JPS61106662A - Heat-resistant polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to impact and heat, by blending a resin contg. an unsaturated nitrile compd. and a resin contg. an ethylenically unsaturated dicarboxylic acid anhydride with a polyphenylene ether resin. CONSTITUTION:A heat-resistant polyphenylene ether resin compsn. having excel lent impact resistance contains 65-95wt% (hereinafter briefly %) polyphenylene ether resin (A) [e.g. poly(2,6-dimethyl-1,4-phenylene)ether, etc.]. 2-30% resin (B) contg. 18-40% unsaturated nitrile [e.g. (meth)acrylonitrile], 30-70% arom. vinyl compd. and 5-30% diene rubber, and 2-30% resin (C) contg. 2-18% ethylenically unsaturated dicarboxylic acid anhydride (e.g. maleic anhydride), 65-95% arom. vinyl compd. and 0-12% elastomer (e.g. ethylene/propylene copolymer).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyphenylene ether resin composition having excellent impact resistance and heat resistance. More specifically, a resin containing an unsaturated nitrile compound and an ethylenically unsaturated dicarboxylic anhydride in a polyphenylene ether resin.

It relates to a polyphenylene ether resin composition having excellent impact resistance and heat resistance, which is prepared by combining the following.

[Conventional technology]

Polyphenylene ether resin is disclosed in U.S. Patent No. 33068.
No. 74, 5306B No. 75, No. 5257357, 525
It is a known resin disclosed in various known documents such as No. 7558 and No. 4011200, No. 6, and Japanese Patent Application Laid-open No. 126800/1983.

Polyphenylene chill resin has excellent heat resistance, but it requires extrusion and molding at high temperatures. Extrusion and molding processes at high temperatures lead to deterioration of the polyphenylene ether resin, thereby impairing the inherent properties of the polyphenylene ether resin. As a method to improve these drawbacks of polyphenylene ether resin, US Patent No. 55854
No. 55 discloses a resin composition containing polyphenylene ether and a vinyl aromatic resin. Since the molding temperature of the vinyl aromatic resin is lower than that of polyphenylene ether, the molding temperature of the resin composition obtained by blending the two is lower than the molding temperature of polyphenylene ether alone.

Said 1! Although a wide variety of vinyl aromatic resins are listed in IJ Specification I, the main ones are polystyrene or rubber-modified polystyrene. Resins containing unsaturated dihydrocarbons, vinyl aromatic compounds, and elastomers, commonly called ABS resins (hereinafter referred to as rAB
It is called "S resin". ) is also cited as an example of vinyl aromatic resin [ □; Although moldability is similarly improved, physical properties such as impact strength are significantly impaired.Therefore, the IRHr! composition consisting of polyphenylene ether and ABS resin is not practical.

Therefore, polyphenylene ether c! -Resin compositions with improved physical properties by improving compatibility with ABSm fat are disclosed in US Pat. No. 4,560,618 and US Pat.
It is disclosed in each specification of No. 753. In the former, ABS
Based on the recognition that the acrylonitrile component in the resin is the cause of poor compatibility between polyphenylene ether and ABS resin, we selected an ABS resin with an acrylonitrile content of 2 to 8% by weight, and Overcoming poor compatibility.

In the latter case, an ABS resin having an acrylonitrile content of 2 to 15% by weight is used, and a resin containing an ethylenically unsaturated dicarboxylic acid anhydride, a vinyl aromatic compound, and optionally an elastomer as a third component (hereinafter referred to as
rSMA resin. ), AB
Proposals have been made to improve the compatibility of S resins with topolyphenylene ethers.

[Problem that the invention seeks to solve]

In the resin composition disclosed in the above document, although the compatibility between polyphenylene ether and ABS resin is improved, the amount of A used is small, and J
The characteristics inherent to ABS resin are largely dependent on the acrylonitrile component, and a decrease in the acrylonitrile content will correspondingly deteriorate the characteristics inherent to ABS resin. Therefore, a resin composition is desired that has improved compatibility with the commonly commercially available ABS resin topolyphenylene ether and takes advantage of the inherent characteristics of ABS resin. The inventors
Polyphenylene ether resin, normal ABS resin,
It has been discovered that by combining SMA resin and SMA resin in a certain ratio, a polyphenylene ether resin composition having good compatibility and excellent M impact properties can be obtained. However, in this polyphenylene ether resin composition, the blending ratio of ABS resin and SMA resin in the resin composition is large, so the excellent heat resistance originally possessed by polyphenylene ether resin inevitably decreases. It's hard to avoid. Therefore, we created a resin composition that uses a commonly commercially available ABS resin, improves the compatibility between the ABS resin and the polyphenylene ether resin, and maintains as much as possible the excellent heat resistance inherent to the polyphenylene ether resin. It is an object of the present invention to provide.

[Means for solving problems]

As a result of intensive study to solve the above problems, the present inventors found that polyphenylene ether resin, ordinary ABS resin,
It was discovered that a polyphenylene ether resin composition having excellent impact resistance and heat resistance can be obtained by combining and blending SMA resin and SMA resin in a specific ratio, and the present invention was achieved based on this discovery.

That is, the present invention provides (a) polyphenylene ether resin
Resin containing 65-95% by weight, (bJ18-40% by weight unsaturated dil+ful compounds, 30-70% vinyl aromatic compounds, and 5-30% by weight diene rubber)
and (c) 2-30% by weight of an ethylenically unsaturated dicarboxylic acid anhydride, 65-95% by weight of a vinyl aromatic compound, and 0-12% by weight of an elastomer. %.This is a heat-resistant polyphenylene ether resin composition with excellent impact resistance.

The polyphenylene ether resin (a) used in the present invention is a monocyclic phenol represented by the general formula CI) (in the formula, R
1 is a lower alkyl group having 1 to 3 carbon atoms, and R2 and R3 are a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.

) polyphenylene ether theal obtained by oxidative polycondensation of one or more of

This polyphenylene ether may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the general formula (I) include 2.6-diethylphenol, 2.6-diethylphenol, 2.6-dipropylphenol, 2-
Methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,5-dimethylphenol, 2゜3-diethylphenol, 2,6-dipropylphenol , 2-methyl-5-ethylphenol, 2-methyl-
3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-7'-pylphenol, 2-
Propyl-5-methylphenol, 2-propyl-3-
Ethylphenol, 2,3.6-1-diethylphenol, 2,5.6-driethylphenol, 2゜3.6-
Examples include dolipropylphenol, 2.6-dimethyl-3-ethylphenol, 2.6-dimethyl-3-propylphenol, and the like.

Examples of polyphenylene ethers obtained by polycondensation of one or more of these monocyclic phenols include BoIJ (2,6-cymethyl-1,4-)elasin).
Ether, poly(2゜6-diethyl-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-methyl-6-nityl-1,4-phenylene) ether, poly(2-methyl-6
-broby-1,4-phenylene)ether, poly(2
-ethyl-6-broby-11,4-)unilene)ether, 2,6-dimethylphenol/2,3.6-11
Methylphenol copolymer, 2.6-dimethylphenol/2,3.6-)diethylphenol copolymer, 2.
6-diethylphenol/2,3.6-dodiethylphenol copolymer, 2,6-diprobylphenol/2,
3.6-1-diethylphenol copolymer and the like. In particular, poly(2,6-dimethyl-1,4-)unilene) ether and 2,6-dimethylphenol/2,5°6-dolimethylphenol copolymer are preferred as the polyphenylene ether resin used in the present invention. It is something.

The resin used as component (b) of the present invention is generally A
This resin is well known to those skilled in the art as BS resin. This resin is, for example, unsaturated nitrile compounds, vinyl aromatic compounds,
and diene rubber by polymerization operations such as emulsion polymerization, suspension polymerization, or bulk polymerization, or by polymerizing by combining these methods,
Furthermore, it can also be obtained by mechanically mixing a butadiene/acrylonitrile copolymer elastomer and a styrene/acrylonitrile copolymer.

(The unsaturated dil-IJ compound in the bl component resin is
(acrylonitrile, methacrylonitrile, ethacrylonitrile) or its analogues; acrylonitrile and methacrylonitrile are preferably used. Furthermore, the vinyl aromatic compound refers to a compound represented by the following general formula 〇. (In the formula, R4 represents a hydrogen atom or a lower alkyl group, Z represents a halogen atom or a lower alkyl group, and p is 0 or a positive integer of 1 to 3.) Physically, styrene, p- Methylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, chlorstyrene,
Examples include bromustyrene. Among them, styrene, p
-Methylstyrene and chlorstyrene are preferably used.

Furthermore, diene rubber includes butadiene, isoprene,
Rubbery polymers, which are polymers of conjugated diene compounds such as chloroprene, and rubbery polymers of conjugated diene compounds and common comonomers such as vinyl aromatic compounds such as styrene and p-methylstyrene. It does not only mean copolymers, but also all forms of natural and synthetic diene rubbers. Preferred diene rubbers are polybutadiene or rubbery butadiene-styrene copolymers.

Generally, the proportions of unsaturated nitrile compounds, vinyl aromatic compounds, and elastomers in the ABS resin can vary widely depending on the purpose. Incidentally, in the above-mentioned US Pat. No. 4,405,753, which is a known document, the content of unsaturated nitrile compounds is 2 to 15% by weight, the content of vinyl aromatic compounds is 65 to 94% by weight, and the content of diene rubber is 5% by weight. It is disclosed to use a special ABS resin that is ~20 wt%.

On the other hand, in the resin composition of the present invention, the unsaturated nide IJ
It is preferable to use an ABS resin having a vinyl aromatic compound content of 18 to 40% by weight, a vinyl aromatic compound content of 50 to 70% by weight: R96, and an elastomer content of 5 to 30% by weight. In light of the concept of ordinary ABS resin, the former ABS resin is special, and in the present invention, general-purpose ABSvR resin is used.

In the present invention, resin (S) used as component (C)
MA resin) is obtained by polymerizing a predetermined amount of an ethylenically unsaturated dicarboxylic acid anhydride and a vinyl aromatic compound as described below, and optionally an elastomer, by a polymerization method known per se, that is, a bulk, solution or emulsion polymerization method. A copolymer that is

Such copolymers and their production methods are described, for example, in Latter Day Patent Nos. 2769804, 2971939 and 33362.
It is specifically described in each specification of No. 67, Osinda Publication Patent No. 7212714, and the like.

The ethylenically unsaturated dicarboxylic acid anhydride in the component resin (C) refers to compounds exemplified by maleic anhydride, citraconic anhydride, itaconic anhydride, and anicontic anhydride, and preferably maleic anhydride.

Further, as the vinyl aromatic compound, the same compound as the vinyl aromatic compound used in the above-mentioned component resin (①) is used, and styrene is preferably used. Furthermore, elastomer is an elastomer in the general sense, for example A.

V, ToboAsky rProperties a
nd 5true-tures of Polymer
s J (John Wi-eeey & 5ons,
Inc., 1960), pp. 71-78. According to this definition, an elastomer has a Young's modulus of 10' to 10 at room temperature.
dynes/m (manufactured by 0.1 to 1020). Specific examples of elastomers include polybutadiene, polyisoprene, butyl rubber, A-B-A'
ff Elastomeric block copolymer CA, A indicates a block based on a vinyl aromatic compound, B indicates a block based on a diene compound. ), a copolymer of a diene compound and a vinyl aromatic compound, 2) IJ rubber, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer (EPDM), and natural rubber.

The content of ethylenically unsaturated dicarboxylic acid anhydride in the resin suitable as component (C) of the resin composition of the present invention is 2
~18% by weight, the content of vinyl aromatized metals is 65~9
5% by weight, and the content of elastomer is 0-12% by weight. Such resins are commercially available, for example, as "Dylark" (trade name, Arco Chemical Company) and "Lytron" (trade name, Monsanto Company), and are easily available.

The blending amounts of component (a), component (b) and component (C) in the resin composition of the present invention are generally from 65 to 65, respectively.
95 weight t96.2 to 33% by weight and 2 to 30% by weight, preferably the ratio of ABS resin to SMA resin is in the range of 80/20 to 20/80, and (
The content of component a) is selected within the range of 65 to 85% by weight.

Tsukasa: Resin components and elastomer components other than those mentioned above and various additives and fillers known per se can be appropriately selected and blended into the resin composition of the present invention, as desired. .

In preparing the polyphenylene ether resin composition of the present invention, any conventionally known method may be employed,
For example, after mixing each component with a high-speed mixer such as a turnpull mixer or a Henschel mixer,
A method of kneading with a Banbury mixer, rolls, etc. is appropriately selected.

Hereinafter, the resin composition of the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following description, parts and percentages are expressed on a weight basis unless otherwise specified.

〔Example〕

Examples 1 to 4 and Comparative Example 1.2 2.6-dimethylphenol/21S,6-dolimethylphenol copolymer with an intrinsic viscosity of 0.52 d-g/7 (25°C, in chloroform) (the ratio of the latter is 5 mol%, P
It is abbreviated as PE. ), ABS.

Resin (acrylonyl-IJ content: 21%, butadiene content: 15%, styrene content: 64%; trade name: TAFLEX 710J, manufactured by Mitsubishi Monsando Chemical Co., Ltd.) and styrene-maleic anhydride copolymer (maleic anhydride) Content: 1596, Bia96 containing polybutadiene, IT containing styrene 7596; Product name: "Dylark 350"
J, manufactured by Alco, USA, abbreviated as SMA) were blended in the proportions shown in Table 1.

To these resin components were added 0.6 parts of 2,2-methylene-bis(4-methyl-6-tert-butylphenol) and 0.4 parts of tetrakis(2,4-di-tar), respectively.
t-butylphenyl)-4,4! -biphenylene diphosphonite were added and the mixture was thoroughly mixed using a Henschel mixer. The resulting mixture is A
It was extruded into pellets using an S-30 twin-screw extruder a (manufactured by Nakagama Kikai Seisakusho), and then molded into a test piece using a 5J-353 injection molding machine (manufactured by Nagi Seisakusho). Table 1 shows the measured notched Izot impact strength (1/4" thickness) and heat distortion temperature (264 psi) for each composition.

Table 1 Example 1 7020 10 25 O164,4z
27015152t0 165.2z 570102
019.2 1664z 4801o 1o 24.6
177.5 Comparative Example 1 7030 - 4.7
159.8#28020-6.4・17
2.8# 5100-- 7.1 19t4 # 45035.5147148 128.7 [Effect of the invention] As is clear from the examples, polyphenylene ether resin, ABS resin containing an unsaturated nitrile compound of 18 Fkg6 or more, In the resin composition of the present invention obtained by combining and blending SMA resin in a predetermined ratio, the compatibility between the polyphenylene ether resin and general-purpose ABS resin is improved, and the impact strength of the resin composition is improved. At the same time, heat resistance is also maintained.

Claims (1)

[Claims] (a) Polyphenylene ether resin 65-95% by weight
, (b) 18-40% by weight of unsaturated nitrile compound, 3
0-70% by weight vinyl aromatics, and 5-30%
2-30% by weight of a resin containing % by weight of diene rubber, and (c) 2-18% by weight of an ethylenically unsaturated dicarboxylic acid anhydride, 65-95% by weight of a vinyl aromatic compound;
and resin 2 containing 0-12% by weight of elastomer.
A heat-resistant polyphenylene ether resin composition with excellent impact resistance, containing ~30% by weight.