JPS63130658A - Impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent impact resistance, by blending a modified polyphenylene ether resin with a polyamide and a specified rubbery elastomer. CONSTITUTION:0.1-10wt% (based on the amount of a copolymer to be grafted) alpha,beta-unsaturated dicarboxylic acid anhydride (a) is grafted onto a block copolymer wherein at least 80% of unsaturated carbon-to-carbon bonds of the component (b) is hydrogenated, obtd. by reacting a block copolymer (b) composed of two or more non-elastomer blocks contg. an arom. vinyl hydrocarbon polymer and two or more elastomeric polymer blocks contg. a conjugated diene compd. polymer with hydrogen (c) in the presence of a hydrogenation catalyst under a pressure of 5-100atm at 25-300 deg.C to obtain a rubbery elastomer (c) having the arom. vinyl hydrocarbon unit and the conjugated diene compd. unit in a weight ratio of 10-55:90-45. A modified polyphenylene ether resin (A) obtd. by reacting a polyphenylene having a main chain composed of a unit of formula with a 1,2-substd. olefin compd. having an acid anhydride structure in the absence of a catalyst in a molten state is blended with a polyamide resin (B) and the component C.

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 provides a polyphenylene ether resin composition with excellent impact resistance.
-Related.

[Conventional technology]

Although polyphenylene ether resin has excellent properties such as thermal properties, mechanical properties, and electrical properties, it has the disadvantage of poor moldability due to its high melt processing temperature and low fluidity. 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 (% Kosho 45-9
No. 97), a method of blending polyamide with polyphenylene ether in a range of 30 to 95 inches (Japanese Patent Publication No. 59-41
No. 663). When a small amount of polyamide is blended, the molding processability is improved to some extent; however, from the perspective of oil resistance, this is hardly a sufficient improvement, and when a relatively large amount is blended, the solvent resistance is improved! , it lacks 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 PPE) and polyamide (hereinafter referred to as PA).

For example, in molecules such as maleic acid and maleimide, carbon-carbon double bonds and carboxylic acid groups, acid anhydride groups, acid amide groups, etc.
A method of blending a compound having a functional group such as an imide group as a third component (JP-A-56-26913), a method of blending a copolymer of a styrene compound and an α,β-unsaturated dicarboxylic acid ( Japanese Patent Publication No. 59-33614). Even if maleic anhydride or maleimide is blended as a third component, sufficient compatibility improvement cannot be achieved, but high temperature and high speed molding such as injection molding causes St, delamination, and poor appearance. It is difficult to obtain materials with toughness. or,
When a copolymer of maleic anhydride and styrene is blended, heat resistance decreases.

As a result of intensive studies to improve the compatibility between PPE and PA, the present inventors developed a modified PPIB in which a 1,2-substituted olefin compound having an acid anhydride structure was thermally grafted onto the side chain methyl group of PPIB. It has been shown that when PA is blended with POIJ phenicine ether resin (hereinafter abbreviated as modified PPE), a resin composition with toughness can be obtained over a wide composition range, unlike when unmodified PPB and PA are blended. I'm finding out.

However, this resin composition was found to have one drawback: it could only obtain an extremely low value in notched Izot impact strength, which is one method of measuring impact resistance, that is, it had very high notch sensitivity. .

[Problem that the invention seeks to solve]

The present inventors have conducted intensive studies to improve the impact resistance (notched Izot impact strength) of this modified PPE/PA resin composition, and have found that by incorporating a specific rubber-like elastic body, the impact resistance can be significantly improved. The present invention has been achieved based on the discovery that this can be improved.

[Means to solve the problem]

That is, 1 the present invention provides (1. 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. ) A modified polyphenylene ether resin obtained by reacting a 1゜2-substituted olefin compound having an acid anhydride structure in the melt state in the absence of a catalyst with a polyphenylene ether resin having a main chain of the structural unit represented by (b) This is an impact-resistant resin composition formed by blending the following specific rubber-like elastic body (elastomer) into a resin mixture consisting of a polyamide resin. The specific elastomer used here is a rubber-like elastic body. (11) consisting of a non-elastomeric polymer block containing a vinyl aromatic hydrocarbon polymer and an elastomeric polymer block containing a conjugated diene compound polymer, at least two non-elastomeric polymer blocks; and at least two elastomeric polymer blocks, fiii. an unsaturated carbon in the block copolymer.
It is a saturated thermoplastic elastomer that is an acid-modified block copolymer in which 80% or more of the carbon bonds are hydrogenated and one (M) α,β-unsaturated dicarboxylic acid anhydride is grafted.

Such an acid-modified block copolymer type saturated thermoplastic elastomer is available from Asahi Kasei Corporation, for example.
It is commercially available under the trade name 5201J.

In this elastomer, the non-elastomeric polymer block includes a vinyl aromatic hydrocarbon polymer as described above, and polystyrene blocks are particularly preferred. The elastomeric polymer block before hydrogenation is a polymer of a conjugated diene compound alone or a mixture thereof, and particularly preferably a polybutadiene block or a polyisoprene block. Hydrogenation of the elastomeric polymer block is carried out using known hydrogenation catalysts such as nickel, Raney nickel, copper chromate, molybdenum sulfide, etc., and according to known methods at desired temperatures and pressures. However, it is usually 0 at 25-300℃ under 5-100 atmospheres
．． It is carried out under conditions of 1 to 10 hours. The obtained hydrogenated elastomer is preferably hydrogenated so that the number of unsaturated carbon-carbon bonds in the block copolymer is 20 or less of the number of the same bonds before hydrogenation.

Any known method may be used to graft-add an α,β-unsaturated dicarboxylic acid anhydride, such as maleic anhydride, to the thus obtained hydrogenated elastomer block copolymer, such as , a method in which α,β-unsaturated dicarboxylic acid anhydride and a small amount of a radical initiator are added to a hydrogenated elastomer block copolymer and reacted in the melt, or a method in which a radical initiator is added to a hydrogenated block copolymer in a suspended state. A method may be adopted in which the mixture is added with an α,β-unsaturated dicarboxylic acid anhydride and reacted with heating and stirring, but it is preferable to react while melting.

Examples of α,β-unsaturated dicarboxylic anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, and maleic anhydride is particularly preferred. The amount of α,β-unsaturated dicarboxylic acid anhydride to be grafted is 0.1 to 10% by weight based on the hydrogenated block copolymer.
, preferably in the range of 0.2 to 5% by weight.

Examples of vinyl aromatic hydrocarbons in the saturated thermoplastic elastomer used in the resin composition of the present invention are:
Examples include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof, with styrene being particularly preferred. Further, examples of the conjugated diene compound include 1.
'5-butadiene, 2. '5-dimethylbutadiene, isoprene, 1,3-pentadiene, etc.

The modified polyphenylene ether resin (modified PPE) used in the resin composition of the present invention is a polyphenylene ether resin (PPE) described below and a polyphenylene ether resin (PPE) having an acid anhydride structure.
, and a 2-substituted olefin compound in the absence of a catalyst. For melt-kneading, a 21-der, Banbury Mixer 1 extruder, etc. may be used.
Although there are no particular restrictions, it is preferable to use an extruder from the viewpoint of operability. Here, examples of the 1,2-ff substituted olefin compound having an acid anhydride structure include maleic anhydride,
Examples include itaconic anhydride and citraconic anhydride, with maleic anhydride being particularly preferred.

The polyphenyresoether tree used here (in the formula, R
1 is a lower alkyl group having 1 to 5 carbon atoms, and R2 and R3 are a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) A polymer having a structural unit represented by Ether, poly(2,6-diethyl-1,4
-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-methyl-6)
-ethyl-1,4-phenylene)ether, poly(2-
Examples include methyl-6-brobyl-1,4-phenylene) ether, particularly poly(2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol/2°3.6-) Limethylphenol copolymers are preferred.

The amount of the 1,2-substituted olefin compound having an acid anhydride structure required for modification of PPP is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, particularly preferably 0. The amount ranges from .1 to 1% by weight. 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.

The polyamide resin (PA) used in the resin composition of the present invention is a polymer having -〇-N)(- bond in the main chain, such as 4-nylon, 4゜6-nylon, 6-nylon, Examples include 6.6-f nylon, 12-nylon, 11-nylon, 6.10-nylon, MXD-nylon, and the like.

The blending ratio of modified PPE and PA can be selected within a wide range, but is preferably PPR/PA=0.1-5.
, # is preferably in the range of PPE/PA=0.3 to 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-reinforced materials such as carbon fibers can be blended.

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

〔Example〕

Hereinafter, the polyphenylene ether resin composition of the present invention will be specifically illustrated by Examples and Comparative Examples, and the numbers in the examples are based on weight.

Examples and Comparative Examples Intrinsic viscosity measured in chloroform at 25°C is 0.4
7 di/9 2.6-xylenol/2°3.6-)
Limethylphenol copolymer polyphenylene ether (
2,6-xylenol 95 mol%) powder 5 (mixed with 15 g of maleic anhydride in a super mixer for 3 minutes, melt-kneaded using a twin screw extruder at 290°C, extruded, and modified with maleic anhydride. A polyphenylene ether pellet was obtained.

45 parts of the obtained modified polyphenylene ether resin; 6.
47.5 parts of 6-nylon and a hydrogenated acid-modified block copolymer-type saturated thermoplastic elastomer (manufactured by Asahi Kasei Corporation, trade name rift 3201J)
7.5 parts were mixed and melted and kneaded using an injection molding machine,
It was molded into various test pieces.

The physical properties measured using the test piece are shown in Table 1. Instead of the above thermoplastic elastomer rHR3201J,
When using a hydrogenated block copolymer-type saturated thermoplastic elastomer (manufactured by Asahi Kasei Corporation, trade name rHR1041J) that has not been grafted with α,β-unsaturated dicarboxylic acid anhydride (Comparative Example 1) , and polystyrene-polybutadiene-polystyrene type hydrogenated triblock copolymer elastomer (manufactured by Shell Chemical Co., Ltd., USA, trade name [Krayton
G 1.65 [1") was used (Comparative Example 2), compositions were obtained in the same manner as in the examples, test pieces were prepared, and various physical properties were measured. The results are shown in Table 1. Also listed.

Table 1 [Effects] A comparison of the results of Examples and Comparative Examples shows that the resin compositions of the present invention clearly show improvement in elongation and Izot 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 the following in its main chain, (b) a polyamide resin and (c) an impact-resistant resin composition comprising the following rubber-like elastic body: (i) the composition component is composed of a vinyl aromatic hydrocarbon unit and a conjugated diene compound unit; , the composition ratio is in the range of 10:90 to 55:45 on a weight basis, (ii) a non-elastomeric polymer block containing a vinyl aromatic hydrocarbon polymer and an elastomeric polymer block containing a conjugated diene compound polymer; (iii) an unsaturated carbon-carbon bond in the block copolymer; It is a saturated thermoplastic elastomer which is an acid-modified block copolymer in which 80% or more of is hydrogenated and (iv) an α,β-unsaturated dicarboxylic acid anhydride is grafted thereto.