JPH09227775A - Polyphenylene ethereal resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene ethereal resin composition remarkably improved in stress cracking characteristics while maintaining excellent properties in aspects of mechanical properties, fluidity and molding product appearance. SOLUTION: This polyphenylene ethereal resin composition comprises the following components (A) to (D): (A) a polyphenylene ethereal resin, (B) a styrene-based resin, (C) a rubber-like polymer and (D) a styrene-based polymer graft polyolefin. The content of the component D is 0.1-20 pts.wt. based on 100 pts.wt. total amount of the components A, B and C and the contents of the components A, B and C are 1-100 pts.wt. component A, 0-99 pts.wt. component B and 0-50 pts.wt. component C (the total amount of the components A, B and C is 100 pts.wt.).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene ether resin composition. More specifically, the present invention relates to a polyphenylene ether resin composition having improved stress crack resistance, which contains a polyphenylene ether resin and a styrene polymer graft polyolefin as essential components. Here, the polyphenylene ether resin composition means a resin composition containing a polyphenylene ether resin as a component.

[0002]

2. Description of the Related Art Polyphenylene ether-based resins are known resins having excellent physical properties such as dimensional stability and dielectric properties, and polyphenylene ether-based resin compositions composed of polyphenylene ether-based resins and styrene-based resins are known. It is a known composition that is excellent in impact resistance, workability, heat resistance, and mechanical properties.

However, the polyphenylene ether-based resin or the polyphenylene ether-based resin composition comprising the polyphenylene ether-based resin and the styrene-based resin is contacted with an organic solvent such as acetone, alcohol, hexane, coconut oil or grease under stress. However, it has a drawback that cracks easily occur (stress crack resistance is not good), so that its use is extremely limited.

As an invention of a polyphenylene ether-based resin composition for which the stress crack resistance of the polyphenylene ether-based resin has been improved, JP-A-48-42047, JP-A-48-47943 and JP-A-48-4943 are disclosed. There is an invention described in Japanese Patent No. 62851.

JP-A-48-42047 discloses that in a composition comprising polyphenylene ether and rubber-modified polystyrene, the polystyrene matrix in the rubber-modified polystyrene has an intrinsic root viscosity of at least about 1.0 dl / g. A polyphenylene ether-based resin composition which is a "high impact strength thermoplastic composition" is described.

Further, JP-A-48-62851 discloses that "polyphenylene ether, vinyl aromatic compound-conjugated diene elastomer block copolymer, and styrene homopolymer or random copolymer resin as an optional component. A polymer composition containing "a polyphenylene ether-based resin composition" is described.

Further, in JP-A-48-47943, there is disclosed a polyphenylene ether resin composition which is "a polymer composition containing polyphenylene ether, an acrylic resin-modified acrylonitrile-diene rubber-styrene resin and a polystyrene resin as an optional component". Things are listed.

[0008]

However, in the polyphenylene ether resin compositions described in JP-A-48-42047 and JP-A-48-62851, there are other mechanical properties such as rigidity. There is a problem that it is significantly impaired. Further, in the polyphenylene ether-based resin composition described in JP-A-48-47943, the compatibility between the polyphenylene ether-based resin and the acrylic resin-modified acrylonitrile-diene rubber-styrene resin is extremely poor, so that the acrylic resin-modified acrylonitrile is used. There is a problem that a sufficient effect cannot be obtained because the content ratio of -diene rubber-styrene resin is extremely limited.

An object of the present invention is to provide a polyphenylene ether-based resin composition in which stress crack resistance is greatly improved while maintaining excellent properties in terms of mechanical properties, fluidity and appearance of molded articles. is there.

[0010]

Means for Solving the Problems The inventors of the present invention have been earnestly researching the development of a polyphenylene ether resin composition having improved stress crack resistance. As a result, they have found that the object of the present invention can be achieved by using a styrene polymer graft polyolefin as a constituent component of the composition, and have completed the present invention.

That is, the present invention provides the following components (A) to
A polyphenylene ether-based resin composition containing (D), wherein the content ratios of the component (D) are the component (A) and the component (B).
0.1 to 100 parts by weight of the total amount of the component (C) and
It is 20 parts by weight, and the content ratio of the component (A), the component (B) and the component (C) is 1 to 100 parts by weight of the component (A), 0 to 99 parts by weight of the component (B) and 0 of the component (C). To 50 parts by weight (the sum of the content ratios of the component (A), the component (B) and the component (C) is 100 parts by weight), and the polyphenylene ether resin having improved stress crack resistance. It is a composition. Component (A) Polyphenylene ether-based resin Component (B) Styrene-based resin Component (C) Rubber-like polymer Component (D) Styrene-based polymer Grafted polyolefin

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) polyphenylene ether resin according to the present invention means a compound represented by the following general formula (in the formula, R ₁ ,
R ₂ , R ₃ , R ₄ and R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and one of them is always a hydrogen atom. ) Is a polymer obtained by oxidatively polymerizing one or more of the phenol compounds represented by the formula (1) with oxygen or an oxygen-containing gas using an oxidation coupling catalyst, and a known polyphenylene ether resin can be used.

[0013]

R ₁ , R ₂ , R ₃ , R _{4 according to the} above general formula
Specific examples of R ₅ and R ₅ are hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, Hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl,
Methylphenyl, dimethylphenyl, ethylphenyl,
Allyl etc. are mentioned.

Specific examples of the above general formula include phenol; o-, m-, or p-cresol; 2,6-, 2,
5-, 2,4- or 3,5-dimethylphenol; 2-
Methyl-6-phenylphenol; 2,6-diphenylphenol; 2,6-diethylphenol; 2-methyl-6-ethylphenol; 2,3,5-, 2,3,6-
Or 2,4,6-trimethylphenol; 3-methyl-
6-t-butylphenol; thymol; 2-methyl-6
-Allylphenol and the like.

The component (A) according to the present invention is further a phenol compound other than the above general formula, for example, bisphenol-.
A, a polymer obtained by similarly oxidatively polymerizing a copolymer of a polyvalent hydroxyaromatic compound such as tetrabromobisphenol-A, resorcin, hydroquinone, and a novolak resin with a phenol compound represented by the above general formula. You may.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used.
The method for producing such a polyphenylene ether resin is described in, for example, U.S. Pat. Nos. 3,306,874, 3,306,875 and 3,257,357, and Japanese Patent Publication No.
2-17880, JP-A-50-51197 and JP-A-1-304119.

Specific examples of the component (A) include poly (2,2)
6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether),
Poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenyl)
Phenylene ether), poly (2,6-dipropyl-)
1,4-phenylene ether), poly (2-ethyl-6)
-Propyl-1,4-phenylene ether), poly (2,6-dibutyl-1,4-phenylene ether),
Poly (2,6-dipropenyl-1,4-phenylene ether), poly (2,6-dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly ( 2,6-dimethoxy-1,
4-phenylene ether), poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy) -1,4-phenylene ether), poly (2-methyl-6-phenyl-)
1,4-phenylene ether), poly (2-methyl-
1,4-phenylene ether), poly (2-ethoxy-
1,4-phenylene ether), poly (2-chloro-
1,4-phenylene ether), poly (3-methyl-6)
-T-butyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether),
Poly (2,5-dibromo-1,4-phenylene ether), poly (2,6-dibenzyl-1,4-phenylene ether), and various copolymers containing a plurality of repeating units constituting these polymers You can list coalescence.
2,3,6-trimethylphenol in the copolymer,
Copolymers of polysubstituted phenols such as 2,3,5,6-tetramethylphenol and 2,6-dimethylphenol are also included.

Poly (2,6-dimethyl-1,4-phenylene ether) is preferred as component (A),
Poly (2,6-diphenyl-1,4-phenylene ether) and a large part of 2,6-dimethylphenol and a small part of 3-methyl-6-t-butylphenol or 2,3
Examples thereof include copolymers with 6-trimethylphenol.

The molecular weight of the component (A) cannot be unconditionally defined because its preferred range varies depending on the purpose, but it is generally 0.1 to 0.0.1 expressed as an intrinsic viscosity measured in chloroform at 30 ° C. 7 dl / g, more preferably 0.2 to 0.6 dl / g.

The component (A) according to the present invention includes those obtained by modifying the above-mentioned polymers or copolymers by graft-polymerizing styrene-based monomers such as styrene and α-methylstyrene.

The component (B) styrene resin according to the present invention is a polymer or copolymer having at least 25% by weight of a repeating unit represented by the following general formula and derived from a styrene monomer. Well-known polymers and copolymers can be used.

[0023]

In the above general formula, R is hydrogen and has 1 carbon atom.
~ 6 alkyl or halogen; Y is hydrogen, vinyl, halogen, amino group, hydroxyl group or alkyl having 1 to 6 carbon atoms; n is 0 or an integer of 1 to 5.

Examples of the component (B) are homopolymers such as polystyrene and polychlorostyrene; for example, ethylene-α-olefin- (non-conjugated diene) copolymer rubber and polybutadiene having a crystallinity of less than 15%. Rubber, styrene-butadiene random copolymer rubber, styrene-butadiene block copolymer rubber, hydrogenated styrene-butadiene block copolymer rubber (having repeating units derived from butadiene hydrogenated), polyisoprene rubber, Styrene-isoprene random copolymer rubber, styrene-isoprene block copolymer rubber, hydrogenated styrene-isoprene random copolymer rubber (hydrogenated repeating units derived from isoprene), urethane rubber, natural rubber, etc. Polystyrene modified with rubber in rubber modified copolymer Styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-methyl acrylate copolymer, etc. A copolymer of a monomer and a styrene-based monomer; a mixture of these.

The component (C) rubber-like polymer according to the present invention means natural and synthetic polymers which are elastic at room temperature, and known rubber-like polymers can be used. Examples of the component (C) include ethylene-α-olefin- (non-conjugated diene) -based copolymer rubber having a crystallinity of less than 15%, and ethylene-α-olefin- (non-copolymer of a crystallinity of less than 15%. Copolymer rubber obtained by graft-polymerizing styrene-based monomer to conjugated diene) copolymer rubber, polybutadiene rubber, styrene-butadiene random copolymer rubber, styrene-butadiene block copolymer rubber, hydrogenated styrene- Butadiene block copolymer rubber (hydrogenated repeating units derived from butadiene), copolymer rubber made by graft-polymerizing styrene monomer to polybutadiene rubber, styrene-butadiene random copolymer rubber Styrene was added to the copolymer rubber and styrene-butadiene block copolymer rubber that are obtained by graft-polymerizing styrene monomers. Graft-polymerization of styrene-based monomer onto copolymer rubber and hydrogenated styrene-butadiene block copolymer rubber (hydrogenated repeating units derived from butadiene) Copolymer rubber, polyisoprene rubber, styrene-isoprene random copolymer rubber, styrene-isoprene block copolymer rubber, hydrogenated styrene-isoprene random copolymer rubber (repeating units derived from isoprene are hydrogen A copolymer rubber obtained by graft-polymerizing a styrene-based monomer onto a polyisoprene rubber, a copolymer rubber obtained by graft-polymerizing a styrene-based monomer onto a styrene-isoprene random copolymer rubber ,
Styrene-isoprene block copolymer rubber copolymer rubber made by graft-polymerizing styrene-based monomer, hydrogenated styrene-isoprene random copolymer rubber (hydrogenated repeating units derived from isoprene) Examples thereof include a copolymer rubber obtained by graft-polymerizing a styrene-based monomer, a polyurethane rubber, and a mixture of these rubbers. Furthermore, a modified rubber modified by reacting these rubbers with a compound having a functional group such as a carboxyl group or an epoxy group is also included in the component (C).

A copolymer rubber obtained by graft-polymerizing the above-mentioned various styrene-based monomers relating to the component (C),
The content of the repeating unit derived from the styrene-based monomer is preferably less than 25%, and styrene is most preferable as the styrene-based monomer.

The ethylene-α-olefin- (non-conjugated diene) type copolymer rubbers relating to the components (B) and (C) include ethylene-propylene copolymer rubber and ethylene-butene-1 copolymer. Combined rubber, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene-butene-1
-Non-conjugated diene copolymer rubber and the like.

Further, the above-mentioned, for example, styrene-butadiene block copolymer rubber, hydrogenated styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber and hydrogenated product relating to the components (B) and (C) are added. The number of each block in the styrene-isoprene block copolymer rubber is not particularly limited. Taking the styrene-butadiene block copolymer rubber as an example, the copolymer rubber is a styrene-butadiene block copolymer rubber. Besides, for example, styrene-butadiene-styrene block copolymer rubber and styrene-butadiene-styrene-
It may be a butadiene block copolymer rubber.

The component (D) styrene polymer-grafted polyolefin according to the present invention is a styrene monomer or a styrene monomer and a repeating unit derived from an unsaturated monomer copolymerizable therewith. The polymer is a component formed by grafting onto a polyolefin.

The styrenic monomer for deriving the styrenic polymer as the component (D) is a compound represented by the following general formula, not only one of the compounds represented by the general formula but also 2
More than one species can be used in combination.

[0032]

In the general formula, R is hydrogen and has 1 to 6 carbon atoms.
Alkyl or halogen; Y is hydrogen, vinyl, halogen, amino group, hydroxyl group or alkyl having 1 to 6 carbon atoms;
n is 0 or an integer of 1 to 5. As the compound represented by the above general formula, styrene, α-methylstyrene, α-
Examples thereof include chlorostyrene, vinyltoluene, and divinylbenzene, and styrene is particularly preferable.

Specific examples of the unsaturated monomer copolymerizable with the styrene monomer as the component (D) include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl (meth) acrylate, ethyl (meth) ) Alkyl ester derivatives of unsaturated carboxylic acids such as acrylate and butyl (meth) acrylate; fumaric acid, maleic acid, maleic anhydride,
Dicarboxylic acids or acid anhydrides such as itaconic acid, mono- or diethyl esters of maleic acid, N-phenylmaleimide, N, N'-metaphenylenebismaleimide and the like derivatives of such dicarboxylic acids or acid anhydrides; acrylamide, N- ( Hydroxymethyl) acrylamide; glycidyl derivatives of (meth) acrylic acid such as glycidyl (meth) acrylate; vinyl acetate; acrylonitrile,
Includes vinyl cyanide compounds such as methacrylonitrile. Among these, acrylonitrile is mentioned as a preferable unsaturated monomer.

The polyolefin in the component (D) is, for example, propylene, butene-1, pentene-1, hexene-1,3-methylbutene-1,4-methylpentene-.
1, a homopolymer of α-olefin such as heptene-1, octene-1, a mixture of the homopolymers, a copolymer of two or more kinds of these α-olefins in the form of a random or block, these α -A copolymer in the form of a random or block, which comprises one or more majority of olefin and ethylene, and a random copolymer of one or more majority of these α-olefins and another unsaturated monomer, It is a copolymer in the form of a block or a graft, a mixture of these copolymers, or a product obtained by oxidizing, halogenating or sulfonated these polymers, and at least partially having crystallinity.

Examples of the other unsaturated monomer include acrylic acid, maleic acid, itaconic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic anhydride, aryl maleic acid imide, alkyl maleic acid imide and the like. Unsaturated organic acids or derivatives thereof; vinyl esters such as vinyl acetate and vinyl butyrate; aromatic vinyl compounds such as styrene and methylstyrene; vinylsilanes such as vinyltrimethylmethoxysilane and γ-methacryloyloxypropyltrimethoxysilane; dicyclopentadiene A non-conjugated diene such as 4-ethylidene-2-norbornene or the like can be used.

When the polyolefin as the component (D) is polypropylene, the polypropylene is a polypropylene homopolymer which is a homopolymer of propylene, a polypropylene random copolymer of propylene and ethylene, butene-1, etc. After the propylene is polymerized in the step, the second step further includes a polypropylene block copolymer obtained by copolymerizing ethylene with propylene and an α-olefin such as butene-1. In the first step in the production of polypropylene block copolymer, propylene may be homopolymerized, or the content of propylene and the polymer produced in the step may be 6% or less.
Mol% or less of ethylene or α-of 4 to 6 carbon atoms
You may copolymerize with an olefin. The copolymer segment, which is the second segment polymerized in the second step, is a homopolymer of ethylene or a copolymer of ethylene and propylene in which the ethylene content in the polymer produced in the step is 10 mol% or more, or A copolymer of ethylene, propylene and an α-olefin having 4 to 6 carbon atoms is preferable. The polymer produced in the second step is 10 based on the total polymerization amount.
７０70% by weight. The crystallinity of the polymer portion in the first step of the above-mentioned polypropylene homopolymer, polypropylene random copolymer and polypropylene block polymer is 20% or more.

The crystallinity is widely known by a method such as a method of measuring the heat of fusion of crystals by DSC, a method of measuring a density, a method of measuring by an X-ray diffraction method, and the like. Among them, the measurement of the crystallinity in the present invention is described in G. N
X-ray diffraction method reported by atta (Mac
romol. Chem, 35, 94 (1960)).

The homopolymer, block or random copolymer of propylene can be obtained, for example, by reacting in the presence of a Ziegler-Natta type catalyst. It can also be obtained by a homogeneous catalyst represented by a metallocene catalyst. Among these polypropylenes, a polypropylene random copolymer is preferable from the viewpoint of maintaining impact strength and improving stress cracks.

In the component (D), the ratio of the repeating unit derived from the unsaturated monomer copolymerizable with the styrene-based monomer: the repeating unit derived from the styrene-based monomer: polyolefin is 0. ˜18.4% by weight: 20 to 80% by weight: 80 to 20% by weight (the sum of the three is 100%), and is a repeat derived from an unsaturated monomer copolymerizable with a styrene monomer. The weight ratio of the unit to the total amount of the repeating unit and the repeating unit derived from the styrenic monomer is 0.45 or less.

When the content of the polyolefin in the component (D) is less than 20% by weight, the stress crack resistance of the obtained polyphenylene ether resin composition is unsatisfactory, and when it exceeds 80% by weight, it is combined with the component (D). Since the compatibility with (A) decreases, there is a possibility that problems such as deterioration of physical properties of the obtained polyphenylene ether resin composition and deterioration of moldability may occur. Further, the weight ratio of the repeating unit derived from the unsaturated monomer copolymerizable with the styrene-based monomer to the total amount of the repeating unit and the repeating unit derived from the styrene-based monomer is 0. When it exceeds 45, the compatibility between the component (D) and the component (A) is deteriorated, and the properties of the polyphenylene ether resin composition obtained in the same manner are deteriorated and the moldability is deteriorated. May occur.

The component (D) may be a known method, for example, an emulsion polymerization method, a bulk polymerization method (see Japanese Patent Publication No. 42-662, US Pat. No. 3435096), a solution polymerization method (US Pat. No. 3,538,190, the same). 3538191), and suspension polymerization method (Japanese Patent Publication No. 49-10831, Japanese Patent Publication No. 57-40166, Japanese Patent Publication No. 62-10).
565). When the polyolefin is polypropylene, the styrene monomer and optionally the unsaturated monomer may be graft-copolymerized onto the polypropylene in the presence of an arbitrary amount of a free radical initiator and a dispersant in an aqueous suspension. The turbid polymerization method is particularly preferred.

Examples of the suspending agent include polyvinyl alcohol, cellulose compounds, acrylic acid compounds, inorganic salts and alkylene oxides. Examples of free radical initiators include organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylhydroperoxide and dicumyl peroxide, azobisisobutyronitrile. ,
Examples thereof include azo compounds such as azobisdimethylvaleronitrile.

Component (D) is generally produced by graft-polymerizing a styrenic monomer and optionally an unsaturated monomer onto a polyolefin. Therefore, generally, a styrene-based monomer is added to the polyolefin. Graft polymer in which polymer or unsaturated monomer is grafted, homopolymer of styrene monomer or unsaturated monomer, copolymer of styrene monomer and unsaturated monomer And a polyolefin which is not grafted with a styrene monomer or an unsaturated monomer.

Examples of the preferred component (D) include styrene-acrylonitrile copolymer graft polypropylene, styrene-methyl methacrylate copolymer graft polypropylene, styrene-maleic anhydride copolymer graft polypropylene and the like. Further, as more preferable component (D), for example, styrene-acrylonitrile copolymer graft crystalline polypropylene, styrene-
An example is a methyl methacrylate copolymer grafted crystalline polypropylene.

The essential components of the polyphenylene ether resin composition of the present invention are the component (A) polyphenylene ether resin and the component (D) styrene polymer graft polyolefin, and the component (B) styrene resin is It is mainly used for improving the moldability of the polyphenylene ether resin composition, and the component (C) rubbery polymer is mainly used for improving the impact resistance improvement of the polyphenylene ether resin composition.

When the content ratio of the component (D) is less than 0.1 parts by weight, the effect of improving the stress crack resistance is unsatisfactory, and when it exceeds 20 parts by weight, the moldability becomes poor, so that it is not preferable. . Further, if the content ratio of the component (A) is less than 1% by weight, the heat resistance of the polyphenylene ether resin composition is impaired, which is not preferable. When the amount of the component (C) exceeds 50% by weight, the heat resistance and mechanical strength of the polyphenylene ether resin composition are deteriorated, which is not preferable.

The preferred content ratios of the components constituting the polyphenylene ether resin composition of the present invention are as follows in view of the balance of fluidity, heat resistance and mechanical properties. Component (A) 10 to 100% by weight Component (B) 0 to 90% by weight Component (C) 0 to 30% by weight Component (A) + (B) + (C) = 100 parts by weight Component (D) 1 to 15 Parts by weight

More preferable content ratios are as follows. Component (A) 10 to 90% by weight Component (B) 10 to 90% by weight Component (C) 0 to 30% by weight Component (A) + (B) + (C) = 100 parts by weight Component (D) 1 to 15 Parts by weight

If desired, the composition of the present invention may contain a crystalline olefin polymer having a crystallinity of 15% or more in addition to the components (A) to (D). Examples of such olefin polymers include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, propylene-ethylene copolymer, ethylene-butene-1 copolymer, ethylene-pentene copolymer, ethylene- Olefin polymers such as hexene copolymer and poly-4-methylpentene-1; predominant amount of olefin and vinyl monomer copolymerizable therewith (eg, acrylic acid esters, methacrylic acid esters, vinyl acetate) ,styrene,
Examples thereof include copolymers with acrylonitrile and glycidyl (meth) acrylate. The above copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer. These polymers and copolymers can be used alone or as a mixture of two or more. Of these, polypropylene, polyethylene of various densities and propylene-ethylene copolymers are preferable, and particularly preferable are polypropylene, propylene-ethylene random copolymer and propylene-ethylene block copolymer.

If necessary, the composition of the present invention may further contain other polymer compounds and auxiliaries. As other polymer compounds, for example, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyvinyl pyridine, polyvinyl carbazole, polyacrylamide,
Polymers such as polyacrylonitrile, polycarbonate, polysulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polyarylene esters (for example, U-polymer of Unitika Ltd.), polyphenylene sulfide, 6-nylon,
Polyamides such as 6,6-nylon and 12-nylon,
Examples thereof include condensation polymer compounds such as polyacetal, and various thermosetting resins such as silicone resin, fluororesin, polyimide, polyamideimide, phenol resin, alkyd resin, unsaturated polyester resin, and dabon resin.

The composition of the present invention may contain various fillers for the purpose of strengthening or imparting functions. As the filler, glass fiber, carbon fiber, polyamide fiber, metal fiber such as aluminum and stainless steel and fiber such as metal whiskers, silica, alumina, calcium carbonate,
Talc, mica, clay, kaolin, magnesium sulfate, wollastonite, carbon black, TiO ₂ ,
Inorganic fillers such as ZnO and Sb ₂ O ₃ can be used. Any of these can be used as a reinforcing material for the composition, but fillers such as carbon fiber, metal fiber, and carbon black reduce the surface resistivity and volume resistivity of the resin composition, so that conductivity is imparted. A resin composition can also be obtained.

For the purpose of improving the rigidity and heat resistance of the resin composition of the present invention, an inorganic filler such as glass fiber, potassium titanate whiskers, talc, mica, calcium carbonate, or carbon fiber is used as a filler. It is particularly preferable to use.

The resin composition of the present invention further comprises Sb ₂ O ₃ ,
Flame retardants or flame retardants such as halogen compounds and phosphates, other lubricants, nucleating agents, plasticizers such as triphenyl phosphate and phthalates, stabilizers, dyes, pigments, antistatic agents, antioxidants , A weather resistance-imparting agent and the like may also be contained.

Examples of flame retardants are triphenyl phosphate, tricresyl phosphate, phosphates obtained from a mixture of isopropylphenol and phenol,
Phosphate esters exemplified by phosphates obtained from a mixture of a bifunctional phenol such as benzohydroquinone, resorcin or bisphenol A and other alcohols or phenols; decabromobiphenyl, pentabromotoluene, decabromodiphenyl ether , Brominated compounds exemplified by hexabromobenzene, brominated polystyrene, brominated epoxy resin and the like; nitrogen-containing compounds such as melamine and melamine triisosinurate.

Other examples of stabilizers include sterically hindered phenols, organic phosphites, oxalic acid diazides, and sterically hindered amines, and examples of lubricants include polyethylene wax and paraffin. Can be mentioned.

Although the compounding ratio of the other substances mentioned above can be arbitrarily selected according to the purpose, the general guideline for using them is to show the sum of the components (A) and (B). The flame retardant is 30 parts by weight or less, preferably 1 to 20 parts by weight, the stabilizer is 20 parts by weight or less, preferably 0.001 to 10 parts by weight, and the lubricant is 2 parts by weight or less with respect to 100 parts by weight. is there.

The method for producing the polyphenylene ether resin composition of the present invention is not particularly limited, and various methods such as a solution blending method and a melt kneading method can be exemplified, but the preferable method is the melt kneading method. As a specific method, after mixing each component with a known mixer such as a Henschel mixer, a super mixer, a ribbon blender, a V blender, etc., the mixture is mixed with a Banbury mixer, a plastomill, a Brabender plastograph, a uniaxial or biaxial extrusion. Examples of the method include melt kneading with a known kneader such as a kneader. The kneading temperature is 150 to 400 ° C, preferably 200 to 350 ° C
You can choose from the range.

The order of blending and kneading each component is arbitrary,
For example, in the case of melt-kneading using an extruder or the like, after kneading any combination of each component separately, all the combinations may be blended and kneaded, or a plurality of components may be supplied to one extruder. A port (feed port) may be provided, and one kind or two or more kinds of components may be sequentially fed from each feed port. For example,
A method in which the components (A) to (D) are collectively added and melt-kneaded at the same time, the components (A), (B) and (C) are melt-kneaded in advance, and then the component (D) is additionally added. Melt kneading method, components (A), (C) and (D) are melt kneaded in advance, and then component (B) is additionally added to melt knead the components (B) and (D). Preliminary kneading may be performed in advance, and then component (A) may be additionally added and melt kneading may be performed.

Examples of the use of the polyphenylene ether resin composition of the present invention include various cases, frames, connectors, switches and other mechanical parts in the electric / electronic / OA fields; magnet flywheels and door mirrors in the automotive / vehicle fields. Stays, lamp reflectors, cylinder head covers, various gears; various housings in the mechanical field, pulleys, handles and the like.

[0061]

The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited by the examples. All the examples and comparative examples are shown in the table below.

The components used and their abbreviations are as follows. Component (A) polyphenylene ether-based resin PPE has an intrinsic viscosity of 0.46 as measured in chloroform at 30 ° C.
dl / g of poly (2,6-dimethyl-1,4-phenylene ether).

Component (B) Styrenic resin PS1 Sumibright (registered trademark) E1 manufactured by Sumitomo Chemical Co., Ltd.
83N (grade) polystyrene. The weight average molecular weight is 30 × 10 ⁴ , and the MI is 2.4 g / 10 min under the measurement conditions of 200 ° C. and 5 kg load. PS2 Sumitomo Chemical Co., Ltd. Sumibright (registered trademark) M5
High impact polystyrene of 88 (grade). The rubber content is 9.0 wt%, the weight average molecular weight is 21.5 × 10 ⁴ ,
MI is 3.0 g / 200 ° C. under a measurement condition of 5 kg load.
10 min.

Component (C) Rubber-like polymer A hydrogenated styrene-butadiene-styrene block copolymer, Kraton (trade name) G1657 (grade) manufactured by SEBS Shell Chemical.

Component (D) Styrene-based polymer graft poly
In a 5 liter autoclave equipped with an olefin ASgPP1 stirrer, 2200 ml of pure water obtained by dissolving 6 g of Pluck (trade name) F68 (grade) made by Asahi Denka Co., Ltd. and Sumitomo Noblen made by Sumitomo Chemical Co., Ltd. (Registered trademark) W531 (grade) of polypropylene random copolymer (a crystalline polypropylene having MI of 8.0 units at 230 ° C. and 2.16 kg?) 300 g, and stirred and suspended. Made cloudy. Then, as a polymerization initiator, t
-Butyl peroxypivalate 9 g and P-benzoquinone 0.18 g, and 81 g of styrene as a monomer and 48 g of acrylonitrile were added, and immediately placed in an oil bath in which the autoclave was preheated to 30 ° C. The temperature rise was started. 110 at a rate of about 1 ℃ per minute
The temperature was raised to 0 ° C, and the temperature was kept at 110 ° C for 30 minutes to carry out a polymerization reaction. The formed granular graft product was washed with water and dried in vacuum at 95 ° C. to obtain a styrene-acrylonitrile copolymer grafted polypropylene random copolymer.
(ASgPP1) was obtained.

ASgPP2 In the above production method of ASgPP1, W531 was added to Sumitomo
A styrene-acrylonitrile copolymer-grafted polypropylene homopolymer (ASgPP2) was obtained in the same manner except that the polypropylene homopolymer Bren (registered trademark) W501 (grade) was used.

MSgPP The same method as in the above production method of ASgPP1 except that acrylonitrile was changed to methyl methacrylate to obtain a styrene-methyl methacrylate copolymer-grafted polypropylene homopolymer (ASgPP). It was

SgPP A styrene polymer-grafted polypropylene homopolymer (SgPP) was obtained in the same manner as in the production method of ASgPP1 except that 129 g of styrene was the only monomer used.

Other Ingredients Polyolefin Sumitomo Noblen (registered trademark) W manufactured by Sumitomo Chemical Co., Ltd.
531 (grade) is a random copolymer of ethylene and propylene having an ethylene content of 3 wt% and M
I is 8 g / under measurement conditions of 230 ° C. and 2.16 kg load.
10 minutes, the crystallinity is 56 wt%. Abbreviated as PP1. Sumitomo Chemical Co., Ltd.'s Sumitomo Noblene (registered trademark) W501 (grade) propylene homopolymer
The MI was 8 g / 10 min under the measurement conditions of 230 ° C. and a load of 2.16 kg, and the crystallinity was 60 wt%. PP
It is abbreviated as 2. Sumikasen (registered trademark) F210 (grade) low-density polyethylene manufactured by Sumitomo Chemical Co., Ltd. Abbreviated as LL.

Filler Glass fiber TP64 (grade) manufactured by Nippon Sheet Glass Co., Ltd., fiber diameter 10 μ, fiber length 3 mm. Abbreviated as GF.

The methods for measuring the physical properties of the resin composition are as follows. Notched Izod impact strength (Unit: kg ・ cm / c
m) It is a value measured according to ASTM D256 with respect to a 3.2 mm-thick test piece prepared by an injection molding method. It is abbreviated as Izod.

Stress crack resistance (unit is time) A semi-circular jig having a curvature R of 165 mm and having a test piece of 100 mm × 12.7 mm × 3 mm mounted thereon is dipped in kerosene or tri-n-butylphthalate (TnBP). Then, the time from the immersion to the start of cracking of the test piece was measured. The longer the time until crack generation, the better the stress crack resistance. Abbreviated as "stoke resistant".

Example 1 30 parts by weight of PPE, 60 parts by weight of PS1 and SEBS10
Parts by weight and 4 parts by weight of ASgPP1 were charged from the first hopper of a continuous twin-screw kneader (TEM-50 manufactured by Toshiba Machine Co., Ltd.), the cylinder temperature was set to 260 ° C., and the melt was kneaded at a screw rotation speed of 330 rpm. Granulate,
A polyphenylene ether resin composition was obtained. The obtained composition was injection molded at 260 ° C. to prepare a test piece, and the test piece was evaluated for physical properties and stress crack resistance against kerosene.

Example 2 The same procedure as in Example 1 was carried out except that ASgPP1 in Example 1 was changed to ASgPP2.

Example 3 Example 1 was repeated except that ASgPP1 in Example 1 was changed to SgPP.

Comparative Example 1 Example 1 was repeated except that ASgPP1 in Example 1 was not added.

Comparative Example 2 The ASgPP1 used in Example 1 was replaced with Sumitomo Noblen W53.
Example 1 was repeated except that the random copolymer of ethylene and propylene was changed to 1.

Comparative Example 3 The ASgPP1 used in Example 1 was replaced by Sumitomo Noblen W50.
Example 1 was repeated except that the propylene homopolymer No. 1 was changed.

Comparative Example 4 The same procedure as in Example 1 was carried out except that ASgPP1 in Example 1 was changed to low-density polyethylene called Sumikasen F210.

Example 4 40 parts by weight of PPE, 60 parts by weight of PS1 and ASg
4 parts by weight of PP1 was charged from the first hopper of a continuous twin-screw kneader (TEM-50 manufactured by Toshiba Machine Co., Ltd.), the cylinder temperature was set to 260 ° C., and the screw rotation speed was 330.
Melt kneading at rpm and granulation were performed to obtain a polyphenylene ether resin composition. The obtained composition was injection molded at 260 ° C. to prepare a test piece, and the test piece was evaluated for physical properties and stress crack resistance against kerosene.

Example 5 Example 4 was repeated except that MSgPP was used instead of ASgPP1.

Example 6 30 parts by weight of PPE, 50 parts by weight of PS2, 20 parts by weight of glass fiber TP64 manufactured by Nippon Sheet Glass Co., Ltd. and 3 parts by weight of ASgPP1 were continuously twin-screw kneader (TEM-50 manufactured by Toshiba Machine Co., Ltd.). Was charged from the first hopper, the cylinder temperature was set to 260 ° C., and the mixture was melt-kneaded at a screw rotation speed of 330 rpm and granulated to obtain a polyphenylene ether-based resin composition. The composition obtained is 2
A test piece was prepared by injection molding at 60 ° C., and the test piece was evaluated for physical properties and stress crack resistance to tri-n-butyl phthalate.

Example 7 The procedure of Example 6 was repeated, except that the amount of ASgPP1 added in Example 6 was changed to 7 parts by weight.

Comparative Example 5 Example 6 was repeated except that ASgPP1 in Example 6 was not added.

The mixing ratios (parts by weight) of the components used in the examples and comparative examples and the evaluation results are summarized in the table below.

[0086]

From the comparison between the examples and the comparative examples, it can be seen that the component (D) significantly contributes to the improvement of stress crack resistance. The polyphenylene ether resin composition of the present invention having greatly improved stress crack resistance can be used, for example, in automobile parts, motor housings and the like.

[0087]

Table 1 ──────────────────────────────────── Example 1 Example 2 Example 3 Comparison Example 1 Comparative Example 2 Comparative Example 3 ───────────────────────────────────── Component (A) PPE 30 30 30 30 30 30 30 ───────────────────────────────────── Component (B) PS1 60 60 60 60 60 60 60 ───────────────────────────────────── Component (C) SEBS 10 10 10 10 10 10 10 ───────────────────────────────────── Ingredient (D) ASgPP1 4 ASgPP2 4 SgPP 4 ───────────────────────────────────── Other ingredients PP1 4 PP2 4 ───────────────────────────────────── Physical property Izod 29 25 25 25 29 25 20 Stoke resistance No occurrence No occurrence 24 hours 30 minutes 10 minutes 10 minutes ──────────────────────────── ─────────

[0088]

[Table 2] ──────────────────────────────────── Comparative Example 4 Example 4 Example 5 Implementation Example 6 Example 7 Comparative Example 5 ───────────────────────────────────── Component (A) PPE 30 40 30 30 30 30 30 ───────────────────────────────────── Component (B) PS1 60 60 60 PS2 50 50 50 50 ───────────────────────────────────── Component (C) SEBS 10 ───────────────────────────────────── Ingredient (D) ASgPP1 4 37 MSgPP 4 ───────────────────────────────────── Other ingredients LL 4 GF 20 20 20 ───────────────────────────────────── Physical property Izod 23 15 15 9 9 9 10 Stoke resistance 10 minutes 24 hours 24 hours 23 hours 23 hours 2 hours ────────────────────────────── ───────

Front Page Continuation (72) Inventor Takeshi Fujii 5-1 Anezaki Kaigan, Ichihara, Chiba Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. A polyphenylene ether-based resin composition containing the following components (A) to (D), wherein the content ratio of the component (D) is as follows: component (A), component (B) and component (C). The total amount is 0.1 to 20 parts by weight with respect to 100 parts by weight, and the content ratio of the component (A), the component (B) and the component (C) is 1 to 100 parts by weight of the component (A) and the component (B). ) 0 to 99 parts by weight and component (C) 0 to 50 parts by weight (the total content of components (A), (B) and (C) is 100 parts by weight). A polyphenylene ether resin composition having improved stress crack resistance. Component (A) Polyphenylene ether-based resin Component (B) Styrene-based resin Component (C) Rubber-like polymer Component (D) Styrene-based polymer Grafted polyolefin 2. The polyphenylene ether resin composition according to claim 1, wherein the component (D) is a styrene-acrylonitrile copolymer graft polypropylene. 3. The component (D) is a styrene-acrylonitrile copolymer-grafted crystalline polypropylene.
The polyphenylene ether resin composition described.