polymerization product of an acrylic comonomer or an acrylic monomer and a diene rubber alone or further with styrene, or a core-shell consisting of a core phase made of acrylic rubber and a rigid thermoplastic shell phase. type elastomers, specifically, the former is KM-653 from Ou Chemical Industry ■.
Examples of the latter include an elastomer commercially available under the trade name rM-x9t6 from Takeda Pharmaceutical Company Limited.

In the thermoplastic resin composition of the present invention, the blending ratio of (a) polyphenylene ether resin and (b) aromatic polycarbonate resin is 10 to 9011% by weight of (a) polyphenylene ether resin, preferably 30 to 7011!1
%, (b) aromatic polycarbonate resin 90 to 10% by weight, preferably 70 to 30% by weight. If the blending ratio of the aromatic polycarbonate resin exceeds 901 iffi%, the heat resistance will decrease, and if it is less than 10% by weight, the moldability will decrease, which is undesirable. The blending ratio of (e) core-shell type elastomer is 5 to 35 parts by weight of (c) A-B-A' type block copolymer elastomer to 100 parts by weight of the above (a) + (b). , preferably 10 to 25 parts by weight, (d) acrylic core-shell type elastomer 5
~35 parts by weight, preferably 10 to 25 parts by weight,
In addition, when adding only the A-B-A' type block copolymer elastomer in which the total amount of (c) and (d) does not exceed 40 parts by weight, preferably 5 to 30 parts by weight, the impact resistance Although it is improved, the heat resistance is significantly lowered. Moreover, the effect of improving impact resistance is insufficient if the core-shell type elastomer is used alone. Furthermore, if the total amount of the A-B-A' type block copolymer elastomer and the acrylic core-shell type elastomer exceeds 40 parts by weight, the heat resistance will deteriorate, which is undesirable.

The moldability of the thermoplastic resin composition of the present invention is further improved by the acid imide compound. Examples of acid imide compounds include cyclic imides derived from -m with NH3 or a primary amine compound and an acyl group of a dibasic acid; examples of the primary amine compounds include aniline, cyclohexylamine, etc. , 4-hydroxyaniline, 4-carboxyaniline, 4-chloroaniline, etc. are used, and 2
Examples of the basic acid include succinic acid, glutaric acid, phthalic acid, and maleic acid. Representative examples of acid imide compounds include succinimide, glutarimide, phthalimide, N
-Phenylphthalimide, N-phenylmaleimide, N
-Cyclohexylmaleimide, N-(4-hydroxyphenyl)maleimide, N-(4-carboxyphenyl)
Examples include maleimide, N-(4-chlorophenyl)maleimide, and the like.

In the thermoplastic resin composition of the present invention, the blending ratio of (e) the acid imide compound is 0.5 to 20 parts by weight based on a total of 100 parts by weight of (a) polyphenylene ether resin and (b) aromatic polycarbonate resin. parts, preferably 1 to 10
Parts by weight. 20 acid imide compounds! Exceeding the setting point is not preferable because impact resistance and heat resistance decrease.

There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and any commonly known method can be employed. That is, (a) polyphenylene ether resin, (b) aromatic polycarbonate) H (fat), (C') A-B-A' type block copolymer elastomer, (d) core-shell type elastomer, (e) A method may be adopted in which the acid imide compound is uniformly mixed using a high-speed stirrer or the like, and then melt-kneaded using a single-screw or multi-screw extruder with sufficient kneading capacity.

The thermoplastic resin composition of the present invention may include fillers, dyes, reinforcing agents such as glass fibers, metal fibers, and carbon fibers, fillers such as talc and calcium carbonate, antioxidants, and ultraviolet absorbers, depending on the specifications. 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) Impact resistance Evaluated by Izont impact strength.

Compliant with JTS-7110.

(2) Heat resistance Evaluated by heat distortion temperature.

Compliant with JIS-7207.

Bending stress 18.56 kg/c (3) Molding processability Evaluated by melt flow index.

Compliant with JIS-7210.

Load: 2.16 kg, temperature: 300'C Example 1 Polyphenylene ether resin [manufactured by G-M Polymer ■ Co., Ltd.]
Lo! 1%, aromatic polycarbonate resin 90% by weight
, Kraton G-1650 (manufactured by Shell Chemical Co., Ltd.) as an A-B-A' type block copolymer elastomer, and Acryloid K as a core-shell type elastomer.
M330 (manufactured by Rohm and Haas) was blended in the proportions shown in the table and kneaded into pellets in the range of 270 to 310°C. Injection molded test pieces were made from the pellets and the above physical properties were measured. As shown in the table, impact resistance,
It has excellent heat resistance and moldability, and has sufficient practical physical properties.

Example 2 Core-shell type elastomer °ζ, IM-1916
[Manufactured by Takeda Pharmaceutical Co., Ltd.] was used, except that the proportions of the polyphenylene ether resin, aromatic polycarbonate resin, and A-B-A'' block copolymer elastomer used in Example 1 were changed as shown in the table. It was carried out in the same manner as in Example 1. The results are shown in the table, which shows that it has excellent 11 impact resistance, heat resistance, and moldability, and has sufficient practical physical properties.

Examples 3-4 A-B-A' type block copolymer elastomer,
Using Califlex TR-1101 (manufactured by Shell Kagaku ■), the compounding ratio of polyphenylene ether resin, aromatic polycarbonate resin, and core-shell type elastomer was changed as shown in the table, and the rest was carried out in the same manner as in Example 1. . All had sufficient practical physical properties.

Example 5 IM-1916 (
[manufactured by Takeda Pharmaceutical Co., Ltd.], using phthalimide as the acid imide compound, polyphenylene ether resin, aromatic polycarbonate resin, and AB-A' type block copolymer elas 1-mer in the proportions shown in the table, and the others were carried out. It was carried out in the same manner as in Example 1. The results are shown in the table. U resistance,
It has excellent heat resistance and moldability, and has sufficient practical physical properties.

Example 6 In Example 3, cyclohexylmaleimide (CHMI) was used instead of phthalimide as the acid imide compound, and polyphenylene ether resin, aromatic polycarbonate resin, A-B-A'' block copolymer elastomer, and core - Shell-type elastomers were tested at the blending ratios shown in the table. The results are shown in the table. Endurance 1i111
It has excellent I properties, heat resistance, and moldability, and has sufficient practical physical properties.

Example 7 In Example 1, cyclohexylmaleimide (CHMI) was used instead of phthalimide as the acid imide compound, and polyphenylene ether resin, aromatic polycarbonate resin, A-B-A'' block copolymer elastomer, and a core-shell type elastomer at the blending ratios shown in the table. The results are shown in the table. It has excellent 11 impact resistance, heat resistance, and moldability, and has sufficient practical physical properties.

Comparative Examples 1 to 2 The same procedure as in Example 1 was carried out using only polyphenylene ether resin and aromatic polycarbonate resin. The results are shown in the table, and all of them lacked a balance in impact resistance, heat resistance, and moldability.

Comparative Example 3 A mixture of polyphenylene ether resin and aromatic polycarbonate resin was carried out in the same manner as in Example 1. The results are shown in the table, and the impact resistance and moldability were poor.

Comparative Examples 4 to 6 Implemented except that the polyphenylene ether resin, aromatic polycarbonate resin, A-B-A' type block copolymer elastomer, and core-shell type elastomer used in Example 3 were blended in the proportions shown in the table. Although the same procedure was used as in Example 1, Comparative Examples 4 and 5 were both inferior in impact resistance, and Comparative Example 6 had a significant decrease in heat resistance.

〔Effect of the invention〕

The thermoplastic resin composition of the present invention has impact resistance, moldability,
It has excellent heat resistance and is suitable for use in automobile parts, industrial parts, electrical materials, etc.

Claims (1)

[Claims] 1. (1) (a) Polyphenylene ether resin 10-9
0% by weight, (b) aromatic polycarbonate resin 90-1
(2)(
c) A-B-A' type block copolymer elastomer (where A and A' are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block or a polymerized conjugated diene block) (d) 5 to 35 parts by weight of a core-shell elastomer, and the total amount of (c) and (d) does not exceed 40 parts by weight. A thermoplastic resin composition. 2. (e) 0.5 to 20 parts by weight of an acid imide compound is used in 100 parts by weight of a resin composition consisting of (a) 10 to 90% by weight of polyphenylene ether resin and (b) 90 to 10% by weight of aromatic polycarbonate resin. The thermoplastic resin composition according to claim 1, which is formed by: