JPH0525384A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent organic solvent resistance, moldability and mechanical characteristics such as impact resistance. CONSTITUTION:The objective thermoplastic resin composition comprising 100 pts.wt. blend of (A) a modified polyphenylene ether alone or a mixture of the modified polyphenylene ether with a polyphenylene ether and (B) a modified polyolefin alone or a mixture of the modified polyolefin with a polyolefin, (C) an alkenyl group-containing aromatic compound-conjugated diene copolymer and (D) an epoxy group-containing polyolefin-based resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition having excellent mechanical properties such as organic solvent resistance, moldability and impact resistance.

[0002]

2. Description of the Related Art Polyolefins are excellent in molding processability, toughness, water resistance, organic solvent resistance, chemical resistance, etc., and have low specific gravity and are inexpensive.
Widely used for seats, etc.

However, in general, polyolefins are not so high in heat resistance and rigidity, and it is required to further improve these properties in order to be used for new applications.

On the other hand, the polyphenylene ether resin has excellent heat resistance and rigidity, but has a drawback in molding processability and organic solvent resistance, so that its range of use is limited.
Therefore, in order to improve the molding processability, impact strength, etc. of the polyphenylene ether resin, a styrene resin is blended, but the organic solvent resistance is not improved and the range of use thereof is limited. For example, it is not suitable for fields requiring resistance to oily solvents such as gasoline containers.

Various compositions have been proposed in order to combine the advantages of these polyolefins and polyphenylene ether resins and to make up for the drawbacks. For example, various compositions in which a block copolymer of styrene and butadiene and / or a hydrogenated product thereof are blended have been proposed for the purpose of improving the compatibility between the polyolefin and the polyphenylene ether resin and improving the mechanical strength. (JP-A-53-71158, JP-A-54-88950 and JP-A-59-100159). Moldability and mechanical strength are improved with these compositions, but the organic solvent resistance of polyolefin is not sufficiently exhibited. Further, a polyphenylene ether resin is mixed with a large amount of polyolefin exceeding 20% by weight, and in order to further improve the compatibility, a diblock copolymer composed of an alkenyl group-containing aromatic compound and a conjugated diene, or a radial teleblock copolymer is used. Combined products and compositions containing these hydrogenated products (JP-A-58-103557 and JP-A-60-57557)
No. 76547) or a technique of grafting a styrene compound to a polyolefin and then blending it with polyphenylene ether (Japanese Patent Publication No. 56-22544), or blending a polyolefin copolymerized with glycidyl methacrylate with polyphenylene ether. Technology (Japanese Patent Laid-Open No. 57-108153 and 58-225150)
Gazettes) are disclosed respectively.

Further, a technique of blending a polyphenylene ether with a polymer having a glycidyl group and a polyolefin having a group capable of reacting with the glycidyl group (Japanese Patent Laid-Open No. Sho 60)
-260449) or a technique of blending a styrene compound with a copolymer of glycidyl (meth) acrylate and olefin in polyphenylene ether (JP-A-61-61).
Japanese Patent Application Laid-Open No. 63-128056) and a technique of blending a modified polyphenylene ether and a modified polyolefin with a binder having a specific structure (Japanese Patent Application Laid-Open No. 63-128056).

[0007]

However, in these conventional techniques, the compatibility between the polyphenylene ether and the polyolefin is not always sufficiently satisfactory, and therefore, improvement in solvent resistance and mechanical strength is unsatisfactory. The current situation is that a material that is sufficient and practically satisfactory has not been obtained.

Therefore, an object of the present invention is to have both excellent properties of organic solvent resistance and impact resistance, which are the excellent properties of polyphenylene ether and polyolefin, respectively, and to have higher mechanical strength and moldability. Another object of the present invention is to provide a novel thermoplastic resin composition having both of the above.

[0009]

SUMMARY OF THE INVENTION In order to improve the deficiencies in the mechanical properties of conventional blends of polyolefins and polyphenylene ethers, the present inventors have developed various polyolefins, modified polyolefins, polyphenylene ethers and modified polyphenylenes. Ether, as a result of further studies on various compounding agents, from a mixture of polyphenylene ether and a modified polyolefin having a carboxyl group or an acid anhydride group, and a mixture of a polyolefin and a modified polyolefin having a carboxyl group or an acid anhydride group By blending an alkenyl group-containing aromatic compound-conjugated diene copolymer and an epoxy group-containing polyolefin-based resin, the compatibility between the polyolefin and the polyphenylene ether is improved and mechanical properties such as impact strength are improved. It found that the thermoplastic resin composition excellent in gender and organic solvent resistance can be obtained, thereby achieving the present invention.

That is, according to the present invention, a modified polyphenylene ether having a carboxyl group and / or an acid anhydride group alone or a mixture (A) of the modified polyphenylene ether and polyphenylene ether (A) in an amount of 5 to 95% by weight,
And 95 to 5% by weight of a modified polyolefin containing a carboxyl group and / or an acid anhydride group alone or a mixture of the modified polyolefin and a polyolefin (B).
Alkenyl group-containing aromatic compound-conjugated diene copolymer (C) 1 to 100 parts by weight of the compound consisting of
The present invention provides a thermoplastic resin composition containing 0.01 part by weight and 0.01 to 15 parts by weight of an epoxy group-containing polyolefin resin (D).

The thermoplastic resin composition of the present invention (hereinafter referred to as "the composition of the present invention") will be described in detail below.

The component (A) of the composition of the present invention is a modified polyphenylene ether having a carboxyl group and / or an acid anhydride group alone or a mixture of the modified polyphenylene ether and polyphenylene ether.

The polyphenylene ether which is the main component of the polyphenylene ether or the modified polyphenylene ether as the component (A) has the following general formula (I):

[0014]

[Chemical 1]

At least one homopolymer selected from the monocyclic phenol compounds represented by or a polycondensation product of at least one of these.

In the above general formula (I), R ¹ is a lower alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group. R ² and R ³ may be the same or different and each is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. Examples of the lower alkyl group include a methyl group, an ethyl group and a propyl group. Be done.

Specific examples of the monocyclic phenol represented by the general formula (I) include 2,6-dimethylphenol,
2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, o-cresol, 2,3- Dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol,
2-methyl-3-propylphenol, 2-ethyl-3
-Methylphenol, 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6-trimethylphenol, 2,3,6-triethylphenol, 2 ，
3,6-Tripropylphenol, 2,6-dimethyl-
Examples include 3-ethylphenol and 2,6-dimethyl-3-propylphenol. These are 1 alone or 2
It is also used in combination of two or more species.

Specific examples of those obtained by polycondensing at least one kind selected from the monocyclic phenols represented by the general formula (I) are poly (2,6-dimethyl-1,4-). Phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-)
Dipropyl-1,4-phenylene) ether, poly (2
-Methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-)
1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer,
2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol /
2,3,6-trimethylphenol copolymer, 2,6-
Examples thereof include dipropylphenol / 2,3,6-trimethylphenol copolymer and the like. Among these, especially
Poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer are preferred.

The modified polyphenylene ether containing a carboxyl group and / or an acid anhydride group is obtained by modifying polyphenylene ether with a modifier having a carboxyl group or an acid anhydride group in the molecule.

The content of the modifier having a carboxyl group or an acid anhydride group in this modified polyphenylene ether is usually about 0.1 to 2.5% by weight.

The modifier for modifying the polyphenylene ether has (a) an ethylenic double bond and (b) at least one functional group selected from a carboxyl group and an acid anhydride group in the molecule. An organic compound (i), or (c) an acid halide group in the molecule,
(D) Organic compound having at least one functional group selected from carboxylic acid group and carboxylic acid anhydride group (i
i) are mentioned.

In the molecule, (a) an ethylenic double bond,
Specific examples of the organic compound (i) having (b) at least one functional group selected from a carboxyl group and an acid anhydride group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, 2- Norbornene-
Α, β-Unsaturated mono- and dicarboxylic acids such as 5,6-dicarboxylic acid or derivatives thereof; maleic anhydride, itaconic anhydride, citraconic anhydride, 2-norbornene-5,6
-An unsaturated carboxylic acid anhydride such as a dicarboxylic acid anhydride. Among these, maleic acid, acrylic acid, methacrylic acid and maleic anhydride are preferable, and maleic anhydride is particularly preferable.

Specific examples of the organic compound (ii) having (c) an acid halide group and (d) at least one functional group selected from a carboxylic acid group and a carboxylic acid anhydride group in the molecule are shown below. Examples thereof include a monohalide of an aromatic polycarboxylic acid compound or an aliphatic polycarboxylic acid compound, preferably an aromatic polycarboxylic acid compound or a monochloride of an aliphatic polycarboxylic acid compound. Examples of the aromatic polycarboxylic acid compound include terephthalic acid, isophthalic acid, phthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, diphenyldiacetic acid, Diphenyl-p, p-dicarboxylic acid, diphenyl-4,4-diacetic acid, diphenylmethane-p, p-dicarboxylic acid, diphenylethane-p, p-
Dicarboxylic acid, stilbene dicarboxylic acid, benzophenone-4,4-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid Acid, p-carboxyphenoxyacetic acid, trimellitic acid and the like, and examples of the aliphatic polycarboxylic acid compound include oxalic acid, succinic acid, adipic acid, corkic acid, azelaic acid, sebacic acid, dodecadicarboxylic acid and undecane. Dicarboxylic acid etc. are mentioned.

The modified polyphenylene ether may be prepared by the method used for producing a modified resin of this type,
There is no particular limitation. For example, a method in which the polyphenylene ether and the modifier are melt-kneaded at a temperature of 200 to 350 ° C. using a roll mill, a Banbury mixer, an extruder or the like to react; in a solvent such as benzene, toluene, xylene, decalin or tetralin. Then, a method of heating the polyphenylene ether and the modifier to react them can be mentioned.
The modified polyphenylene ether is preferably prepared in the presence of a radical polymerization initiator. In particular, a method of preparing the modified polyphenylene ether which can be practically used is a method of melt-kneading in the presence of a radical polymerization initiator.

The radical polymerization initiator used is
For example, organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, etc. Can be mentioned.

When a modified polyphenylene ether is prepared using this radical polymerization initiator, the amount of the radical polymerization initiator used is usually 0.01 to 10 parts by weight, preferably 0.1 part by weight per 100 parts by weight of the polyphenylene ether. 1
~ 5 parts by weight.

In the preparation of the modified polyphenylene ether, the amount of the modifier used is appropriately selected according to the purpose, but is usually 100 parts by weight or less, preferably 50 parts by weight or less, relative to 100 parts by weight of the polyphenylene ether. More preferably 20 parts by weight or less, particularly preferably 0.0
It is 1 to 10 parts by weight or less.

When a mixture of the modified polyphenylene ether and the polyphenylene ether is used as the component (A) in the composition of the present invention, the mixing ratio of the modified polyphenylene ether and the polyphenylene ether in the mixture is such that Although it depends on the degree of modification, usually modified polyphenylene ether 3
~ 97 parts by weight of polyphenylene ether 97 ~
A proportion of 3 parts by weight is preferred. At this time, if the mixing ratio of the modified polyphenylene ether is less than 3 parts by weight, the impact strength of the obtained composition is lowered, which is not preferable.

The component (B) of the composition of the present invention is a modified polyolefin having a carboxyl group and / or an acid anhydride group alone or a mixture of the modified polyolefin and a polyolefin.

As the polyolefin, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-
Pentene, 1-hexene, 1-octene, 1-decene,
Homopolymer containing at least one selected from α-olefin components such as 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, or at least two selected from these α-olefin components. It is a copolymer mainly composed of a combination and is a low crystalline or crystalline polymer.

In addition to the above α-olefin component, this polyolefin includes butadiene, isoprene, 1,4
-Hexadiene, 5-ethylidene-2-norbornene,
Diene components such as 5-vinyl-2-norbornene and dicyclopentadiene, vinyl acetate, acrylic acid (salt), methacrylic acid (salt), acrylic acid ester, methacrylic acid ester, maleic acid, maleic anhydride, maleic acid ester, 2-norbornene-5,6-dicarboxylic acid, 2-
A small amount of unsaturated carboxylic acid such as norbornene-5,6-dicarboxylic acid anhydride or its derivative may be contained.

The crystallinity of this polyolefin as measured by X-ray diffraction is usually 0.5 to 95%, preferably 1
It is about 90%. In addition, 13 of this polyolefin
The intrinsic viscosity [η] measured in decalin at 5 ° C was 0.
01 to 30 dl / g, preferably 0.1 to 25 dl
/ G.

Among these polyolefins, a specific example of an amorphous or low crystalline polyolefin is ethylene-
Propylene copolymer, ethylene-1-butene copolymer,
Ethylene-1-hexene copolymer, propylene-1-butene copolymer, propylene-1-butene-4-methyl-
1-pentene copolymer, 1-hexene-4-methyl-1
-Pentene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-5-vinyl-2-norbornene copolymer, ethylene-propylene -1,4-hexadiene copolymer, ethylene-1-butene-cyclohexadiene copolymer, ethylene-1-butene-5-ethylidene-2-norbornene copolymer, ethylene-1-butene-1,4-hexadiene Examples thereof include copolymers. Moreover, as specific examples of the crystalline polyolefin, polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene,
Poly-1-hexene, poly-1-octene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-
1-hexene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid (salt) copolymer, ethylene-
Methacrylic acid (salt) copolymer, ethylene-methacrylic acid ester copolymer, ethylene-maleic acid copolymer, ethylene-maleic anhydride copolymer and the like can be mentioned.

The modified polyolefin used as the component (B) of the composition of the present invention is a polyolefin containing a carboxyl group or an acid anhydride group, and a specific modifier is grafted on a part or all of the polyolefin. It is a polymer having a carboxyl group or an acid anhydride group in the molecule by copolymerization or random copolymerization.

The modifier used is an organic compound having (a) an ethylenic double bond and (b) at least one group selected from a carboxyl group and an acid anhydride group in the molecule. Examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, 2-
Unsaturated carboxylic acids such as norbornene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, and the like, and the like. Can be mentioned. These may be used alone or in combination of two or more. Among these, maleic acid, acrylic acid, methacrylic acid and maleic anhydride are preferable, and maleic anhydride is more preferable.

The content ratio of these modifiers contained in the modified polyolefin is usually 0.01 to 50% by weight,
It is preferably in the range of 0.1 to 30% by weight.

In the preparation of this modified polyolefin,
As a method of preparing by graft copolymerization, a method of melt-kneading a polyolefin and the modifier with heating in the presence or absence of a radical polymerization initiator;
Examples thereof include a method of reacting a polyolefin and the modifier with heating in an inert solvent in the presence or absence of a radical polymerization initiator. The temperature in the graft copolymerization reaction is usually 50 to 330 ° C, preferably about 60 to 250 ° C.

Specific examples of the modified polyolefin prepared by random copolymerization include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic acid copolymer, ethylene-maleic anhydride copolymer. Examples include coalescence.

The random copolymer can be prepared by a conventionally known method.

The intrinsic viscosity [η] of these modified polyolefins measured in decalin at 135 ° C. is usually 0.
01 to 30 dl / g, preferably 0.1 to 25 dl
/ G.

In the present invention, when a mixture of a modified polyolefin and a polyolefin is used as the component (B), the mixing ratio of the modified polyolefin and the polyolefin depends on the modification degree of the modified polyolefin to be used, but usually the modified polyolefin. A ratio of 97 to 3 parts by weight of polyolefin is preferable with respect to 3 to 97 parts by weight, and if the amount of the modified polyolefin is less than 3 parts by weight, the impact strength of the resulting composition is lowered, which is not preferable.

The alkenyl group-containing aromatic compound-conjugated diene copolymer which is the component (C) of the composition of the present invention is a copolymer of an alkenyl group-containing aromatic compound and a conjugated diene.

As the alkenyl group-containing aromatic compound,
For example, styrene; lower alkyl group-substituted styrene such as chlorostyrene, α-methylstyrene and vinyltoluene;
Examples thereof include vinylnaphthalene, and these may be used alone or in combination of two or more kinds in the alkenyl group-containing aromatic compound-conjugated diene copolymer. Of these, styrene is preferred.

Examples of the conjugated diene include aliphatic linear dienes such as butadiene and isoprene; lower alkyl group-substituted aliphatic linear dienes such as 2,3-dimethylbutadiene; cyclopentadiene and its derivatives. These may be contained in the alkenyl group-containing aromatic compound-conjugated diene copolymer alone or in combination of two or more. Of these, butadiene is preferred.

In the present invention, the alkenyl group-containing aromatic compound-conjugated diene copolymer which is the component (C) is a random, graft or block containing the above alkenyl group-containing aromatic compound and conjugated diene as the main monomer components. It may be a copolymer having a bonding mode such as, and may partially contain a crosslinked structure. Among them, preferable ones are random copolymers and block copolymers, more preferable ones are block copolymers, and particularly preferable ones are:
It is a linear block copolymer represented by the following formula: XY- (XY) _m- (X) _n (II). In the formula (II), X represents a polymer block derived from an alkenyl group-containing aromatic compound, Y represents an elastomeric block copolymer block derived from a conjugated diene, m is 0 or a positive integer, n is 0 or 1.

In the present invention, the solution viscosity, which is a measure of the molecular weight of the alkenyl group-containing aromatic compound-conjugated diene copolymer, is usually a Brookfield viscosity at 25 ° C. in a 25 wt% toluene solution of 200 to 40, 000
It is preferably in the range of cps, 600 to 30,000
More preferably in the range of 0 cps, 800-2
The range of 5,000 cps is particularly preferable.

Further, the alkenyl group-containing aromatic compound-conjugated diene copolymer as the component (C) may be one in which at least a part of the double bond derived from the conjugated diene present in the molecule is hydrogenated.

The content ratio of the structural unit derived from the alkenyl group-containing aromatic compound in the alkenyl group-containing aromatic compound-conjugated diene copolymer is preferably in the range of 20 to 70% by weight, and 25 to 60% by weight. Is more preferable, and the range of 28 to 50% by weight is particularly preferable.

The alkenyl group-containing aromatic compound-conjugated diene copolymer can be prepared by various methods and is not particularly limited. For example, as a method for preparing the above block copolymer, Japanese Patent Publication No. 40-23798, US Pat. No. 3,595,942 and US Pat.
As described in the specification of No. 90996 and the like, there may be mentioned a method of carrying out block copolymerization in an inert solvent using a lithium catalyst or a Ziegler type catalyst.

Among the alkenyl group-containing aromatic compound-conjugated diene copolymers, as a specific example of the above block copolymer, "KRAION-
D ”,“ Califlex ”, and those marketed by Nippon Synthetic Rubber Co., Ltd. under the trade name“ TR ”.

Among the alkenyl group-containing aromatic compound-conjugated diene copolymers, the treatment for obtaining the hydrogenated product of the above block copolymer is described, for example, in JP-B-42-8.
No. 704, No. 43-6636, or No. 46-
According to the method described in 20814, etc., it can be carried out by a method of hydrogenating in the presence of a hydrogenation catalyst in an inert solvent.

Also, the Journal of Polymer. Science Part
Hydrogenation can also be carried out using p-toluenesulfonyl hydrazide or the like in an inert solvent according to the method described in documents such as B Polymer Letters Volume 11.427 to 434 (1973).

As a specific example of this hydrogenated block copolymer, "KRAITON-G" from Shell Chemical Co., Ltd.
The products sold under the brand name are listed.

In the present invention, as the alkenyl group-containing aromatic compound-conjugated diene copolymer as the component (C), a plurality of copolymers selected from the hydrogenated block copolymers obtained as described above. You may use together.

Further, in the present invention, as the alkenyl group-containing aromatic compound-conjugated diene copolymer as the component (C), the block copolymer obtained as described above or the hydrogenated block copolymer is used. Also included are modified compounds modified with various modifying compounds in the molecule. Examples of the modifying compound include a compound containing at least one selected from a carboxyl group, an amino group, an imino group, an epoxy group, an amide group, a vinyl group, an isocyanate group, and a hydroxyl group in the molecule, or an acid anhydride. And at least one selected from carboxylic acid esters and oxazoline rings.

As a specific example of this modified product, acrylic acid,
Styrene-butadiene copolymer (XY or XYX block, random or graft copolymer) modified with hymic acid anhydride, glycidyl methacrylate, maleic anhydride, or the like, and hydrogenated copolymer thereof A styrene-isoprene copolymer (XY or XYX block, random or graft copolymer) and a hydrogenated copolymer thereof.

The modified product can be prepared by a known method such as graft copolymerization or random copolymerization.

In the composition of the present invention, as the alkenyl group-containing aromatic compound-conjugated diene copolymer as the component (C), the block copolymer may include one kind alone or a combination of two or more kinds. Good.

The epoxy group-containing polyolefin resin which is the component (D) of the composition of the present invention is a copolymer of an unsaturated epoxy compound and an olefin, or an unsaturated epoxy compound, an olefin and a vinyl compound. The unsaturated epoxy compound is a compound having both an unsaturated group and an epoxy group which can be copolymerized with an olefin or a vinyl compound in the same molecule. For example, unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes and para-glycidyl styrenes represented by the following general formulas (II), (III) and (IV) These may be used alone or in combination of two or more.

[0060]

[Chemical 2] (In the formula, R has 2 to 1 carbon atoms having an ethylenic double bond.
8 hydrocarbon groups. )

[Chemical 3] (In the formula, R has 2 to 1 carbon atoms having an ethylenic double bond.
8 is a hydrocarbon group in the range of 8 and X is —CH ₂ —O.
-,

[Chemical 4] Is. )

[Chemical 5] (In the formula, R has 2 to 1 carbon atoms having an ethylenic double bond.
8 is a hydrocarbon group, and R ′ is hydrogen or a methyl group. )

Examples of R in the above formulas (II) to (IV) include a vinyl group, an allyl group, an isopropenyl group and a butenyl group.

Specific examples of the unsaturated epoxy compound include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butenecarboxylic acid glycidyl esters, allyl glycidyl ether,
2-methylallyl glycidyl ether, parastyryl-
Glycidyl ether, 3,4-epoxy butene, 3,4
-Epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1
-Pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, paraglycidyloxystyrene and the like. Among these, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and paraglycidyl oxystyrene are preferable, glycidyl methacrylate, allyl glycidyl ether are more preferable, and glycidyl methacrylate is more preferable.

The olefinic monomers or vinyl compounds copolymerizable with these unsaturated epoxy compounds are as follows. That is, examples of the olefin include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, and the like, and more preferably selected from ethylene, propylene, and 1-butene. And ethylene is more preferable.

In the present invention, the vinyl compound is used in a broad sense, and the vinyl compound has 2 to 6 carbon atoms.
Vinyl esters containing saturated carboxylic acid components in the range of
Acrylic acid esters, methacrylic acid esters and maleic acid esters containing saturated alcohol components having 1 to 10 carbon atoms, vinyl halides, vinyl ethers, N-vinyl lactams, N-vinyl carboxylic acid amides, etc. Which may be used alone or in combination of two or more. Of these, preferably selected from vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether. And more preferably selected from vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. The unsaturated epoxy compound, olefin, or vinyl compound constituting the copolymer as the component (D) can be bonded in various ways such as block type, random type, graft type, etc., but they can be used. Random type and graft type are easy to use.

With respect to the molecular weight (or degree of polymerization) of the epoxy group-containing olefin copolymer which is the component (D), those having various ranges can be used. Among them, among the olefins constituting the copolymer, When the main component is ethylene or propylene, a more preferable range is 0.001 to 100 when expressed as a melt flow rate value (JIS X7210-1975), which is one of the criteria of molecular weight.
0 g / 10 minutes, more preferably 0.01 to 100 g /
10 minutes, particularly preferably 0.1 to 50 g / 10 minutes,
Especially preferably, it is in the range of 1 to 20 g / 10 minutes. Over 1000g / 10min and 0.001g / 1
When it is less than 0 minutes, the mechanical strength of the composition and the weld strength tend to be unsatisfactory, which is not preferable.

The epoxy group-containing olefin copolymer which is the component (D) can be prepared by various methods. For example, an unsaturated epoxy compound and an olefin, and in some cases, a vinyl compound in the presence of a radical generator, in an amount of 50 to 4
A method of contacting at 000 atm and 40 to 300 ° C., a method of mixing a polypropylene with an unsaturated epoxy compound and optionally a vinyl compound, and irradiating with gamma rays under high vacuum to produce a polymer, or polypropylene,
Polyethylene, a polyolefin such as ethylene-propylene copolymer and an unsaturated epoxy compound, optionally further mixed with a vinyl compound, and a method of producing a polymer by allowing a radical generator to exist in an organic solvent such as xylene. Be done.

Among the above epoxy group-containing polyolefin resins, preferred are unsaturated epoxy compounds. It is an olefin or vinyl compound copolymerized in the range of 5 to 50% by weight, and particularly preferably an epoxy group-containing olefin copolymer copolymerized with ethylene in the range of 1 to 30% by weight of glycidyl methacrylate. is there.

In the composition of the present invention, the mixing ratio of the component (A) and the component (B) is 5 to 95% by weight of the component (A).
On the other hand, the proportion of the component (B) is 95 to 5% by weight.
When the blending ratio of the component (A) is less than 5% by weight, the heat resistance rigidity of the obtained composition becomes insufficient, and when it exceeds 95% by weight, the organic solvent resistance of the obtained composition becomes insufficient. Further, the mixing ratio of the component (A) and the component (B) may be appropriately selected within the above range in consideration of the balance of properties such as heat resistance, moldability, chemical resistance, mechanical properties and the like. In particular, when importance is attached to chemical resistance, it is preferable to select a blending ratio such that the polyolefin resin becomes a matrix phase.

Further, the blending ratio of the component (C) in the composition of the present invention is 10 in total of the components (A) and (B).
1 to 100 parts by weight, preferably 50 parts, relative to 0 parts by weight
The proportion is not more than 30 parts by weight, more preferably not more than 30 parts by weight. When the blending ratio of the component (C) is less than 1 part by weight, the impact strength of the resulting composition is insufficient, and when it exceeds 100 parts by weight, a composition having sufficient rigidity cannot be obtained.

Further, the compounding ratio of the component (D) in the composition of the present invention is 1 in total of the components (A) and (B).
It is 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, relative to 00 parts by weight. If the blending ratio of the component (D) is less than 0.01 part by weight, the effect of improving the solvent resistance and impact resistance, which are the objects of the present invention, tends to be small, and
The resulting composition in excess of parts by weight easily causes gelation, coloring and decomposition. In particular, the melting temperature and the viscosity increase remarkably, which makes molding difficult.

The composition of the present invention comprises the above-mentioned component (A),
In addition to the component (B), the component (C) and the component (D), various compounding agents used in this type of composition can be blended, if necessary. For example, a reinforcing agent such as glass fiber, carbon fiber, potassium titanate fiber, highly elastic polyamide fiber, an inorganic or organic filler such as carbon black, silica, TiO ₂ , talc, calcium carbonate, magnesium sulfate and wollastonite, Examples thereof include plasticizers such as triphenyl phosphate and phthalic acid ester, lubricants, stabilizers, flame retardants such as Sb ₂ O ₃ , halogen compounds and phosphoric acid esters, dyes and pigments. These may be used alone or in combination of two or more.

The method for producing the composition of the present invention is not particularly limited, and an ordinary known method can be used. For example, various methods such as a method of mixing the respective components in a solution state and evaporating the solvent, a method of adding the solvent to a non-solvent to cause precipitation, a method of kneading in a molten state, or the like can be adopted. The method of kneading is industrially effective. For the melt-kneading, a kneading device such as a commonly used uniaxial or biaxial extruder and various kneaders can be used. A biaxial high kneader is particularly preferable.

In the production of the composition of the present invention, the order of kneading each component is not particularly limited, and each component may be kneaded at once, or the components (A) and (D) may be kneaded in advance. After that, the components (C) and (B) may then be supplied for kneading. Other kneading orders may be used.

The kneading is preferably carried out by uniformly mixing each of the components in a powder or pellet state in advance by using a device such as a tumbler or a Henschel mixer and then supplying the kneading device, but the mixing is omitted. It is also possible to employ a method in which a fixed amount of each is supplied to the kneading device.

As described above, the composition of the present invention is prepared by kneading the components, and then the obtained composition is molded into a desired molded article by injection molding, extrusion molding or other various molding methods. Alternatively, without preparing the composition in advance by kneading,
Alternatively, each component may be directly supplied to an injection molding machine or an extrusion molding machine, dry-blended, and melt-kneaded to obtain a molded product.

[0076]

EXAMPLES The present invention will be described more specifically below based on Examples of the present invention and Comparative Examples.

(1) Measurement and Evaluation Each physical property value and various properties in the following Examples and Comparative Examples were measured or evaluated by the following methods. Bending test: ASTM D using a 1/8 "thick test piece
Bending elastic modulus FM (kg / cm
² ) was measured. Izod impact test: A 1/8 "thick test piece was used
It measured based on STM D-256. Thermal deformation test: ASTM under load 4.6 kg / cm ²
The HDT (° C) was measured according to D-648. Solvent cracking: A 1/8 "thick test piece with 1% strain added is immersed in acetone at room temperature for 48 hours, and the presence or absence of cracks is visually determined and evaluated according to the following criteria. ○ No cracks occurred × Cracks occurred

(2) Component (A) Component (A) Polyphenylene ether resin Poly 2,6-dimethyl-1,4-phenylene ether (Intrinsic viscosity [η] 0.4 at 30 ° C. in chloroform)
5 dl / g) was used. (Hereinafter, abbreviated as "PPE".) (B) Modified polyphenylene ether resin Reference Example 1 2 kg of the above PPE was mixed with 40 g of maleic anhydride and 7 g of dicumyl peroxide by a Henschel mixer, and the obtained mixture was biaxially mixed. Supply to the extruder 300 ~ 3
The mixture was melt-kneaded and reacted at a temperature of 30 ° C. to obtain pelletized modified polyphenylene ether resin. The carboxyl group content of the obtained modified polyphenylene ether resin (hereinafter abbreviated as "M1-PPE") was measured by a titration method and infrared absorption (IR) analysis. It was found that 0.8 mol% of maleic anhydride was bound.

Reference Example 2 Modified polyphenylene ether was prepared in the same manner as in Reference Example 1 except that a mixture of 2 kg of PPE and 500 g of hydrogenated styrene-butadiene-styrene block copolymer (Califlex TR-1101 manufactured by Shell Chemical Co., Ltd.) was used. A resin was obtained. (Hereinafter, abbreviated as "M2-PPE")

Reference Example 3 10 kg of xylene was added to 2 kg of PPE, and 100 g of succinic acid monochloride was further added, and the mixture was reacted under reflux of xylene for 5 hours while stirring. After cooling, the reaction mixture is poured into 30 l of methanol, the precipitate is filtered off,
When dried, polyphenylene ether (hereinafter referred to as "M3-PP
Abbreviated as "E").

Component (B) (a) Polypropylene resin As a propylene / ethylene copolymer, Sumitomo Chemical Co., Ltd.
Made, Sumitomo 1-Blen AW564 (MI = 9.0, below,
(Abbreviated as "PP-1") and (AH561 (MI
= 3.0, hereinafter abbreviated as "PP-2") was used.

(B) Modified polypropylene resin Reference Example 4 To 1 kg of PP-1 described above, 30 g of maleic anhydride and 3 g of t-butylperoxypivalate were added, mixed well, and then fed to a twin-screw extruder. The mixture was melt-kneaded and reacted at a temperature of 180 to 230 ° C. to obtain pellet-shaped maleic anhydride-modified polypropylene resin. The obtained maleic anhydride-modified polypropylene resin (hereinafter, "M1-PP")
The content of maleic anhydride in (hereinafter abbreviated as) was 1.2% by weight.

Reference Example 5 To 1 kg of the above PP-1, 30 g of methacrylic acid and 2,
After adding 0.5 g of 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and mixing them well, 2
It was supplied to the axial extruder and melt-kneaded at a temperature of 210 to 240 ° C. to cause a reaction to obtain a pellet-shaped methacrylic acid-modified polypropylene resin. The content of methacrylic acid in the obtained methacrylic acid-modified polypropylene resin (hereinafter abbreviated as “M2-PP”) was 1.7% by weight when measured by elemental analysis.

Reference Example 6 1 kg of the above PP-2, 50 g of maleic anhydride and 8 liters of dichlorobenzene were mixed, and the resulting mixture was heated to 110 ° C. to dissolve it, and then dichlorobenzene containing 10 g of benzoyl peroxide. The solution was added slowly.
After that, the temperature was further maintained for 5 hours for reaction. After cooling, the reaction mixture was poured into a large excess of acetone, the precipitate was filtered off and dried to obtain a maleic anhydride modified polypropylene resin. The content of maleic anhydride in the obtained maleic anhydride-modified polypropylene resin (hereinafter abbreviated as “M3-PP”) was measured and found to be 2.4% by weight.

Component (C) (a) Alkenyl Group-Containing Aromatic Compound-Conjugated Diene Copolymer Hydrogenated product of styrene-butadiene-styrene block copolymer (Kreton G- 1650, hereinafter abbreviated as “SEBS”), hydrogenated styrene-isoprene block copolymer (Kreton G-1701, hereinafter abbreviated as “SEP”) or maleic anhydride-modified styrene-butadiene-styrene block copolymer Polymer (Clayton FG190
1X, hereinafter abbreviated as "M-SEBS") was used.

Component (D) (a) Epoxy group-containing polyolefin copolymer Ethylene-glycidyl methacrylate copolymer (trade name Bond First E, manufactured by Sumitomo Chemical Co., Ltd., hereinafter EP-1
And an ethylene-glycidyl methacrylate vinyl acetate copolymer (trade name: Bondfast-2B, manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as EP-2).

(Example 1) 40 parts by weight of modified polyphenylene ether (M1-PPE), modified polypropylene (M1-PPE)
1-PP) 60 parts by weight, styrene-butadiene-styrene block copolymer hydrogenated product (SEBS) 15 parts by weight, and ethylene-glycidyl methacrylate copolymer (EP-1) 7 parts by weight in a supermixer. After supplying and dry blending, the obtained mixture was supplied to a twin-screw extruder (TEM-35 manufactured by Toshiba Machine Co., Ltd.),
A composition was prepared by melt-kneading at about 280 ° C.

The composition thus obtained was fed to an injection molding machine,
Cylinder temperature 270 ℃, injection pressure 700kg / c
Injection molding was performed at m ² and a mold temperature of 60 ° C., and the molded product was subjected to measurement and evaluation of physical properties. The results are shown in Table 1.

When the cross section of the molded product was observed with an electron microscope, it was found that the polyphenylene ether had a particle size of 0.2 to 0.
It was dispersed in the composition constituting the molded product as extremely fine dispersed particles of 8 μm.

(Examples 2 to 5, Comparative Examples 1 to 4) In each example, a composition having a formulation shown in Table 1 was prepared, and Example 1 was prepared.
Melting, kneading and injection molding were carried out in the same manner as in, and the physical properties of the obtained molded product were measured and evaluated. The results are shown in Table 1.
Shown in.

[0091]

[Table 1]

[Table 2]

(Examples 6 to 14 and Comparative Examples 5 to 7) In each example, a composition having the formulation shown in Table 2 was prepared and melted, kneaded and injection molded in the same manner as in Example 1 to obtain The physical properties of the obtained molded product were measured and evaluated. The results are shown in Table 2.

[0093]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

Example 16 As each component, 50 parts by weight of modified polyphenylene ether (M2-PPE), 50 parts by weight of modified polypropylene (M1-PP), hydrogenated product of styrene-butadiene-styrene block copolymer (S).
EBS) 8 parts by weight and ethylene-glycidyl methacrylate copolymer (EP-1) 7 parts by weight except that a composition was prepared, and melt kneading and injection molding were performed in the same manner as in Example 1 to obtain a composition. The physical properties of the molded product were measured and evaluated. As a result, the flexural modulus was 12.100 (kg / c
m ² ), Izod impact strength was 36 kg · cm / cm 2, and heat distortion temperature (under 4.6 kg / cm ² ) was 138 ° C. No solvent crack was observed.

[0095]

The thermoplastic resin composition of the present invention is excellent in mechanical properties such as organic solvent resistance, moldability and impact resistance. This means that, as can be seen from Tables 2 and 3, in the composition of the present invention, that is, in the composition containing polyphenylene ether and polyolefin, the modified polyphenylene ether having a carboxyl group or an acid anhydride group alone, or A mixture of a modified polyphenylene ether and a polyphenylene ether (A), a modified polyolefin having a carboxyl group or an acid anhydride group alone, or a mixture of this modified polyolefin and a polyolefin (B), and a hydrogenated styrene-butadiene block copolymer An alkenyl group-containing aromatic compound-conjugated diene copolymer (C) typified by a polymer and an epoxy group-containing polyolefin resin (D) typified by a polyethylene-based copolymer containing glycidyl methacrylate as a copolymerization component. The composition containing Compared to a composition using only unmodified polyphenylene ether as the component (A) or only unmodified polyolefin as the component (B), the flexural modulus and heat resistance are remarkably high, and at the same time the polymorphic organic solvent property is also good. It is also clear from that.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C08L 53/02 LLY 7142-4J (72) Inventor Hideto Iwasaki 1 Kawasaki-cho, Chiba-shi, Chiba (72) Inventor Taichi Ogawa 1 Kawasaki-cho, Chiba-shi, Chiba Kawasaki Steel Co., Ltd. Technical Research Division

Claims (1)

1. A modified polyphenylene ether containing a carboxyl group and / or an acid anhydride group alone or a mixture (A) of the modified polyphenylene ether and polyphenylene ether (A) in an amount of 5 to 95% by weight, and a carboxyl group. A modified polyolefin containing a group and / or an acid anhydride group alone or a mixture (B) of the modified polyolefin and a polyolefin (B) in an amount of 95 to 5% by weight.
Alkenyl group-containing aromatic compound-
Conjugated diene copolymer (C) 1 to 100 parts by weight, and epoxy group-containing polyolefin resin (D) 0.01 to
A thermoplastic resin composition containing 15 parts by weight.