JPH08259798A - Resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin composition having mechanical properties, heat resistance and molding flowability in a good balance. CONSTITUTION: This composition is composed of 100 pts. (in wt., the same hereafter) (A) plus (B) and 1 to 100 pts. (C), wherein (A) is 5-95 pts. polyphenylene resin or the mixture of said resin and a polystyrene resin, (B) is 5-95 pts. saturated polyester resin and (C) is a graft modified polyolefin resin made in a way that a water suspension containing (b), (c) and (d) in an amount of 100 pts. (b) plus (c) per 0.01-10 pts. of (d) is prepared and (b) and (c) in the suspension are impregnated into (a) and polymerized, wherein (a): 100 pts. polyolefin resin, (b): 0.1-30 pts. modifier composed of a compound as expressed by the formula (Ar is 6-23C aromatic hydrocarbon group having at least one glycidyloxy group. R is hydrogen atom or methyl group) or of said compound and glycidyl methacrylate or of glycidyl methacrylate, (c): 0.1-500 pts. vinyl monomer and (d): an initiator for radical polymerization.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, and more particularly to a resin composition having well-balanced physical properties such as mechanical properties, heat resistance and molding fluidity.

[0002]

2. Description of the Related Art Polyphenylene ether is used in applications such as office automation equipment parts and home electric appliance parts because it has excellent elastic modulus, heat resistance, electrical properties, and good dimensional stability. However, there are drawbacks in moldability, oil resistance and impact strength, and improvement is desired. On the other hand, since polystyrene-based resins are inexpensive and have excellent moldability, a composition that improves the moldability of polyphenylene ether by adding the polystyrene-based resin is disclosed. For example, a typical example is Noril (registered trademark), a product of General Electric Company. However, only the addition of the polystyrene resin has a drawback that the effect of improving the impact strength is small and the oil resistance is poor. Also, polyethylene terephthalate,
Saturated polyester typified by polybutylene terephthalate is excellent in elastic modulus, heat resistance, oil resistance, and moldability, but has a drawback that dimensional changes (mainly shrinkage and warpage) of the molded product are large.

If the respective disadvantages of polyphenylene ether and saturated polyester can be compensated for in their advantages, further applications can be opened. For example, JP-A-49-50050 and JP-A-59-159847 disclose compositions of polyphenylene ether and saturated polyester.
JP-A-75662 discloses a composition of polyphenylene ether having a degree of polymerization of 10 or more and a saturated polyester. However, because of poor compatibility of the polyphenylene ether and the saturated polyester, delamination of the molded article occurs. There are drawbacks such as impairing the appearance and insufficient improvement of impact strength. In order to solve such a problem, for example, JP-A-60-260649 discloses a method of using a copolymer of a styrene compound and an epoxy group-containing unsaturated compound as a compatibilizer. However, this method does not sufficiently improve the impact resistance. In addition, JP-A-62-1
Japanese Patent No. 27457 discloses the combined use of a copolymer of a styrene compound and an epoxy group-containing unsaturated compound and an impact imparting agent. However, although this method has an effect of improving compatibility, the improvement of impact resistance is insufficient.

On the other hand, the polyolefin resin is characterized by being lightweight and excellent in impact resistance, and also excellent in moldability, water resistance, chemical resistance and the like. Therefore, by blending polyphenylene ether, styrenic resin, saturated polyester and polyolefin resin, each of which has excellent characteristics, for example, there is little decrease in heat resistance, light weight, elastic modulus, impact resistance, and oil resistance. Attempts have been made to produce a resin composition having characteristics such as excellent properties and dimensional change resistance. However, merely adding a polyolefin-based resin causes further deterioration of compatibility, and it is difficult to obtain a stable resin composition, and the mechanical properties such as impact strength of a molded product obtained from the kneaded product are However, there is a problem in that the mechanical properties of the molded product vary greatly.

Therefore, as a method for improving such problems, for example, Japanese Patent Application Laid-Open No. 62-12760 discloses a method using a copolymer of ethylene and an epoxy group-containing unsaturated compound. However, with this method, although the effect of improving the impact resistance can be seen, there is a problem in that the elastic modulus and molding fluidity decrease. JP-A-63-8956
Japanese Patent Publication No. 4 discloses a method of using a styrene resin obtained by modifying an olefin copolymer with styrene and glycidyl methacrylate. However, the compatibilizing effect cannot be obtained unless the total amount of styrene and glycidyl methacrylate is 9 to 0.25 times that of the olefin copolymer. Further, since styrene and glycidyl methacrylate are used in a large amount, it is difficult to bring out the original characteristics of the olefin-based copolymer. Further, JP-A-64-48853 discloses a method using a multi-phase structure thermoplastic resin comprising an epoxy group-containing olefin copolymer part and a vinyl-based (co) polymer part obtained from a vinyl monomer. Has been done. However, this method is insufficient in the effect of improving impact resistance and molding fluidity. Further, JP-A-1-126365 discloses the combined use of a polymer containing an aromatic polycarbonate unit and an EPDM terpolymer modified with glycidyl methacrylate. Although this method has an effect of improving impact resistance, there is a problem that the molding fluidity is not sufficiently improved, and the cost is high because a polymer containing an aromatic polycarbonate unit is used.

[0006]

DISCLOSURE OF THE INVENTION The present invention improves such compatibility and provides a polyphenylene ether resin, or a mixture thereof with a polystyrene resin, a saturated polyester,
Made of graft-modified polyolefin resin, heat resistance,
Provided is a resin composition excellent in stability of dimensions and mechanical properties when absorbing water, impact resistance, and moldability.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polyphenylene ether resin, or a mixture thereof with a polystyrene resin,
The saturated polyester, the polyolefin resin and a modifier having a specific glycidyl group and a vinyl monomer are reacted in the presence of a radical polymerization initiator to obtain the graft-modified polyolefin resin obtained by blending the above object. They found what they could achieve and reached the invention.

That is, the first aspect of the present invention comprises the following components (A), (B) and (C), wherein (A) is 5 to 95:
Parts by weight, (B) 95 to 5 parts by weight, (C) the above (A)
1 to 100 parts by weight based on 100 parts by weight of the total amount of (B) and (B). (A) polyphenylene ether resin, or a mixture of polyphenylene ether resin and polystyrene resin,
(B) saturated polyester, (C) (a) 100 parts by weight of polyolefin resin, (b) the following general formula (I)

[0009]

[Chemical 4]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). Modifier consisting of compounds 0.1 to 30
Parts by weight, 0.1 to 500 parts by weight of vinyl monomer (c),
And 0.001 of the radical polymerization initiator (d) per 100 parts by weight of the total amount of the components (b) and (c).
An aqueous suspension containing 10 to 10 parts by weight is prepared, the component (b) and the component (c) in the aqueous suspension are impregnated in the component (a), and the components (b) and (c) are added. A graft-modified polyolefin resin obtained by polymerizing the component (a).

The second aspect of the present invention is to provide the following component (A),
(B) and (C), (A) is 5 to 95 parts by weight,
(B) is 95 to 5 parts by weight, (C) is the above (A) and (B)
1 to 100 parts by weight with respect to the total amount of 100 parts by weight of the resin composition. (A) polyphenylene ether resin, or a mixture of polyphenylene ether resin and polystyrene resin,
(B) Saturated polyester, (C) (a) 100 parts by weight of polyolefin resin, (b) (b1) the following general formula (I)

[0012]

Embedded image

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). It is composed of a mixture of a compound and (b2) glycidyl methacrylate, and its mixing ratio (b1) /
[(B1) + (b2)] is 0.01 to 0.99, 0.1 to 30 parts by weight of a modifier, and (c) a vinyl monomer 0.1.
To 500 parts by weight and (d) a radical polymerization initiator in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the total amount of the components (b) and (c) are prepared. A graft-modified polyolefin system obtained by impregnating the component (a) with the component (b) and the component (c) in the aqueous suspension and polymerizing the component (b) and the component (c) with the component (a). resin.

The third aspect of the present invention is to provide the following component (A),
(B) and (C), (A) is 5 to 95 parts by weight,
(B) is 95 to 5 parts by weight, (C) is the above (A) and (B)
1 to 100 parts by weight with respect to the total amount of 100 parts by weight of the resin composition. (A) polyphenylene ether resin, or a mixture of polyphenylene ether resin and polystyrene resin,
The total amount of (B) a saturated polyester, (C) (a) a polyolefin resin, 100 parts by weight, (b) a glycidyl methacrylate modifier and (c) a vinyl monomer is 0.1 to less than 25 parts by weight. And the amount of the component (b) and the component (c) is (b) / [(b) + (c)] = 0.01-
And an amount of 0.95 and (d) a radical polymerization initiator in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the total amount of the components (b) and (c). A graft-modified polyolefin obtained by impregnating the component (a) with the component (b) and the component (c) in the aqueous suspension, and polymerizing the component (b) and the component (c) with the component (a). Resin 1 to 100 parts by weight.

The polyphenylene ether resin (A) used in the present invention is represented by the following general formula (III)

[0016]

[Chemical 6]

(In the formula, R ¹ , R ² , R ³ and R ⁴ represent the same or different residues such as alkyl group, aryl group, halogen and hydrogen, and n represents the degree of polymerization of 400 to 4200)
And a specific example thereof is poly (2,6-dimethylphenylene-1,4-ether),
Poly (2,6-diethylphenylene-1,4-ether), poly (2,6-dibromophenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-)
1,4-ether), poly (2-chloro-6-methylphenylene-1,4-ether), poly (2-methyl-6)
-Isopropylphenylene-1,4-ether), poly (2,6-di-n-propylphenylene-1,4-ether), poly (2-chloro-6-bromophenylene-)
1,4-ether), poly (2-chloro-6-ethylphenylene-1,4-ether), poly (2-methylphenylene-1,4-ether), poly (2-chlorophenylene-1,4-). Ether), poly (2-phenylphenylene-1,4-ether), poly (2-methyl-6-phenylphenylene-1,4-ether), poly (2-bromo-6-phenylphenylene-1,4-). ether),
Poly (2,4'-methylphenylphenylene-1,4-
Ether) and the like, copolymers of two or more kinds of those monomers, styrene compounds thereof, graft copolymers of epoxy group-containing unsaturated compounds and the like, and mixtures thereof.

The polystyrene resin used in the present invention is a polystyrene polymer having a styrene content of 10% or more,
It means a copolymer or a graft copolymer. For example, polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-rubbery polymer copolymer, styrene-rubbery polymer-acrylonitrile copolymer, styrene monomer and maleimide, N-phenylmaleimide, etc. And a copolymer with an acrylamide monomer such as acrylamide. These may be used alone or in combination of two or more. Further, all or part of styrene of the polystyrene polymer can be replaced with α-methylstyrene, p-methylstyrene, pt-butylstyrene, o-ethylstyrene, op-dichlorostyrene, or the like.

Here, as the rubbery polymer, polybutadiene, styrene-butadiene copolymer rubber, styrene-acrylonitrile copolymer rubber, polybutyl acrylate, ethylene-propylene-diene rubber, ethylene-
A rubbery polymer that can be copolymerized or graft-copolymerized with an olefin rubber such as a propylene rubber or an isoprene rubber is used. The polymer containing a rubbery polymer means a copolymer or a graft copolymer, and can be obtained by using a usual method such as a bulk polymerization method, a suspension polymerization method or an emulsion polymerization method. The amount of the rubbery polymer is 90% by weight or less, preferably 80% by weight or less. A polystyrene resin containing a rubbery polymer in an amount of more than 90% by weight has low heat resistance and is not preferable because it is too flexible. Among the polystyrene-based resins, from the viewpoint of cost and performance, polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-rubbery polymer copolymer, styrene-rubbery polymer-acrylonitrile copolymer is preferable. . The amount of polystyrene resin in the mixture of polyphenylene ether resin and polystyrene resin is 6
It is preferably 0% by weight or less. If it exceeds 60% by weight, the heat resistance of the polyphenylene ether is impaired. It is more preferably 5 to 50% by weight.

The (B) saturated polyester used in the present invention is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or its ester-forming derivative and a diol or its ester derivative as main components. , Or a ring-opening polymer of a lactone, and these may be used alone or in combination of two or more.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenylcarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, or an ester-forming derivative thereof or the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The diol component is a C ₂ -C ₁₀ aliphatic diol, that is, ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6. -Hexanediol, 1,8-octanediol, cyclohexanediol, etc., or long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-
1,3-polypropylene glycol, polytetramethylene glycol, etc. are mentioned, and these are used individually or in combination of 2 or more types.

Specifically, polyethylene terephthalate,
Polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1,2-
Examples thereof include bis (phenoxy) ethane-4,4'-dicarboxylate, and these may be used alone or in combination of two or more kinds. Among them, polybutylene terephthalate, polyethylene terephthalate or a mixture thereof is preferable from the viewpoints of mechanical properties, heat resistance and moldability. The molecular weight of the saturated polyester of the present invention is not particularly limited, but those having an intrinsic viscosity η of 0.5 or more are preferable in terms of mechanical strength and heat resistance.

The amount of the (A) polyphenylene ether-based resin or the mixture of the polyphenylene ether-based resin and the polystyrene-based resin and (B) the saturated polyester used is
(A) Polyphenylene ether-based resin, or mixture of polyphenylene ether-based resin and polystyrene-based resin 9
5 to 5 parts by weight, and (B) saturated polyester to 5 to 95 parts by weight. If it is out of these ranges, a resin composition having both characteristics cannot be obtained. It is preferably 85 to 15 parts by weight of (A) polyphenylene ether resin or a mixture of polyphenylene ether resin and polystyrene resin, and (B) 15 to 85 parts by weight of saturated polyester.

The (C) graft-modified polyolefin resin of the present invention comprises (a) a polyolefin resin, (b) the following general formula (I):

[0026]

[Chemical 7]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). A modifier comprising a compound, a modifier comprising a mixture of the compound and glycidyl methacrylate,
Alternatively, it is produced by polymerizing a modifier composed of glycidyl methacrylate and (c) a vinyl-based monomer in an aqueous suspension in the presence of (d) a radical polymerization initiator.

Regarding the blending ratio of the constituent components of the (C) graft-modified polyolefin resin, the first or second aspect of the present invention can be used.
In (a) a polyolefin resin in an aqueous suspension, (b) a modifier comprising a compound having a glycidyl group represented by the general formula (I), or (b1) the compound and (b2) glycidyl methacrylate. The blending ratio of the modifier consisting of a mixture of
The amount of the (b) modifier is 0.1 to 30 parts by weight, preferably 0.1 to 15 parts by weight, based on 0 parts by weight. When it is more than the above range, the mechanical properties and fluidity of the resin composition are deteriorated, and when it is less than the above range, the compatibilizing effect is poor. The mixing ratio of the vinyl monomer (c) is 0.1 part of the vinyl monomer (c) with respect to 100 parts by weight of the polyolefin resin (a).
To 500 parts by weight, preferably 0.1 to 200 parts by weight, more preferably 0.1 to 100 parts by weight. When the amount is more than the above range, the polymerization of vinyl-based monomers becomes the main component, so that excessive aggregation, fusion bonding, agglomeration, etc. occur in the aqueous suspension during the polymerization. Further, (b1) general formula (I)
The mixing ratio (b1) / [(b1) + (b2)] of the modifier consisting of a mixture of the compound having a glycidyl group represented by the formula (b2) and glycidyl methacrylate is 0.01 to 0.
99. Outside this range, a good compatibilizing effect cannot be obtained. It is considered that this is because the graft structure is modulated.

In the third aspect of the present invention, the compounding amounts of the (a) polyolefin resin, (b) glycidyl methacrylate modifier, and (c) vinyl monomer in the aqueous suspension are as follows: The total amount of (b) glycidyl methacrylate and (c) vinyl monomer is 0.1 to 25 parts by weight with respect to 100 parts by weight of the polyolefin resin, and (b) glycidyl methacrylate ( c) The mixing ratio (b) / [(b) + (c)] of the vinyl-based monomer is 0.01 to 0.95. When the total amount of (b) glycidyl methacrylate and (c) vinyl-based monomer is 25 parts by weight or more, the effect of compatibility is saturated and no further effect can be expected, and the vinyl monomer lowers heat resistance. Invite. If the amount is less than 0.01 part by weight, the compatibilizing effect is small.
Preferably, it is from 0.5 to less than 25 parts by weight.
If the mixing ratio of (b) glycidyl methacrylate and (c) vinyl monomer is out of the above range, the compatibilizing effect is small. It is preferably 0.1 to 0.9.

Examples of the radical polymerization initiator (d) used in the present invention include methyl ethyl ketone peroxide, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylcyclohexane, n-butyl-4,
4-bis (t-butylperoxy) valerate, 2,5
-Dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5
-Dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, organic peroxides such as benzoyl peroxide, Alternatively, for example, 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1
-Cyano-1-methylethyl) azo] formamide, 2
-Phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile,
Examples of the azo compound include 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-acetoxypropane), and 2,2'-azobis (2-acetoxybutane). , And these are used alone or in combination of two or more kinds.

(D) The amount of radical polymerization initiator used is
The total amount of the (b) modifier and (c) vinyl monomer is 0.001 to 10 parts by weight based on 100 parts by weight. 0.
If the amount is less than 001 parts by weight, the amount of grafting sufficient to develop the characteristics of the modified polyolefin resin cannot be achieved, and if it exceeds 10 parts by weight, the crosslinking reaction by the radical of the polyolefin type part by weight or the reduction of the molecular weight due to the main chain cleavage is caused. It is not preferable because the mechanical properties of the resin are deteriorated. It is preferably 0.01 to 5 parts by weight.

As the (a) polyolefin resin, which is one of the constituents of the (c) graft-modified polyolefin resin, ethylene, propylene, 1-butene, 1-
Pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,3-cyclohexadiene, 1,4-hexadiene, 1,3-octadiene, 1,5-cyclooctadiene, methylenenorbornene, 1,5 -Norbornadiene, ethylidene norbornene and homopolymers or copolymers selected from the group of monomers of α, ω-non-conjugated dienes, a mixture of two or more of the homopolymers, and 2 of the copolymers.
Examples thereof include a mixture of one or more kinds, or a mixture of one or more kinds of the homopolymer and one or more kinds of the copolymer. The molecular weight of the polyolefin resin is not particularly limited, but is preferably 10,000 or more from the viewpoint of mechanical strength and the like.

The modifier (b) having a glycidyl group represented by the general formula (I) for modifying the polyolefin resin is an important component of the present invention, and at least one acrylamide is contained in each molecule. Derived from denaturants with a glycidyl group. The acrylamide group includes a methacrylamide group in addition to the acrylamide group.

Such a compound is disclosed in, for example, JP-A-60.
It can be manufactured by the method described in No. 130580. That is, the target compound is obtained by condensing an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide in the presence of an acidic catalyst, and then glycidylating the hydroxyl group with epihalohydrin. Is obtained. As the aromatic hydrocarbon having at least one phenolic hydroxyl group, a phenol compound having 6 to 23 carbon atoms is used. Specific examples of the phenol compound include phenol, cresol, xylenol, carvacrol, thymol, naphthol, resorcin, hydroquinone, pyrogallol, phenanthrol and the like. Among them, monohydric phenol having an alkyl substituent is preferable.

For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, a compound represented by the following structural formula (II) can be obtained.

[0036]

Embedded image

When orthocresol and N-methylolacrylamide are used as starting materials, a compound represented by the following structural formula (V) can be obtained.

[0038]

[Chemical 9]

The vinyl monomer (c), which is one of the constituents of the graft-modified polyolefin resin (C), is, for example, an aromatic vinyl compound such as styrene, o-methylstyrene or p-. Methylstyrene, m-
Methyl styrene, α-methyl styrene, vinyltoluene, divinylbenzene and the like are, as the methacrylic acid alkyl ester having 1 to 22 carbon atoms, methyl methacrylate, ethyl methacrylate, methacrylic acid-i-propyl, methacrylic acid-n. -Butyl, methacrylic acid-t-butyl, allyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc., have 1 carbon atoms.
Examples of the alkyl acrylates having a pH of 22 include methyl acrylate, ethyl acrylate, acrylic acid-i-
Propyl, acrylic acid-n-butyl, acrylic acid-t-
Butyl, 2-ethylhexyl acrylate, stearyl acrylate, etc., as vinyl alkyl ethers having 1 to 22 carbon atoms, vinyl methyl ether, vinyl ethyl ether, vinyl-n-propyl ether, vinyl-i-propyl ether. , Vinyl-i-butyl ether, vinyl-n-amyl ether, vinyl-i-amyl ether, vinyl-2-ethylhexyl ether and vinyl octadecyl ether, and unsaturated nitrile compounds include acrylonitrile and methacrylonitrile. Examples of the saturated amide compound include acrylamide and methacrylamide, and examples of the maleic acid di-alkyl ester include maleic acid di-n-amyl ester, maleic acid di-n-butyl ester, maleic acid di-i-amyl ester, and maleic acid. Acid di-i-butyl ester, maleic acid dimethyl ester, maleic acid di-n-propyl ester, maleic acid di-octyl ester, maleic acid di-nonyl ester, and the like are allylalkyl ethers having 1 to 8 carbon atoms. , Allyl ethyl ether, allyl-n-octyl ether, etc., as diene compounds, dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1 , 4-cyclohexadiene, 1,5-
Examples thereof include cyclohexadiene and 1,3-cyclooctadiene, and examples of other vinyl monomers include acrylic acid and vinyl acetate. These are used alone or in combination of two or more.

In the present invention, the amount of the graft-modified polyolefin resin (C) used is 1 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). If it is less than 1 part by weight, the effect of compatibility becomes insufficient, and if it is more than 100 parts by weight, heat resistance and elastic modulus are lowered. It is preferably 3 to 50 parts by weight.

As the filler used in the present invention, silica, talc, mica, glass fiber, glass beads, hollow glass beads, neutral clays, carbon fibers, aromatic polyamide fibers, aromatic polyester fibers, vinylon fibers, Examples include carbon fiber, silicon carbide fiber, alumina fiber, potassium titanate fiber, metal fiber, etc., which may be used alone or in combination with 2
Used in combination of two or more species. The amount of the filler used is 1 to 100 parts by weight based on 100 parts by weight of the resin composition of the present invention. If it is less than 1 part by weight, the effect of the filler cannot be obtained, and if it is more than 100 parts by weight, the molding fluidity is lowered.
It is preferably 5 to 50 parts by weight.

There is no particular limitation on the method for producing the resin composition of the present invention. For example, polyphenylene ether resin, polystyrene resin, saturated polyester and graft modified polyolefin resin are uniformly mixed using a stirrer or the like. After melt-kneading method, a method of melt-kneading a saturated polyester with a polyphenylene ether-based resin and polystyrene-based resin and graft-modified polyolefin-based resin, after melt-kneading the polyphenylene ether-based resin and polystyrene-based resin, saturated polyester And a graft-modified polyolefin resin are melt-kneaded, a polyphenylene ether resin, a polystyrene resin, and a saturated polyester are melt-kneaded, and then the graft-modified polyolefin resin is melt-kneaded. The melt mixing method is not particularly limited in the present invention, and various conventionally known blenders such as an extruder, a heat roll, a Brabender, and a Banbury mixer may be used. If necessary, a reaction catalyst for a graft-modified polyolefin resin, a flame retardant, a pigment, a stabilizer, or the like can be added to the resin composition of the present invention. Further, a thermoplastic crystalline resin or amorphous resin other than the present invention may be added as long as the characteristics of the present invention are not impaired.

The reaction catalyst for the graft-modified polyolefin resin is, for example, tetraphosphonium bromide, tetra n-butylphosphonium bromide, tetra n.
-Butylphosphonium chloride and the like, which may be used alone or in combination of two or more kinds. The amount of the reaction catalyst used is 0.001 to 2 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). If the amount is less than 0.001 part by weight, a good compatibilizing effect cannot be obtained. Further, if the amount is more than 2 parts by weight, further effect depending on the amount used cannot be obtained. In addition, the saturated polyester is decomposed and the characteristics of the saturated polyester are impaired. The preferred amount used is 0.005 to 1 part by weight.

As the flame retardant, tetrabromobisphenol A, 2,2-bis (4-hydroxy3,5-dibromophenyl) propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate,
2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, halogenated flame retardants such as chlorinated paraffin; ammonium phosphate , Tricresyl phosphate, triethyl phosphate, tris chloroethyl phosphate, tris (β-chloroethyl) phosphate, tris dichloropropyl phosphate, cresyl phenyl phosphate, xylenyl diphenyl phosphate, acidic phosphate ester, Phosphorus flame retardants such as nitrogen-containing phosphorus compounds; inorganic flame retardants such as red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, brominated polystyrene, brominated poly α Examples thereof include polymer flame retardants such as methylstyrene, brominated polycarbonate, brominated polyepoxy resin, chlorinated polyethylene, chlorinated poly α-methylstyrene, chlorinated polycarbonate and chlorinated polyepoxy resin. The flame retardant is the resin composition 10 of the present invention.
1 to 50 parts by weight relative to 0 parts by weight, alone or 2
Used in combination of two or more species. If it is less than 1 part by weight, the flame retardant addition effect becomes insufficient, and if it exceeds 50 parts by weight, molding fluidity is deteriorated and mechanical properties are deteriorated.

As the above-mentioned stabilizer, as an antioxidant,
For example, 2,4-bis- (n-octylthio) -6- (4
-Hydroxy-3,5-di-t-butylanilino)-
1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thiobis (4-methyl-6)
-T-butylphenol), 1,3,5-trimethyl-
Phenol-based such as 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, thioether-based or tetrakis (2,4-di-t-butylphenyl) -4,4 Examples thereof include phosphorus-based compounds such as'-biphenylene phosphonite and tris (2,4-di-t-butylphenyl) phosphite, and examples of the light stabilizer include dimethyl-1- (2-hydroxyethyl) succinate. -4-hydroxy-2,2,6,6, -tetramethylpiperidine polycondensate, poly [[6- (1,1,3,
3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [[2,2,6 , 6-Tetramethyl-4-piperidyl)
Imino]], 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,
Hindered amines such as 2,2,6,6-pentamethyl-4-piperidyl). These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer used is 0. 0 with respect to 100 parts by weight of the resin composition of the present invention.
It is in the range of 1 to 10 parts by weight. If it is less than 0.1 part by weight, the effect of adding a stabilizer is not sufficient, and if it exceeds 10 parts by weight, mechanical properties are deteriorated.

[0046]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples, and various modifications can be made without departing from the scope of the invention. In the following description, "part"
Unless otherwise specified, “%” means “part by weight” and “% by weight”, respectively.

Reference Example 1: Graft-Modified Polyolefin Resin (MPO1) In a pressure-resistant closed reaction tank, ethylene-propylene copolymer rubber (ethylene content 26
%) 531 parts, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 3
1.25 parts, styrene 62.5 parts, 1,1-bis (t-
Butylperoxy) 3,3,5-trimethylcyclohexane 1.3 parts, tribasic calcium phosphate 10.5 parts, and an emulsifier (Latemul PS: registered trademark manufactured by Kao Corporation) 0.
315 parts were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous solution was stirred at 95 ° C for 1 hour and then at 110 ° C for 3 hours.
The polymerization was completed by stirring for a period of time. The obtained particles are washed with water and the residual monomer, tricalcium phosphate, and Latemur P are used.
S, and 1,1-bis (t-butylperoxy) 3,
After removing 3,5-trimethylcyclohexane, it was dried to obtain a graft-modified polyolefin resin (MPO1).

Reference Example 2: Graft-modified polyolefin resin (MPO2) N- [4- (2,3-epoxypropoxy) of Reference Example 1
N- [4- (2,3-epoxypropoxy) -3,5 instead of -3,5-dimethylbenzyl] acrylamide
62.5 parts of a mixed solution of dimethylbenzyl] acrylamide and glycidyl methacrylate (mixing ratio of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide is 0.5) was used. A graft-modified polyolefin resin was obtained in the same manner as in Reference Example 1.

Reference Example 3: Graft-modified polyolefin resin (MPO3) N- [4- (2,3-epoxypropoxy) of Reference Example 1
A graft modified polyolefin resin was obtained in the same manner as in Reference Example 1 except that glycidyl methacrylate was used instead of -3,5-dimethylbenzyl] acrylamide.

Reference Example 4: Graft-modified polyolefin resin (MPO4) Polypropylene particles (ethylene content 3%, DSC melting point 14 per 1400 parts of pure water) in a pressure-resistant closed reaction tank.
7 ° C.) 490 parts, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 3
5 parts, 175 parts of styrene, 1.26 parts of di-t-butyl peroxide, 10.5 parts of tricalcium phosphate, and an emulsifier (Latemul PS: registered trademark manufactured by Kao Corporation).
315 parts were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous solution was stirred at 100 ° C. for 1 hour and then at 140 ° C. for 5 hours to complete the polymerization. The obtained particles are washed with water and the residual monomer, tricalcium phosphate, and Latemur P are used.
After removing S and di-t-butyl peroxide,
It was dried to obtain a graft-modified polyolefin resin composition.

Reference Example 5: Graft-modified polyolefin resin (MPO5) Same as Reference Example 1 except that 20 parts of styrene, 40 parts of methacrylic acid and 2.5 parts of allyl methacrylate were used instead of styrene of Reference Example 1. To obtain a graft-modified polyolefin resin.

Comparative Reference Example 1: Graft-modified polyolefin resin (RPO1) N- [4- (2,3-epoxypropoxy) -3,5-
A graft modified polyolefin resin was obtained in the same manner as in Reference Example 1 except that dimethylbenzyl] acrylamide was not used.

Comparative Reference Example 2: Graft-modified polyolefin resin (RPO2) N- [4- (2,3-epoxypropoxy) -3,5-
Dimethylbenzyl] acrylamide was not used, and polypropylene particles (ethylene content 3%, DSC melting point 147 ° C.) were used instead of the ethylene-propylene copolymer rubber (propylene content 26%) of Reference Example 1 A graft-modified polyolefin resin was obtained in the same manner as in 1.

Comparative Reference Example 3: Graft-modified polyolefin resin (RPO3) The amount of glycidyl methacrylate used in Reference Example 3 was 53.
Example 3 except that the amount of styrene used was 470 parts
A graft-modified polyolefin resin was obtained in the same manner as in.

Examples 1 to 8 and Comparative Examples 1 to 6 Each component of the resin composition of the present invention, (A) polyphenylene ether resin, or a mixture of polyphenylene ether resin and polystyrene resin, (B) saturated polyester,
(C) Graft modified polyolefin resin and (D) 4
Using the following as the primary phosphonium salt, resin compositions were produced in the combinations and blending ratios of the respective components shown in Tables 1 and 2, and test pieces for each characteristic evaluation were produced.

(A) Polyphenylene ether resin, polystyrene resin (1) Polyphenylene ether resin Poly (2,6-dimethylphenylene-1,4-ether) having an intrinsic viscosity of 0.42 (PPE in the table) (2) Polystyrene resin Styrene-acrylonitrile random copolymer (AS-H manufactured by Denki Kagaku Kogyo Co., Ltd., registered trademark, abbreviated as PS in the table.) (B) Saturated polyester polybutylene terephthalate (stock) Duranex 2002 made by Polyplastics Co., Ltd .: registered trademark, PB in the table
Abbreviated as T. ) (C) Graft-modified polyolefin resin Reference Examples 1-5 (MPO1-MPO5), Comparative Reference Example 1-
3 (RPO1 to RPO3) and an ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., Bondfast 2C: registered trademark, abbreviated as BF in the table).
Was used.

The resin composition and the test piece were manufactured by the following methods. First, dry-blend each component in the ratios shown in Tables 1 and 2, and then use a 45 mm twin-screw extruder to make the cylinder temperature 2
It was melt-kneaded at 80 ° C. and pelletized. After vacuum-drying the pellets, the temperature of the cylinder was 285 ° C. with an injection molding machine.
Injection molding was performed at a mold temperature of 70 ° C. to prepare a test piece.

Evaluation of each characteristic of the resin composition (molded product) of the present invention was carried out by the following methods. (1) Flexural modulus: According to ASTM D790. (2) Impact resistance: -30 according to ASTM D256
It was measured at ° C. (3) Heat resistance: After being retained in an injection molding machine at 290 ° C. for 20 minutes, a test piece for Izod impact test measurement was molded and measured. The retention rate against the value when not retained was evaluated. (4) Oil resistance: A test piece having a thickness of 3 mm was loaded with 4% bending strain and immersed in gasoline at 23 ° C. for 48 hours, and the surface thereof was observed. ◯: The surface is cloudy and has no cracks. Δ: Fogging was observed on the surface, and there were some cracks. X: Many cracks on the surface and severe elution. (5) Molding fluidity: injection pressure 600 kg / cm ² , 285 ° C
A rectangular spiral having a thickness of 3 mm was formed at the cylinder temperature of, and the length was evaluated.

The results of characteristic evaluation are shown in Tables 1 and 2. As is clear from the examples of Table 1 and the comparative examples of Table 2, the resin composition of the present invention has well-balanced physical properties such as mechanical properties, heat resistance, and molding fluidity.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

As described in detail above, the resin composition according to the present invention has an excellent balance of physical properties such as mechanical properties, heat resistance and molding fluidity.
It is possible to provide a molded product suitable as an electric / electronic component or the like.

Claims (11)

[Claims] 1. A composition comprising the following components (A), (B) and (C), wherein (A) is 5 to 95 parts by weight, (B) is 95 to 5 parts by weight, and (C) is the above (A). 1 to 100 parts by weight based on 100 parts by weight of the total amount of (B) and (B). (A) polyphenylene ether resin, or a mixture of polyphenylene ether resin and polystyrene resin,
(B) saturated polyester, (C) (a) 100 parts by weight of polyolefin resin, (b) the following general formula (I): (In the formula, Ar represents an aromatic hydrocarbon group having C ₆ -C ₂₃ for at least one chromatic glycidyl group, R represents a hydrogen atom or a methyl group.) Made of a compound having a glycidyl group represented by Modifier 0.1 to 30 parts by weight, (c)
0.1 to 500 parts by weight of a vinyl monomer, and 0.001 to 10 parts by weight of a radical polymerization initiator (d) per 100 parts by weight of the total amount of the components (b) and (c). A component (b) and a component (c) in the aqueous suspension are impregnated in the component (a), and the component (b) and the component (c) are added to the component (a). Graft-modified polyolefin resin obtained by polymerization. 2. The following components (A), (B) and (C), wherein (A) is 5 to 95 parts by weight, (B) is 95 to 5 parts by weight, and (C) is the above (A). 1 to 100 parts by weight based on 100 parts by weight of the total amount of (B) and (B). (A) polyphenylene ether resin, or a mixture of polyphenylene ether resin and polystyrene resin,
(B) saturated polyester, (C) (a) 100 parts by weight of polyolefin resin, (b) (b1) the following general formula (I) (In the formula, Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) And a compound having a glycidyl group ( b2) consisting of a mixture with glycidyl methacrylate, the mixing ratio of which is (b1) / [(b1) + (b
2)] is 0.01 to 0.99, and a modifier 0.1 to 30
Parts by weight, 0.1 to 500 parts by weight of vinyl monomer (c),
And 0.001 of the radical polymerization initiator (d) per 100 parts by weight of the total amount of the components (b) and (c).
An aqueous suspension containing 10 to 10 parts by weight is prepared, the component (b) and the component (c) in the aqueous suspension are impregnated in the component (a), and the components (b) and (c) are added. A graft-modified polyolefin resin obtained by polymerizing the component (a). 3. The following components (A), (B) and (C), wherein (A) is 5 to 95 parts by weight, (B) is 95 to 5 parts by weight, and (C) is the above (A). 1 to 100 parts by weight based on 100 parts by weight of the total amount of (B) and (B). (A) polyphenylene ether resin, or a mixture of polyphenylene ether resin and polystyrene resin,
The total amount of the (B) saturated polyester, (C) (a) polyolefin resin 100 parts by weight, (b) glycidyl methacrylate modifier and (c) vinyl monomer was 0.1.
1 to less than 25 parts by weight, and the amount of the component (b) and the component (c) is (b) / [(b) + (c)] = 0.01 to 0.9.
5 and (d) the radical polymerization initiator is added to the above (b).
The total amount of the component and the component (c) is 0.
An aqueous suspension containing 001 to 10 parts by weight is prepared, and the component (b) and the component (c) in the aqueous suspension are impregnated in the component (a), and the components (b) and (c) are prepared. Graft-modified polyolefin resin 1 obtained by polymerizing
~ 100 parts by weight. 4. The resin composition according to claim 1, wherein the saturated polyester (B) is polyethylene terephthalate, polybutylene terephthalate, or a mixture thereof. 5. The polystyrene resin is polystyrene,
At least one polystyrene resin selected from the group consisting of rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-rubbery polymer copolymer, and styrene-rubbery polymer-acrylonitrile copolymer. The resin composition according to claim 1. 6. The polyolefin resin to be graft-modified is ethylene, propylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,
3-cyclohexadiene, 1,4-hexadiene, 1,
Homopolymers or copolymers of monomers selected from the group consisting of 3-octadiene, 1,5-cyclooctadiene, methylenenorbornene, 1,5-norbornadiene, ethylidenenorbornene and α, ω-nonconjugated dienes, and the homopolymers thereof. Mixtures of two or more polymers, two of the copolymers
The resin composition according to claim 1, which is a mixture of one or more kinds, or a mixture of one or more kinds of the homopolymer and one or more kinds of the copolymer. 7. (b) The compound having a glycidyl group represented by the general formula (1) has the following structural formula (II): The resin composition according to claim 1, which is represented by: 8. The vinyl-based monomer is an aromatic vinyl compound, an acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms, a methacrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms, Vinyl alkyl ether having an alkyl group having 1 to 22 carbon atoms, vinyl alcohol, an unsaturated nitrile compound, an unsaturated amide compound, a maleic acid dialkyl ester having an alkyl group having 1 to 9 carbon atoms, and an alkyl group having carbon number of The resin composition according to claim 1, 2 or 4 to 7, which is at least one selected from the group consisting of allyl alkyl ethers having 1 to 8, diene compounds, acrylic acid, methacrylic acid and vinyl acetate. 9. The vinyl monomer is an aromatic vinyl compound, an alkyl acrylate having an alkyl group having 1 to 22 carbon atoms, a methacrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms, Vinyl alkyl ether having an alkyl group having 1 to 22 carbon atoms, vinyl alcohol, an unsaturated nitrile compound, and an alkyl group having 1 carbon atom
At least one selected from the group consisting of a maleic acid dialkyl ester having 1 to 9 carbon atoms, an allylalkyl ether having an alkyl group having 1 to 8 carbon atoms, a diene compound, acrylic acid, methacrylic acid, and vinyl acetate.
The resin composition according to item 6. 10. The resin composition according to claim 8, wherein the vinyl-based monomer is at least one selected from the group consisting of methyl methacrylate, butyl acrylate and allyl methacrylate. 11. The resin composition 10 according to claim 1.
0 parts by weight of silica, talc, mica, glass fiber, glass beads, hollow glass beads, neutral clays, carbon fibers, aromatic polyamide fibers, aromatic polyester fibers, vinylon fibers, carbonized fibers, silicon carbide fibers 1 to 100 parts by weight of at least one filler selected from the group consisting of alumina fibers, potassium titanate fibers and metal fibers.