JPS6368663A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having excellent hygroscopic characteristics, by blending a modified polyphenylene ether resin with an arom. polyamide resin having arom. rings in its main chain. CONSTITUTION:A resin compsn. consists of a modified polyphenylene ether resin (a) obtd. by reacting a polyphenylene ether resin having a main chain composed of a structural unit of formula I with a 1,2-substd. olefin compd. having an acid anhydride structure in the absence of any catalyst in a molten state, and an arom. polyamide resin (b) having amide linkages having arom. rings, represented by formulas II and III, as repeating units in its main chain. In the formulas, R1 is a 1-3C lower alkyl; R2 and R3 are each H or a 1-3C lower alkyl; R4 is an alkylenephenylene or a dialkylenephenylene; R5 is a member selected from the group consisting of phenylene, a dialkylenephenylene, etc.; and R6 is a member selected from the group consisting of a 3-10C alkylene, phenylene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of 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 that contains a modified polyphenylene ether resin and an aromatic polyamide resin having an aromatic nucleus in its main chain and has particularly excellent moisture absorption properties.

[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 (Japanese Patent Publication No. 45-9
No. 97), 30% of polyamide in polyphenylene ether
Method of blending in the range of 95 to
No. 3). When a small amount of polyamide is blended, the molding processability is improved to some extent, but it is difficult to achieve a sufficient improvement from the perspective of oil resistance.On the other hand, when a relatively large amount is blended, the 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.

Several methods have been proposed to improve the compatibility between polyphenylene ether resin (hereinafter referred to as PPE) and polyamide resin. For example, a method (specially Kaisho 56-26913
method of blending a copolymer of a styrene compound and an α,β-unsaturated dicarboxylic acid (Japanese Patent Publication No. 59-43614
) etc. Even if maleic anhydride or celeimide is blended as a third component, compatibility cannot be sufficiently improved, and when molded at high temperatures and high speeds such as injection molding, molded products exhibit delamination and poor appearance. It is difficult to obtain materials with sufficient toughness. Furthermore, when a copolymer of maleic anhydride and styrene is blended, heat resistance decreases.

[Problem that the invention seeks to solve]

The present inventors thermally grafted a 1,2-substituted olefin compound having an acid anhydride structure to the side chain methyl group of PPE to create a tough resin composition with improved compatibility between PPE and polyamide resin. completed the invention of a resin composition consisting of modified PPE and polyamide resin, and filed a patent application earlier (l￥f Application No. 61-154255 and No. 61-1).
No. 54236).

This resin composition has a small water absorption rate and changes in physical properties upon water absorption when compared to polyamide resin alone, but since it contains a polyamide resin, changes in physical properties upon water absorption cannot be avoided.

However, from the viewpoint of the user of the material, it is desired that the material undergoes as little change in physical properties and dimensions as possible.

The present invention provides a polyphenylene ether resin composition that satisfies such needs.

[Means for solving problems]

As a result of intensive studies to minimize changes in physical properties and dimensions upon water absorption of a resin composition of PPB and polyamide resin, the present inventors found that changes in physical properties and dimensions upon water absorption when using a specific polyamide. It has been discovered that a polyphenylene ether-based resin composition in which the

That is, the present invention provides: (wherein R1 is a lower alkyl group having 1 to !I carbon atoms, R2
and R3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms), and a 1,2-substituted olefin compound having an acid anhydride structure. A modified polyphenylene ether resin obtained by reacting in a molten state in the absence of (b
) An aromatic polyamide resin containing an amide bond having an aromatic nucleus represented by the following general formula (I) or (11) in the main chain as a repeating structural unit: Formula (wherein, R4 is an alkylenephenylene group or a dialkylenephenylene group) , R5 is a phenylene group 1. dialkylene phenylene group, biphenylene group, or a bridge represented by the formula is a bond (wherein l-X is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, a sulfur i atom, a carbonyl bond, or a sulfone bond) ), and R6 means an alkylene group having 3 to 1 o carbon atoms, a phenylene group, or a naphthalene group, respectively.

Polyphenylene ether resin (PP) used in the present invention
E) has a structural unit represented by the above general formula in its main chain, and may be a homopolymer, copolymer or graft polymer. Specifically, for example, PoIJ
(2,6-dimethyl-1,4-phenylene) 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-methyl-6-broby-1,4-phenylene) ether, and especially poly(2,6-dimethyl-1,4-unilene)
Ether, 2.6-dimethylphenol/2゜3.6-
A 1-limethylphenol copolymer and a graft copolymer obtained by graft-polymerizing styrene thereto are preferable as the polyphenylene ether resin used in the present invention.

The modified polyphenylene ether resin (modified PPE) used in the present invention has a 1,2-
It is obtained by melt-kneading the @-converted olefin compound under heating. The melt-kneading method is not particularly limited, such as using a Niegoo extruder or a Banbury Mixer 1 extruder, but it is preferable to use an extrusion tower in terms of operability.

Examples of the 1,2-substituted olefin compound having an acid anhydride structure include maleic anhydride, itaconic anhydride, citraconic anhydride, and maleic anhydride is particularly preferred.

The amount of acid anhydride required for PPE modification is PPE 100
Q, 01 to 10% by weight, preferably 0.
The amount corresponds to 1 to 3% by weight, particularly preferably 0.1 to 1% by weight. If less than this is used, PPE
The effect of improving the compatibility between PA and PA is small, making it difficult to obtain a composition with toughness, and if it is used in an amount exceeding this range, there are problems such as thermal decomposition of excess acid anhydride, and furthermore, there is a decrease in heat resistance and appearance. Undesirable phenomena such as defects occur.

The aromatic polyamide resin (hereinafter abbreviated as PA), which is the other resin component constituting the resin composition of the present invention, is
It is a polyamide polymer containing an amide bond having an aromatic nucleus represented by the above formula (T> or ([)) in the main chain as a repeating structural unit.More specifically, the aromatic polyamide resin of the present invention is , a polymer obtained by reacting an aromatic diamine component and a dicarboxylic acid component by a conventional method, and a polymer obtained by reacting an ω°-carboxyl compound having an aromatic nucleus by a conventional method. Here, as the aromatic diamine component,
1.4-diaminobenzene, 1.3-diaminobenzene, 1゜2-diaminobenzene, 2.4-diaminotoluene, 2.3T diaminotoluene, 2.5-diaminotoluene, 2.6-diaminotoluene, ortho , meta or para xylylene diamine, ortho, meta or para 2.2°-diami/diethylbenzene, 4.4-diaminobiphenyl, 4.4'-diaminodiphenylmethane, 4.4°-diaminodiphenyl ether, 4 .4
A diamine compound having a benzene ring, which can be typically exemplified by '-diaminodiphenylthioether, a,a'-diaminodiphenyl ketone, and 4.4'-diaminodiphenyl sulfone, is used, and the aromatic diamine component is the benzene Even if the diamine compound having a ring is used alone, as long as it contains 50 molti or more,
It may also be a mixture with other diamine compounds, such as aliphatic diamines. Of course, two or more types of diamine compounds having a benzene ring may be used in combination. next,
Dicarboxylic acid components include glutaric acid, adipic acid,
Aliphatic dicarboxyl compounds such as pimelic acid, superric acid, azelaic acid, and sebacic acid; aromatic dicarboxylic compounds such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid; Acid chlorides of carboxyl compounds can be mentioned, and these compounds may be used in combination. Further, examples of the ω-amine-ω'-carboxy compound having an aromatic nucleus include 4-aminophenylcarboxylmethane, 1-(4-aminophenyl)-2-carboxylethane, 3-(4-aminophenyl)- Examples include 1-carboxylpropane and para-(3-amino-6-hydroxy)dipropylbenzene. A preferred aromatic polyamide resin used in the present invention is a polyamide derived from a diamine compound having a benzene ring and an aliphatic dicarboxylic acid, and a more preferred example is a polyamide derived from xylylene diamine and adipic acid. The most preferred example is a polyamide derived from meta-xylylene diamine and adipic acid.

The blending ratio of modified polyphenylene ether resin and aromatic polyamide resin can be selected within a wide range, but preferably PPE/PA=0.1 to 5 in weight ratio, particularly preferably PPB/PA=0.6 to 5. is within the range of Outside this range, the characteristics of the PPP3/FA composition, such as water resistance, dimensional stability, and oil resistance, will be impaired.

The composition of the present invention may contain a rubber-like elastic body (elastomer) to impart impact resistance, if necessary. As such a rubbery elastic body, A.V. Tobolsky (A, V.

Tobolsky) [Properties and Structures of Polymers]
and 5 structures of Polymer
s) J (John Wiley & Sons)
hn Wi Iey & 5ons) (196
You can cite the definition adopted on pages 71-78 of
Elastomer has a Young's modulus of 105 to 10 at room temperature.
dynes/cInt (0, 1~1o 20
Kf/Cm2). Specific examples of elastomers include A-B-A' type elastomeric block copolymers, A-B-A'' type elastomeric block copolymers in which the double bond in the polybutadiene portion is hydrogenated, polybutadiene, polyisoprene, etc. , copolymers of diene compounds and vinyl aromatic compounds, nitrile rubber,
Ethylene-propylene copolymer, ethylene-propylene-diene copolymer (EPDM), thiol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber,
Examples include graft products of butyl rubber and polyethylene, polyester elastomers, and the like. In particular, A-B-A
° type elastomeric block copolymers are preferred. The terminal blocks A and A'' of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, B is a polymerized conjugated diene block, and the molecular weights of the B blocks are A and A.

It is desirable that the molecular weight be greater than the combined molecular weight of the blocks. End blocks A and A.

may be the same or different, and the block is a thermoplastic homopolymer or copolymer derived from a vinyl aromatic compound in which the aromatic moiety may be monocyclic or polycyclic. Examples of such vinyl aromatic compounds include styrene, alpha-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. Central block B is an elastomeric polymer derived from conjugated diene hydrocarbons such as 1,3-butadiene, 2,3-dimethylbutadiene, isoprene and 1,3-pentadiene and mixtures thereof.

The molecular weight of each terminal block A and A' preferably ranges from about 2,000 to about I Do ,000, while the molecular weight of central block B preferably ranges from about 25,000
to about 1.000.000.

The composition of the present invention may contain fiber-reinforced materials such as glass fibers and carbon fibers, and if desired,
Various commonly used additives such as stabilizers, facial dyes, mold release agents, lubricants, fillers, etc. can be appropriately blended into the polymeric material.

〔Example〕

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

Example 1 and Comparative Example 1 Intrinsic viscosity measured in chloroform at 25°C o, 4
Maleic anhydride 259 was added to 5 at/9 PPB 5KIi, mixed for 3 minutes in a super mixer, and then kneaded while being heated and melted in a twin screw extruder lζ to obtain maleic anhydride-modified PPE.

An aromatic polyamide resin with a melting point of 230°C measured by DSC (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "Reny") obtained by polycondensation of 50 parts of the obtained maleic anhydride-modified PPB, metaxylylene diamine, and adipic acid. ”)
50 parts were tri-blended in a tumbler, and then melt-mixed in an extruder to obtain a resin composition.

The obtained resin composition was molded into various test pieces using a molding machine, and various physical property values measured for the obtained test pieces are shown in Table 1.

For comparison, the results of a resin composition obtained using nylon-6,6 instead of the aromatic polyamide resin are also listed in Table 1 as a comparative example (Comparative Example 1).

Qin 1 Drying: Value measured after being left at 23°C and 150°RH for 24 hours after molding 2 Moisture absorption = Value measured after being immersed in water at 26°C for 24 hours, taken out and wiping off the adhering moisture ( Example 2 47.5 parts of modified PPP used in Example 1, Example 1
After tri-blending 5 parts of 47° of the aromatic polyamide resin used in and 5 parts of hydrogenated polystyrene-polybutadiene-polystyrene type elastomeric block copolymer (manufactured by Shell Chemical, trade name "Krayton G1650J"), A resin composition was obtained by melt-kneading.

Various test pieces were obtained by conventional methods and various physical properties were measured. The results are as follows.

Heat deformation temperature 150”C Tensile strength (yield) 750 Kf/c*z elongation (break)
Izot impact strength with 40 width notch 8K
g-tyn/cyn water absorption rate 1.0
3% (soaked at 23°C for 7 days) Examples 3 and 4 and Comparative Examples 3 and 4 Modified PPE used in Example 1 and aromatic polyamide resin,
Further, glass fibers are mixed in the proportions shown in Table 2,
A glass fiber reinforced composition was obtained using an extruder. Various physical properties were measured using test pieces obtained by conventional methods. The results are shown in Table 2 (Examples 3 and 4). For comparison, Example 3.4 was repeated using nylon-6,6 instead of the aromatic polyamide resin (Comparative Examples 3 and 4).

The results are also listed in Table 2.

〔effect〕

As is clear from the results of the examples, the resin composition of the present invention has a low water absorption rate, and in addition, after water absorption, the physical properties decrease only small, and molded products made using this composition can be used for a long time. can do.

Claims (1)

[Claims] (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 and R_3 are hydrogen atoms or lower alkyl groups having 1 to 3 carbon atoms) A polyphenylene ether resin having a structural unit represented by (b) a modified polyphenylene ether resin obtained by reacting in a molten state in the absence of A polyphenylene ether resin composition comprising an aromatic polyamide resin. Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼……(I) or Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼……(II) (In the formula, R_4 is an alkylenephenylene group or a dialkylenephenylene group. , R_5 is a phenylene group, dialkylenephenylene group, biphenylene group, or a bridge bond represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where X is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, a sulfur atom (carbonyl bond or sulfone bond), and R_6 means an alkylene group having 3 to 10 carbon atoms, a phenylene group, or a naphthalene group, respectively.)