JPS63130659A - Resin composition having excellent impact resistance - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent impact resistance, by blending a modified polyphenylene ether resin with a polyamide resin and a specified terpolymer. CONSTITUTION:A polyphenylene ether resin (a) having a main chain composed of a structural unit of the formula (wherein R<1> is a 1-3C lower alkyl; and R<2> and R<3> are each H or R<1>) (e.g., 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer) is reacted with 0.01-10wt% [based on the amount of the component (a)] 1,2-substd. olefin compd. (b) having an acid anhydride structure in the absence of a catalyst in a molten state to obtain a modified polyphenylene ether resin (A). Separately, a monomer mixture of 60-99mol% of ethylene, 0.5-40mol% of an unsaturated carboxylic acid ester (e.g., ethyl acrylate) and 0.5-5mol% of maleic anhydride (derivative) (e) is polymerized to obtain a terpolymer (c). The component A is blended with a polyamide resin (B) (e.g., nylon 66) in a ratio of A to B of 0.1-5, the component C and optionally, a reinforcing fiber, additives (D).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition containing a polyphenylene ether resin and a polyamide resin. More specifically, the present invention relates to a polyphenylene ether resin composition having excellent impact resistance.

[Prior art] Polyphenylene ether resin has excellent properties such as thermal properties, mechanical properties, and electrical properties, but has the drawback of poor moldability due to its high melt processing temperature and low fluidity. be. In addition, it has strong resistance to inorganic chemicals such as acids and alkalis, but it does not dissolve or dissolve in certain organic solvents.
Swelling occurs, and there is a strong demand for improvements in solvent resistance and oil resistance.

Several attempts have been made to improve both moldability and oil resistance. For example, a method of blending polyamide in an amount of 20% or less with polyphenylene ether (Japanese Patent Publication No. 45-9
No. 97), a method of blending polyamide with polyphenylene ether in a range of 30 to 95% (Japanese Patent Publication No. 59-41
No. 665). When a small amount of polyamide is blended, the molding processability is improved to some extent; however, it is difficult to see a sufficient improvement in terms of oil resistance, and when a relatively large amount is blended, solvent resistance is improved. It has no toughness and becomes a brittle material. This is essentially due to poor compatibility between polyphenylene ether resin and polyamide resin. This polyphenylene ether (
Several methods have been proposed to improve the compatibility between polyamide (hereinafter referred to as PPB) and polyamide (hereinafter referred to as PA).

For example, carbon-carbon in the molecule of maleic acid, maleimide, etc.
A method of blending a compound having a carbon double bond and a functional group such as a carboxylic acid group, an acid anhydride group, an acid amide group, or an imide group as an f43 component (Japanese Unexamined Patent Publication No. 56-26913), a styrene compound and α , a method of blending a copolymer with β-unsaturated dicarboxylic acid (Japanese Patent Publication No. 59-53614)
and so on. Even if maleic anhydride or maleimide is blended as a third component, sufficient compatibility improvement cannot be achieved, but in high-temperature, high-speed molding such as injection molding, delamination and poor appearance occur, and sufficient toughness is not achieved. The materials it has are very good. or,
When a copolymer of maleic anhydride and styrene is blended, heat resistance decreases.

[Problem that the invention seeks to solve]

As a result of intensive studies to improve the compatibility between PPFS and PA, the present inventors thermally grafted a 1,2-substituted olefin compound having an acid anhydride structure onto the side chain methyl group of PPE without a catalyst. When PA is added to the modified polyphenylene ether resin (hereinafter abbreviated as modified PPP),
It has been found that, unlike the case of blending unmodified PPE and PA, tough resin compositions can be obtained over a wide composition range. It was found that the notched Izot impact strength had a very low value, that is, the notch sensitivity was very high.

[Means for solving problems]

The present inventors conducted intensive studies to improve the impact resistance (notched isot @ impact strength) of this resin composition, and found that the impact resistance was significantly improved by blending a specific terpolymer. The present invention was achieved based on this discovery. .

That is, the present invention provides: (wherein R1 is a lower alkyl group having 1 to 3 carbon atoms, R2,
R3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. modified polyphenylene ether resin obtained by reacting it in the molten state in the presence of lb)
This is a novel resin composition with improved impact resistance, which is made by blending the following specific terpolymer into a resin mixture consisting of a polyamide resin.

The terpolymer used here is ethylene, n60
~99 mol%, unsaturated carboxylic acid ester 0.5~
40 mol% and maleic anhydride or its derivatives 0
．． It refers to a copolymer obtained by copolymerizing a monomer mixture having a composition of 5 to 5 mol % by a known method. Examples of the unsaturated carboxylic acid esters include (meth)acrylic esters represented by methyl (meth)acrylate and ethyl (meth)acrylate, and examples of maleic anhydride derivatives include Hafesters and diesters. I can do it.

The terpolymer preferably used in the resin composition of the present invention is a copolymer obtained from ethylene, ethyl acrylate, and maleic anhydride, and such a terpolymer is, for example, a copolymer obtained from Sumika Sea - It is commercially available under the trade name "Bondine" from DF Chemical Co., Ltd. and is easily available.

Such a terpolymer has good affinity with modified PPE and PA, and there is no knowledge that by blending this terpolymer, the impact strength of a resin composition of modified PPE and PA can be significantly improved. , which is unexpected.

The modified polyphenylene ether resin (modified PPE) used in the resin composition of the present invention is produced by combining the below-mentioned polyphenylene ether resin (PPFi) and a 1,2-substituted olefin compound having an acid anhydride structure in the absence of a catalyst. Obtained by melt-kneading. The melt-kneading machine is
A kneader, a Banbury mixer 1 extruder, etc. may be used, and although there are no particular limitations, it is preferable to use an extruder from the viewpoint of operability. Here, examples of the 1,2-substituted olefin compound having an acid anhydride structure include maleic anhydride, itaconic anhydride, citraconic anhydride, etc.
Maleic anhydride is preferred.

Polyphenylene ether resin (PPP) used here
) is a general formula (wherein R1 is a lower alkyl group having 1 to 3 carbon atoms, R2,
R3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ), which has a structural unit in its main chain, which may be a homopolymer or a copolymer.
-phenylene)ether, poly(2,6-ethyl-1)
．． 4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-methyl-6-2+-1,4-phenylene) ether, poly(
Examples include 2-methyl-6-brobyl-1,4-phenylene) ether, particularly poly(2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol/2°3.6 -) Limethylphenol copolymer is preferred.

Modification of PPE C4! 1,2- having an acid anhydride structure
The amount of substituted olefin compound is in the range from 0.01 to 10% by weight, preferably from 0.1 to 3% by weight, particularly preferably from 0.1 to 1% by weight, based on 100 parts by weight of PPB. If less than this is used, the effect of improving the compatibility of PPE and PA will be small, and it will be difficult to obtain a composition with toughness.
If it is used in an amount exceeding this range, there will be problems such as thermal decomposition of the excess olefin compound, and further undesirable phenomena such as a decrease in heat resistance and poor appearance will occur.

Polyamide resins used in the resin composition of the present invention include, for example, 4-nylon, 4°6-nylon, 6-nylon,
-nylon, 6.6-nylon, 12-nylon, 11
-nylon, 6.10-nylon, MXD-nylon, etc.

The blending ratio of modified PPE and PA can be selected within a wide range, but is preferably PPM/PA20.1 to 5.
, Particularly preferably PPB, /PA=: 0.3-3. If the composition is smaller than this range, the excellent water resistance and dimensional stability of PPE will be impaired, and if the composition is larger than this range, the effects of improving oil resistance, moldability, etc. will not be sufficient.

The resin composition of the present invention may include glass fibers,
Fiber-reinforcing materials such as carbon fibers can be blended.

Furthermore, various additives commonly used for polymeric materials,
For example, stabilizers, facial dyes, mold release agents, lubricants, fillers, and the like can be added as appropriate. .

"Examples" The polyphenylene ether resin composition of the present invention will be specifically illustrated below through Examples and Comparative Examples, and the numbers in the examples are based on at.

Examples 1 to 4 and Comparative Examples Intrinsic viscosity measured in chloroform at 25°C is 0.50
d//F 2,6-xylenol/2,5.6-1
-Limethylphenol copolymer polyphenylene ether (2,15-xylenol 95 mol%) powder 5Kf
After mixing 25 g of maleic anhydride in a super mixer for 3 minutes, a twin screw extruder (Ikegai Iron Works rPCM-
The mixture was melt-kneaded at 290° C. and extruded to obtain maleic anhydride-modified polyphenylene ether (modified PPP) pellets.

The obtained modified PPB, nylon-6,6, and ethylene/thousand acrylate/maleic anhydride copolymer (monomer composition ratios are shown in the footnotes of Table 1) were mixed in the proportions shown in Table 1. They were blended, melted and kneaded using an injection molding machine, and molded into various test pieces.

Table 1 shows the physical properties measured using the test piece.

For comparison, the physical properties of a composition containing no terpolymer were also measured. The results are also listed in Table-1.

〔effect〕

From the results of Examples and Comparative Examples, in the composition of the present invention,
The molding processability has been improved, and in particular, a remarkable improvement has been achieved in the notched isot impact strength.

Claims (1)

[Claims] 1. (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a lower alkyl group having 1 to 3 carbon atoms, R_
2, R_3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) A modified polyphenylene ether resin obtained by reacting a 1,2-substituted olefin compound having an acid anhydride structure in a molten state in the absence of a catalyst with a polyphenylene ether resin having a structural unit represented by ( A resin composition with excellent impact resistance, comprising a terpolymer obtained from b) a polyamide resin and (c) ethylene, an unsaturated carboxylic acid ester, and maleic anhydride or a derivative thereof. 2. The terpolymer is a monomer mixture consisting of 60 to 99 mol% of ethylene, 0.5 to 40 mol% of an unsaturated carboxylic acid ester, and 0.5 to 5 mol% of maleic anhydride or its derivative. The resin composition according to claim 1, which is a copolymer obtained by polymerization.