JPH04275371A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide an engineering plastic composition excellent in chemical resistance, moldability, impact resistance, heat-resistance, paintability, mechanical properties, appearance of molded article, etc., and usable as electrical and electronic parts, mechanical parts, automobile parts, etc. CONSTITUTION:An engineering plastic composition satisfying the above object can be produced by compounding specific amounts of an ethylene copolymer containing epoxy group and an olefinic copolymer containing acid group to an engineering plastic selected from polyester, polycarbonate, polyamide, polyphenylene ether, polyacetal, polyarylene sulfide, polyarylate, ABS, etc.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent chemical resistance, moldability, impact resistance, heat resistance, paintability, mechanical properties, and molded product appearance. The composition can be used in a wide range of fields such as electrical and electronic parts, mechanical parts, and automobile parts.

0002

[Prior Art] So-called engineering plastics such as aromatic polyester resins, polycarbonate resins, polyamide resins, polyphenylene ether resins, polyacetal resins, polyphenylene sulfide resins, and polyarylate resins have excellent mechanical properties, heat resistance, rigidity,
ABS resins and polypropylene have impact resistance, excellent properties such as chemical resistance and moldability, and are inexpensive, so they are widely used in various molded products. In recent years, a variety of research has been conducted to improve product functionality, lower prices, and reduce weight. Among them, mixing multiple plastics (blends, alloys) to add more functions has been conducted. Many attempts have been made to take advantage of the characteristics of each type of shiso. In engineering plastics, amorphous resins such as polycarbonate resins, polyphenylene ether resins, and ABS resins generally have inferior chemical resistance and fluidity compared to crystalline resins, while aromatic polyester resins and polyphenylene sulfide Although crystalline resins such as resins and polyarylate resins have excellent heat resistance and rigidity, they have drawbacks such as brittleness and anisotropy.

For example, aromatic polyester resins have excellent mechanical properties, but are poor in impact resistance, particularly notched impact strength. Therefore, attempts have been made to improve the impact resistance by blending rubber-like substances with it, but rubber-like polymers that are effective as impact resistance modifiers have a glass transition temperature below room temperature. Therefore, if a large amount of polyester is added in an attempt to increase impact resistance, the heat resistance and rigidity, which are characteristics of aromatic polyester, will decrease, resulting in an undesirable result.

[0004] In recent years, Japanese Patent Application Laid-open No. 144452/1983,
JP-A-52-32045, JP-A-53-1170
α-olefins and α,β- shown in Publication No. 49 etc.
A method of blending a copolymer consisting of a monomer such as an unsaturated acid glycidyl ester, a copolymer consisting of an α-olefin and a non-conjugated diene disclosed in JP-A No. 60-40154, etc. Attempts have been made to blend modified polymers obtained by grafting monomers such as unsaturated acid glycidyl esters, but although relatively good results have been obtained, the results are far from satisfactory. This is the current situation.

[0005] Polycarbonate resin also has heat resistance,
Polyamide resin has excellent mechanical properties and impact resistance, but has the disadvantage of poor chemical resistance. Polyamide resin has excellent moldability, thermal stability, abrasion resistance, and solvent resistance, but has poor moisture absorption. Since it is high, there are problems with dimensional stability, etc. Although polyphenylene ether resins have excellent mechanical and electrical properties, heat resistance, and good dimensional stability, they have problems in processability, oil resistance, and impact resistance. Polyacetal resin has excellent dimensional stability, abrasion resistance, and mechanical strength, but poor impact resistance. Polyphenylene sulfide resin has excellent heat resistance and flame retardancy, but is weak due to poor ductility. Polyarylate resin has poor heat resistance. ABS resins have excellent impact resistance but poor chemical resistance. In order to improve these drawbacks, attempts have been made to blend them with the above-mentioned modifiers, to compose them with fillers, fibers, etc., and to alloy them with other engineering plastics. However, the addition of such rubber-like modifiers causes a decrease in heat resistance, etc., the addition of fibers and fillers reduces impact resistance, and the addition of compatibilizers also sacrifices the properties of engineering plastics to some extent. There must be.

A first object of the present invention is to provide a thermoplastic resin composition that minimizes the deterioration of the properties of engineering plastics and is endowed with new functions. In addition, in recent years, examples of polymer alloys of polyolefin and engineering plastics, particularly polymer alloys of polypropylene and engineering plastics, have begun to be shown for the purpose of lowering the price and weight of products. It would be useful industrially if it could add mechanical properties, heat resistance, rigidity, impact resistance, paintability, etc. while maintaining polypropylene's excellent properties such as moldability and chemical resistance, as well as low cost. It becomes a material. However, polypropylene and the above-mentioned plastics are difficult to mix with each other, and a polymer alloy cannot be obtained by simply melt-mixing them. JP-A-61-62542 and JP-A-61-64741 contain examples of blending polyamide resin with polypropylene.
No. 0744 and Japanese Unexamined Patent Publication No. 61-60746,
An example in which an aromatic polyester resin is blended with polypropylene is disclosed. In these examples, polypropylene modified with an acid anhydride and an epoxy group-containing ethylene copolymer are used to facilitate mixing of the respective resins. In this case, the compatibility is improved compared to simply mixing the two resins, but there are drawbacks such as increased melt viscosity. Furthermore, there were no examples of improving compatibility with resins other than polyamide resins and aromatic polyesters. Therefore, the second object of the present invention is to provide a polypropylene-containing thermoplastic resin composition that has excellent heat resistance, dimensional stability, moldability, impact resistance, and oil resistance, and is further useful for reducing the weight of automobiles. There is a particular thing.

[0007]

[Problems to be Solved by the Invention] Polyolefins and engineering plastics have low compatibility and are difficult to mix with each other, and a polymer alloy cannot be obtained by simply melt-mixing them. While maintaining the excellent properties of polyolefins such as moldability and chemical resistance, as well as low cost,
Mechanical properties and heat resistance of engineering plastics
Thermoplastic resin compositions that minimize deterioration in properties such as rigidity, impact resistance, and paintability, as well as thermoplastic resin compositions containing olefin (co)polymers such as polypropylene, which are useful for reducing the weight of automobiles. to provide.

[0008]

[Means for solving the problem] That is, the first aspect of the present invention
The invention consists of (A) an aromatic polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene ether resin alone or a mixture of these and a styrene polymer, a polyacetal resin, a polyarylene sulfide resin, a polyarylate resin, an ABS resin. 100 parts by weight of at least one resin selected from the group, and (B) an epoxy group-containing ethylene copolymer consisting of the following (a) to (c): (a) 80 to 99.9 mol% of olefin monomer units:
(b) 0.1 to 20.0 mol% of glycidyl ester monomer units of α,β-unsaturated acid: (c) 0 to 19.9 mol% of vinyl monomer units radically copolymerizable with ethylene: 1 to 100% by weight Department and (C)
Acid group-containing olefin (co)polymer
A thermoplastic resin composition consisting of 1 to 100 parts by weight,

The second invention of the present invention provides (A) aromatic polyester resin, polycarbonate resin, polyamide resin,
At least one resin 95 selected from the group consisting of polyphenylene ether resin alone or a mixture of polyphenylene ether resin and styrene polymer, polyacetal resin, polyarylene sulfide resin, polyarylate resin, and ABS resin.
(D) 100 parts by weight of a resin composition consisting of 5 to 95% by weight of at least one olefin-based (co)polymer; and (B) epoxy group-containing consisting of the following (a) to (c). Ethylene copolymer: (a) Olefin monomer unit 80-9
9.9 mol%: (b) 0.1 to 20.0 mol% of glycidyl ester monomer units of α,β-unsaturated acid: (c) 0 to 19.9 mol of vinyl monomer units radically copolymerizable with ethylene %: 1 to 100 parts by weight, and (C)
Acid group-containing olefin (co)polymer
A thermoplastic resin composition characterized by blending 1 to 100 parts by weight,

A third aspect of the present invention provides that (E) an inorganic filler and/or (F) a rubber-like elastic body 1 is added to 100 parts by weight of the thermoplastic resin composition according to claim 1 or 2.
This is a thermoplastic resin composition characterized in that it contains up to 200 parts by weight.

[0011] The aromatic polyester resin used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction containing as a main component. The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, phthalic acid; 2,6
-naphthalene dicarboxylic acid; 1,5-naphthalene dicarboxylic acid; bis(p-carboxyphenyl)methane; anthracene dicarboxylic acid; 4,4'-diphenylcarboxylic acid; 4,4'-diphenyl ether dicarboxylic acid; 1,
Examples include 2-bis(phenoxy)ethane 4,4'-dicarboxylic acid and ester-forming derivatives thereof.

[0012] The diol component has 2 to 1 carbon atoms.
0 fatty acid diols i.e. ethylene glycol; propylene glycol; 1,4-butanediol; neopentyl glycol; 1,5-pentanediol; 1,6-
Hexanediol; decamethylene diglycol; cyclohexanediol, etc., or molecular weight 400-6.0
00 long chain glycols, ie polyethylene glycol; poly 1,3-propylene glycol; polytetramethylene glycol, etc. and mixtures thereof. Preferred thermoplastic aromatic polyester resins used in the present invention include polyethylene terephthalate; polypropylene terephthalate; polybutylene terephthalate; polyhexamethylene terephthalate; polyethylene-2,6-naphthalate; polyethylene-1,2-bis Examples include (phenoxy)ethane-4,4'-dicarboxylate. More preferably,
Polyethylene terephthalate; polybutylene terephthalate. The intrinsic viscosity of these thermoplastic aromatic polyester resins is 25± as a concentration of 0.32 g in 100 ml of trifluoric acid (25)/methylene chloride (75).
Measured below 0.1°C. Preferably the intrinsic viscosity is 0.4
~4.0 dl/g. If it is less than 0.4 dl/g, the thermoplastic aromatic polyester resin will not be able to exhibit sufficient mechanical strength, which is not preferable. Moreover, if it exceeds 4.0 dl/g, the fluidity during melting will decrease and the surface gloss of the molded product will decrease, which is not preferable.

The polycarbonate resin used in the present invention is a 4,4-dioxyallylalkane polycarbonate such as 4,4-dihydroxydiphenyl-2,2-propane (commonly known as bisphenol A), but especially 4,4-dihydroxyphenyl-2,2-propane polycarbonate, number average molecular weight 15,00
0 to 80,000 is preferred. These polycarbonates are manufactured by any method. for example,
In the production of polycarbonate of 4,4-dihydroxydiphenyl-2,2-propane, 4,4-dihydroxydiphenyl-2,2-propane is used as a dioxine compound, and phosgene is blown into the presence of an aqueous caustic alkali solution and a solvent. For example, a method for producing it, or a method for producing it by transesterifying 4,4-dihydroxydiphenyl-2,2-propane carbonate diester in the presence of a catalyst can be exemplified.

The polyphenylene ether resin used in the present invention has the general formula 1

embedded image (wherein R1, R2, R3, R4, and R5 are selected from hydrogen, halogen atoms, hydrocarbon groups, or substituted hydrocarbon groups, and one of them is always a hydrogen atom. ) is a polymer obtained by oxidative polymerization of the phenol compound shown in ) with oxygen or oxygen-containing gas using a coupling catalyst. R1 in the above general formula,
Specific examples of R2, R3, R4, and R5 include hydrogen, chlorine, fluorine, iodine, bromine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, and methoxycarbonylethyl. , cyanoethyl,
Examples include phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl.

Specific examples of the above general formula include phenol, o, m or p cresol, 2.6-, 2.5-, 2.
・4- or 3,5-dimethylphenol, 2-methyl-
6-phenylphenol, 2,6-diphenylphenol, 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6- and 2
- 4,6-trimethylphenol etc. Two or more types of these phenol compounds can be used. In addition, phenol compounds other than the above general formula, such as bisphenol A, tetrabromobisphenol A,
Copolymerization of dihydric phenols such as resorcinol, hydroquinone, etc. and the phenol compound of the above general formula may also be used.

Examples of the styrenic polymer used in the present invention include homopolymers such as polystyrene, poly(α-methylstyrene), and poly(p-methylstyrene), as well as butadiene rubber, styrene-butadiene copolymer, and ethylene-butadiene rubber. High impact polystyrene modified with various rubbers such as propylene copolymer, ethylene-propylene-diene copolymer, styrene-maleic anhydride copolymer, styrene-
Examples include acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, and styrene-methyl methacrylate copolymer. These styrene polymers have a molecular weight of 0 to 9 relative to the polyphenylene ether resin.
It is mixed in a range of 5% by weight.

The polyamide resins used in the present invention include nylon 6, nylon 6.6, nylon 6.10, nylon 6.12, nylon 11, nylon 12, and nylon 4.
．． Aliphatic polyamide resins such as No. 6 and the like: aromatic polyamide resins such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene group-containing polyamide, modified products thereof, or mixtures thereof. . Particularly preferred polyamide resins include nylon 6 and nylon 6.6.

The ABS resin used in the present invention is obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds in the presence of a conjugated diene rubber. This is a graft copolymer (a) obtained by In addition, if necessary, 2 selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds.
It can contain a copolymer (b) obtained by polymerizing more than one type of compound. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile; examples of aromatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, dimethylstyrene, and chlorostyrene; and examples of unsaturated carboxylic acid alkyl ester compounds include methyl. acrylate, ethyl acrylate,
Examples include butyl acrylate, methyl methacrylate, hydroxyethyl acrylate, and the like. Examples of methods for producing ABS resins include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and emulsion-suspension polymerization.

The polyacetal resin (polyoxymethylene resin) used in the present invention is essentially a cyclic oligomer such as formaldehyde monomer or its trimer (trioxane) or tetraoxane (tetraoxane). An oxymethylene homopolymer consisting only of oxymethylene units and the above raw materials, ethylene oxide, propylene oxide, epichlorohydrin, 1,
It includes oxymethylene copolymers consisting of oxymethylene units produced from cyclic ethers such as 3-dioxolane, glycol formals, and diglycol formals, and oxyalkylene units of C2 or more.

The polyarylene sulfide resin used in the present invention is a polymer represented by the general formula -(Ar-S)n -. Here, -Ar- is, for example,
2

It is a divalent aromatic residue containing at least one carbon 6-membered ring such as
Substituents such as H3 may also be introduced. Particularly typical polyarylene sulfide has the general formula 3

It is polyarylene sulfide (hereinafter referred to as PPS) represented by the following formula. The manufacturing method is disclosed in Japanese Patent Publication No. 54-3368, and 160
It can be produced by reacting paradichlorobenzene and sodium sulfide at ~250°C and under pressurized conditions.

[0021] The polyarylate resin used in the present invention is:
It is a polyester obtained from bisphenols represented by the following formula 4 and terephthalic acid and/or isophthalic acid.

[Chemical 4] In the above formula, X is -O-, -S-, -SO2 -, -CO
- or a hydrocarbon group having 1 to 10 carbon atoms, R1 , R2 , R3 , R4 , R1 ', R
2', R3' and R4' represent groups selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups. When X represents a hydrocarbon group having 1 to 10 carbon atoms, it includes an alkylene group, a branched alkyl group, a halogen-substituted alkyl group, and the like. Preferred hydrocarbon groups include methylene, ethylene, propylene, butylene, isopropylidene, cyclohexylmethylene, and chloroethylene, with isopropylidene being particularly preferred. Also, R1, R2, R3, R4, R1
When ', R2', R3' and R4' represent a hydrocarbon group, the hydrocarbon group is preferably an alkyl group, particularly preferably a lower alkyl group. Examples of such bisphenols include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-2,2'-dimethyl-diphenyl ether, and 4,4'-dihydroxydiphenyl ether.
-dihydroxy-3,3'-dichloro-diphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,
4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylmethane, 1,2-bis(4'-hydroxyphenyl)ethane, 2,2-bis(4'-hydroxyphenyl)propane, 1,4-bis(4) '-hydroxyphenyl)n-butane, bis(4'-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4'-
(hydroxyphenyl)-1,1,2-trichloroethane and the like. Among them, 2,2-bis(4'-hydroxyphenyl)propane, or bisphenol A, or 4,4'-dihydroxydiphenylsulfone, or bisphenol S, is most preferred. On the other hand, terephthalic acid and isophthalic acid are used alone or in combination.

The above polyarylate resin is obtained by polymerizing the above bisphenols and terephthalic acid and/or isophthalic acid, and the polymerization method may be any of ordinary interfacial polymerization, solution polymerization, or melt polymerization. . Further, these polyarylate resins preferably have a molecular weight of about 5,000 to 70,000.

The epoxy group-containing ethylene copolymer (B) used in the present invention is a binary copolymer of ethylene and glycidyl ester of an α,β-unsaturated acid, or a binary copolymer of olefin and α,β-unsaturated acid glycidyl ester.
It is a ternary or multicomponent copolymer of glycidyl ester of β-unsaturated acid and ethylene and a radically polymerizable vinyl monomer, with 80 to 99.9 mol% of ethylene, α,
Glycidyl ester of β-unsaturated acid 0.1-20.0 mol%, vinyl monomer radically polymerizable with ethylene 0
A copolymer comprising 19.9 mol % is preferred.

Vinyl monomers radically polymerizable with ethylene include olefins, vinyl esters, α,
At least one monomer selected from β-ethylenically unsaturated carboxylic acids or derivatives thereof, specifically propylene, butene-1, hexene-1, decene-1, octene-1, styrene, etc. Olefins, vinyl acetate,
Vinyl esters such as vinyl propionate and vinyl benzoate, acrylic acid, methacrylic acid, esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, octadecyl, maleic acid, Examples include maleic anhydride, itaconic acid, fumaric acid, maleic acid monoesters and diesters, vinyl ethers such as vinyl chloride, vinyl methyl ether, and vinyl ethyl ether, and acrylamide-based compounds, especially (
Meth)acrylic acid esters are preferred.

Specific examples of the epoxy group-containing olefin copolymer include ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, and ethylene/ethyl acrylate/glycidyl methacrylate copolymer. , ethylene/carbon monoxide/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, and the like. Among these, preferred are ethylene/glycidyl methacrylate copolymer, ethylene/ethyl acrylate/glycidyl methacrylate copolymer, or ethylene/vinyl acetate/glycidyl methacrylate copolymer. These epoxy group-containing olefin copolymers can be used as a mixture. Furthermore, the epoxy group-containing ethylene copolymer of the present invention also includes a modified product obtained by subjecting a conventional olefin homopolymer or copolymer to an addition reaction with the unsaturated glycidyl group-containing monomer.

The above ethylene polymers include low density, medium density, high density polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-4- Copolymers containing ethylene as a main component with other α-olefins such as methylpentene-1 copolymer and ethylene-octene-1 copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer , ethylene-methacrylic acid copolymer, copolymer of ethylene and ester of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, ethylene-maleic acid copolymer, ethylene-propylene copolymer rubber , ethylene-propyl-diene copolymer rubber, ethylene-vinyl acetate-vinyl chloride copolymer and mixtures thereof, or mixtures with different types of synthetic resins or rubbers.

In addition, examples of the ethylene-unsaturated carboxylic acid alkyl ester copolymer or its metal salt, the unsaturated carboxylic acid alkyl ester and vinyl ester monomer of the ethylene-vinyl ester copolymer include methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Isopropyl acrylate, Isopropyl methacrylate,
n-butyl acrylate, n-butyl methacrylate,
Unsaturated carboxylic acids such as cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, monomethyl maleate, monoethyl maleate, diethyl maleate, and monomethyl fumarate. Alkyl ester monomer; vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate can be mentioned. Particularly preferred are ethyl acrylate and vinyl acetate. These monomers can be used even if mixed. Alternatively, a low molecular weight product having a viscosity average molecular weight of 1,000 to 15,000 obtained by thermally decomposing the above ethylene copolymer is also included in the present invention.

Further, in the present invention, a copolymer or a copolymer obtained by addition-modifying the unsaturated carboxylic acid, such as acrylic acid, maleic acid anhydride, etc. to low, medium, or high density polyethylene or an ethylene-α-olefin copolymer, or The random or addition-modified copolymer contains compounds 1 to 1 of groups I, II, III, IV-A and VI of the periodic table.
It also includes ionically crosslinked ethylene copolymers obtained by reacting trivalent metal compounds. Suitable examples of the metal compound include nitrates, acetates, oxides, hydroxides, methoxides, ethoxides, carbonates, and bicarbonates. In addition, metal ions include Na+, K+,
Ca++, Mg++, Zn++, Ba++, Fe++,
Fe+++, Co++, Ni++ and Al+++
It is. Among these, Na+, Mg++ and Zn++ are particularly preferred. These various metal compounds can be used in combination as necessary.

[0029] The method for producing an ethylene copolymer by high-pressure radical polymerization is such that the composition of the copolymer produced is 80 to 99.9 mol% of the above-mentioned ethylene and one or more glycidyl esters of α,β-unsaturated acids. 0.1 to 20.0 mol%, at least one ethylene and radically polymerizable vinyl monomer 0 to 19.9 mol%, based on the total weight of all those monomers. Based on 0.0001
Polymerization pressure 5 in the presence of ~1% by weight radical polymerization initiator
00 to 4,000 kg/cm2, preferably 1,00
0~3,500kg/cm2, reaction temperature 50~400
C, preferably 100 to 350 C, in the presence of a chain transfer agent and, if necessary, an auxiliary agent, in a tank or tubular reactor, the monomers are brought into contact and polymerized simultaneously or in stages. It's a method.

Examples of the radical polymerization initiator include conventional initiators such as peroxide, hydroperoxide, azo compound, amine oxide compound, and oxygen. In addition, as a chain transfer agent, hydrogen, propylene, butene-1
, C1 to C20 or higher saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons, such as methane, ethane, propane, butane, isobutane, n-hexane, n-
Heptane, cyclopuffins, chloroform and carbon tetrachloride, C1 to C20 or higher saturated aliphatic alcohols such as methanol, ethanol, propanol and isopropanol, C1 to C20 or higher saturated aliphatic carbonyl compounds such as carbon dioxide , acetone and methyl ethyl ketone and aromatic compounds such as toluene, diethylbenzene and xylene.

In the present invention, the acid group-containing olefin (co)polymer (C) refers to a binary copolymer of an olefin and an unsaturated carboxylic acid monomer or a derivative thereof, or an olefin produced by high-pressure radical polymerization. and an unsaturated carboxylic acid monomer or a derivative thereof, and another ethylene and a radically polymerizable vinyl monomer. Ethylene is particularly preferred as the olefin of the copolymer, and ethylene 80 ~99.9
%, unsaturated carboxylic acid monomer or its derivative 0.
A copolymer consisting of 1 to 20 mol % and 0 to 20 mol % of a vinyl monomer capable of radical polymerization with other ethylene is preferred.

Examples of the unsaturated carboxylic acid monomers or derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid monoester, fumaric acid monoester and their metal salts, maleic anhydride. Examples include acids, itaconic anhydride, and the like. Other vinyl monomers radically polymerizable with ethylene are as described above. The above acid group-containing olefin system (
Specific examples of co)polymers include ethylene/maleic acid copolymer, ethylene/maleic anhydride copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, and ethylene/ethyl acrylate/maleic acid copolymer. Acid copolymer, ethylene/ethyl acrylate/maleic anhydride copolymer, ethylene/ethyl acrylate/acrylic acid copolymer, ethylene/ethyl acrylate/methacrylic acid copolymer, ethylene/butyl acrylate/maleic anhydride Acid copolymer, ethylene/butyl acrylate/acrylic acid copolymer, ethylene/butyl acrylate/methacrylic acid copolymer, ethylene/vinyl acetate/maleic anhydride copolymer, ethylene/methyl methacrylate/maleic anhydride Examples include acid group-containing olefin (co)polymers such as copolymers. These acid group-containing olefin (co)polymers can also be used as a mixture.

[0033] The method for producing an acid group-containing olefin (co)polymer by high-pressure radical polymerization is such that the composition of the produced copolymer is 80 to 99.9 mol% of the above-mentioned ethylene, and 0.1% of the unsaturated carboxylic acid monomer or its derivative. ~20 mol%, vinyl monomers radically polymerizable with other ethylenes 0-19
．． 0.0001 to 1% by weight based on the total weight of all monomers of a monomer mixture formulated to be 9 mol%
Polymerization pressure in the presence of a radical polymerization initiator of 500 to 4,
000kg/cm2, preferably 1,000-3.5
00 kg/cm2, reaction temperature of 50 to 400°C, preferably 100 to 350°C, the monomers are simultaneously reacted in a tank or tube reactor in the presence of a chain transfer agent and optionally an auxiliary agent. Alternatively, it is a method of contacting and polymerizing in stages. The radical polymerization initiator and chain transfer agent are the same as those used in producing the ethylene copolymer.

Another example of the acid group-containing olefin (co)polymer of the present invention is a modified product obtained by adding the above-mentioned unsaturated carboxylic acid monomer or its derivative to a conventional olefin homopolymer or copolymer. It is. The above olefin polymers include homopolymers such as low density, medium density, and high density polyethylene; polypropylene; polybutene-1; poly-4-methylpentene-1; ethylene-propylene copolymers; ethylene-butyne-1 Copolymer; ethylene-hexene-1 copolymer; ethylene-4-methylpentene-1
Copolymers; copolymers with other α-olefins containing ethylene as a main component, such as ethylene-octene-1 copolymers;
Copolymers of propylene with other α-olefins such as propylene-ethylene block copolymers, ethylene-vinyl acetate copolymers, methyl, ethyl, propyl, isopropyl acrylic acid or methacrylate of ethylene, Copolymers with esters such as butyl and 2-ethylhexyl, ethylene-propylene copolymer rubber, ethylene-propylene-diene-copolymer rubber, liquid polybutadiene, ethylene-vinyl acetate-vinyl chloride copolymers, and mixtures thereof. , or mixtures of these with different types of synthetic resins or rubbers are also included in the present invention. Alternatively, a low molecular weight product having a viscosity average molecular weight of 1,000 to 15,000 obtained by thermally decomposing the above-mentioned olefin-based (co)polymer is also included in the present invention.

The amounts of (B) epoxy group-containing ethylene (co)polymer and (C) acid group-containing olefin (co)polymer each vary depending on the type and combination of engineering plastics added. The total amount used is (A)
100 parts by weight of engineering plastic, or 5-95% of at least one of (A) 95-5% by weight of engineering plastic and (D) olefin copolymer
If the amount is less than 1 part by weight per 100 parts by weight of the resin composition, the effect of improving impact resistance will be insufficient, which is not preferable. Moreover, if the total amount used exceeds 100 parts by weight, a sufficient effect of improving impact resistance can be obtained, but heat resistance decreases, which is not preferable. (B) epoxy group-containing ethylene (co)polymer, (C) for engineering plastics
) The acid group-containing olefin (co)polymer may be added at the same time as (B) the epoxy group-containing ethylene copolymer and (
C) The acid group-containing olefin (co)polymer may be kneaded first and then partially reacted.

In addition, the fluidity (molding processability) of the resin is improved without reducing molding stability and impact resistance, and
In particular, in order to improve low-temperature impact resistance, it is more preferable to use a specific epoxy group-containing ethylene copolymer (B). This effect reduces the glycidyl ester monomer units of (b) α,β-unsaturated acids having reactive sites to the minimum required amount, and (c) lowers the glass transition temperature of vinyl monomers that can be radically copolymerized with ethylene. (c) α,β- such as esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, etc., capable of forming copolymers;
This was made possible through copolymerization using an alkyl ester monomer of an unsaturated acid.

(D) Olefin type (co) in the present invention
The polymer is equivalent to the olefin-based (co)polymer used in the production of the acid group-containing olefin-based (co)polymer (C). Two or more of these (co)polymers may be used in combination. (D) The blending amount of the olefin-based (co)polymer is (A) Engineering plastic resin 9
5 to 5% by weight and (D) olefin (co)polymer 5 to 9
100 parts by weight of a resin composition consisting of 5% by weight, 1 to 100 parts by weight of (B) epoxy group-containing ethylene copolymer, (
C) Acid group-containing olefin (co)polymer The amount is such that it satisfies 1 to 100 parts by weight, and if the amount is less than 5% by weight, the effect of improving impact resistance etc. will not be exhibited, and 95% by weight If it exceeds this, there is a risk that heat resistance etc. will deteriorate. Preferred specific examples include (C) acid group-containing olefin (co-)
By using a maleic anhydride-modified polymer of polypropylene as the polymer, we have created a polypropylene-containing thermoplastic resin composition that has excellent heat resistance, dimensional stability, moldability, impact resistance, and oil resistance, and is also lightweight and inexpensive. Here are some of the things we can offer.

The essence of the present invention is to use (B) an epoxy group-containing ethylene copolymer and (C) an acid group-containing olefin (co)polymer, each of which is a good reactive modifier and a good reactive compatibilizer for engineering plastics. The effect of using copolymerization together is that these copolymers not only react with engineering plastics, but also that the copolymers react with each other (crosslinking), making them even more polymeric, preventing a decrease in heat resistance, and compatibilization. When used as an agent, finer dispersion is possible in the alloying of engineering plastics that have good compatibility with (B) and (C), making it possible to improve impact resistance, mechanical properties, etc. with a small amount. It is in.

When (B+C+D) is used as a modifier, if the purpose is to maintain the characteristics of aromatic polyester resin while improving the notched impact strength, which is a drawback of aromatic polyester resin, 50 to 98% by weight of aromatic polyester resin, Preferably 6
0% to 95% by weight is required. The reason is that if the aromatic polyester resin is less than 50% by weight, the rigidity and dimensional stability, which are characteristics of the aromatic polyester resin, will be impaired.

[0040] If the purpose is to improve chemical resistance and moldability while maintaining the characteristics of polycarbonate, 50 to 90% by weight of polycarbonate, preferably 60 to 95% by weight.
is necessary. If the polycarbonate content is less than 50% by weight, the impact resistance, which is a characteristic of polycarbonate, will be impaired.
If it exceeds 98% by weight, the effect of improving chemical resistance and moldability, which is one of the objectives of the present invention, is not achieved.

If the purpose is to maintain the characteristics of polyphenylene ether while improving its moldability and chemical resistance, it is necessary to use polyphenylene ether in an amount of 50 to 98% by weight, preferably 60 to 95% by weight. If the polyphenylene ether is less than 50% by weight, the heat resistance and dimensional stability of the polyphenylene ether will be impaired, and if it exceeds 98% by weight, the effect of improving moldability and chemical resistance, which is one of the objectives of the present invention, will not be achieved.

If the purpose is to improve water absorption and dimensional stability while maintaining the characteristics of polyamide resin, the polyamide resin should be contained in an amount of 50 to 98% by weight, preferably 60 to 95% by weight. If the content of the polyamide resin is less than 50% by weight, the characteristics of the polyamide resin will be impaired, and if it exceeds 98% by weight, the effect of improving water absorption and dimensional stability, which is one of the objectives of the present invention, cannot be expected.

[0043] If the purpose is to improve the chemical resistance of ABS resin while maintaining its characteristics, the ABS resin should be contained in an amount of 50 to 98% by weight, preferably 60 to 95% by weight. AB
If the S-based resin is less than 50% by weight, the characteristics of the ABS-based resin will be impaired, and if it exceeds 98% by weight, no improvement in chemical resistance can be expected.

[0044] If the purpose is to improve the molding shrinkage rate while maintaining the characteristics of the polyacetal resin, the polyacetal resin should be contained in an amount of 50 to 98% by weight, preferably 60 to 95% by weight. If the polyacetal resin content is less than 50% by weight, the characteristics of the polyacetal resin will be impaired, and if it exceeds 98% by weight, no improvement in molding shrinkage can be expected.

[0045] If the purpose is to improve the brittleness while maintaining the characteristics of polyphenylene sulfide resin, 50 to 98% by weight, preferably 60 to 95% by weight of polyacetal resin is required. Polyphenylene sulfide resin is 50
If it is less than 98% by weight, the characteristics of the polyphenylene sulfide resin will be impaired, and if it exceeds 98% by weight, no improvement in brittleness can be expected.

[0046] If the purpose is to improve the impact resistance while maintaining the characteristics of the polyarylate resin, the polyarylate resin needs to be contained in an amount of 50 to 98% by weight, preferably 60 to 98% by weight. If the content of the polyarylate resin is less than 50% by weight, the characteristics of the polyarylate resin will be impaired, and if it exceeds 98% by weight, no improvement in impact resistance can be expected.

In addition, when (B+C+D) is used as a compatibilizer, the blending ratio and the amount used are changed under the condition that the total amount used is less than 50% by weight, and furthermore, the graft modified product of (B) By adding a compatibilizing agent, it is possible to provide a thermoplastic resin composition that can exhibit the advantages of different types of incompatible engineering plastics without causing phase separation, and that has almost no deterioration in physical properties due to the addition of a compatibilizing agent. can.

[0048] 1 to 150 parts by weight of the inorganic filler (E) can be blended with 100 parts by weight of the resin composition of the present invention. Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, acicular, spherical or hollow, and fibrous, and specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, Powder-like fillers such as alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, etc.: mica, glass plate, sericite, pyrolite, aluminum Metal foil such as flakes,
Flat or scaly fillers such as graphite; hollow fillers such as shirasu balloons, metal balloons, glass balloons, and pumice; glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, asbestos, Examples include mineral fibers such as wollastonite.

If the amount of filler added exceeds 150 parts by weight, the mechanical strength such as impact strength of the molded article will decrease, which is not preferable. Moreover, if it is less than 1 part by weight, the modification effect cannot be exhibited. In addition, the surface of the inorganic filler is treated with stearic acid, oleic acid, palmitic acid or their metal salts, paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate, etc. It is preferable to apply

Further, in the present invention, flame retardation can be easily achieved by blending 5 to 150 parts by weight of a flame retardant to 100 parts by weight of the thermoplastic resin composition. As the flame retardant, tetrabromobisphenol (TBA
), hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), tetrabromobutane (TBB), hexabromocyclodecane (HBCD)
) and chlorinated flame retardants such as chlorinated paraffins, chlorinated polyphenyl, chlorinated polyethylene, chlorinated diphenyl, perchloropentacyclodecane, and chlorinated naphthalene; common halogens such as halogenated diphenyl sulfides. Flame retardants; halogenated polystyrene or its derivatives such as brominated polystyrene and brominated poly-α-methylstyrene, halogenated polycarbonates such as brominated polycarbonate, halogenated polyalkylene tetrabromo terephthalate, brominated terephthalic acid polyester, etc. halogenated epoxy compounds such as polyester, halogenated bisphenol-based epoxy resins,
Examples include flame retardants made of high molecular weight halogen-containing polymers such as halogenated polyphenylene oxide compounds such as poly(dibromophenylene oxide) and cyanuric acid ester compounds of halogenated bisphenols.

Among these, oligomer and polymer type flame retardants made of aromatic halogen compounds are particularly preferred. In addition, phosphorus-based flame retardants include tricresyl phosphate,
Phosphate esters or halogenated phosphate esters such as tri(β-chloroethyl) phosphate, tri(dibromopropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, phosphonic acid compounds, phosphinic acid derivatives, etc. Can be mentioned. Other flame retardants include guanidine compounds such as guanidine nitride. The organic flame retardants may be used alone or in combination of two or more. The amount of the organic flame retardant is 5 parts by weight per 100 parts by weight of the thermoplastic resin composition.
~50 parts by weight, preferably 7 to 40 parts by weight. If the amount is less than 5 parts by weight, the flame retardant effect will be poor, and if it is added in an amount exceeding 50 parts by weight, the flame retardant effect will not be improved any further, which is not preferable as it will increase the cost. When these organic flame retardants, especially halogenated flame retardants, are used in combination with a flame retardant aid, a synergistic effect can be exerted.

[0052] The flame retardant aids include antimony trioxide,
Typical examples include antimony halides such as antimony pentoxide and antimony trichloride, and antimony compounds such as antimony trisulfide, antimony pentasulfide, sodium antimonate, antimony tartrate, and antimony metal.

Further, as inorganic flame retardants, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide,
Basic magnesium carbide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, tin oxide hydrate, hydrates of inorganic metal compounds such as borax, zinc borate, zinc metaborate, barium metaborate, carbonic acid Examples include zinc, magnesium-calcium carbonate, calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, red phosphorus, and the like. These may be used alone or in combination. Among these, hydrates of at least one metal compound selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, and hydrotalcite, especially aluminum hydroxide, Magnesium hydroxide has a good flame retardant effect and is economically advantageous.

The particle size of these inorganic flame retardants varies depending on the type, but for the aluminum hydroxide, magnesium hydroxide, etc., the average particle size is 20 μm or less,
The thickness is preferably 10 μm or less. The inorganic flame retardant is used in an amount of 30 to 150 parts by weight, preferably 40 to 120 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. If the amount is less than 30 parts by weight,
Since it is difficult to achieve sufficient flame retardancy using an inorganic flame retardant alone, it is necessary to use an organic flame retardant in combination. On the other hand, when the amount exceeds 150 parts by weight, it causes deterioration of mechanical strength such as a decrease in impact strength. Further, in the present invention, by using the inorganic filler and a flame retardant together, the amount of flame retardant to be blended can be reduced, and other properties can be imparted. The thermoplastic composition of the present invention has a temperature of 150 to 3
It is produced by melt mixing at 50°C, preferably in the range of 180 to 320°C. If the temperature is lower than 150° C., the melting may be incomplete or the melt viscosity may be high, resulting in insufficient mixing and delamination, which is undesirable. Moreover, if the temperature exceeds 350°C, the resin may decompose or gel, which is not preferable. The melt-mixing method can be carried out using a commonly used kneading machine such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll.

The present invention further includes additives such as other thermoplastic resins, antioxidants, ultraviolet inhibitors, lubricants, dispersants, blowing agents, crosslinking agents, colorants, etc., without departing from the gist of the present invention. It is okay to add.

The rubber-like elastic body (F) used in the present invention preferably includes diene and non-diene rubbers having a glass transition temperature of -20°C or lower, specifically α,β-unsaturated nitrile. - It is a conjugated diene copolymer rubber-like elastic body. Examples of the α,β-unsaturated nitrile include methacrylonitrile, ethacrylonitrile, acrylonitrile, and the like, with acrylonitrile being particularly preferred. Also, conjugated dienes include isoprene and chloroprene:
Examples include 1,3-butadiene:2-methyl-1,3-butadiene:2,3-dimethyl-1,3-butadiene, and 1,3-butadiene:isoprene is particularly preferred. Further, the copolymer rubber may have at least one functional group selected from the group of hydroxyl group, epoxy group, carboxyl group, and amino group. Further, a copolymer rubber in which the degree of hydrogenation of the conjugated diene unit portion in the copolymer rubber is 70 mol% or more is particularly preferred.

The acrylic rubber-like elastic material is a rubber-like polymer formed by polymerizing a (meth)acrylic acid ester or a monomer mainly composed of it, and methyl acrylate:
Ethyl acrylate: Butyl acrylate: Propyl acrylate: 2-ethylhexyl acrylate: (Meth)acrylic acid ester such as n-octyl methacrylate, preferably 4
It is produced by grafting one or more vinyl monomers onto a polymer containing 0% by weight or more. These (meth)acrylic acid ester polymers may contain a diene rubber core such as polybutadiene, and may also contain polyols such as butylene di(meth)acrylate: trimethylolpropane trimethacrylate, and esters of (meth)acrylic acid. Types: Divinylbenzene: Vinyl compounds such as vinyl (meth)acrylate, Allyl (meth)acrylate: Diallyl maleate: Diallyl fumarate: Triallyl cyanurate: One or more crosslinking monomers such as glycidyl methacrylate is 0.05-3% by weight
It may be copolymerized. Vinyl monomers grafted onto these (meth)acrylic acid ester polymers include methyl (meth)acrylate: ethyl (meth)acrylate: butyl (meth)acrylate: styrene: α-methylstyrene: (meth) ) acrylonitrile, etc.

Conjugated diene polymers and conjugated diene-aromatic vinyl compound polymers are polymers consisting of one or more conjugated dienes or copolymers consisting of a conjugated diene and an aromatic vinyl compound. As for 1,
3-Butadiene: Isoprene (2,3-dimethyl-1,
(3-butadiene): Examples include 1,3-pentadiene, and 1,3-butadiene is preferably used.

Examples of uses of the thermoplastic resin composition of the present invention include the following, but the invention is not limited to these unless departing from the gist of the present invention. Electrical related applications include connectors, plugs, sockets, coil bobbins, relays, switches, IC (integrated circuit) carriers, fuse cases, motor parts, end caps, brush holders, commutators, process control equipment, stereo parts, TV parts, Examples include flypack transformers, tuners, CRT sockets, VTR covers and levers, and fluorescent lamp caps.

Automobile-related applications include switches such as ignitions, blinkers, heaters, tail light sockets, fuse cases, voltage regulator parts, ignition coil cases, bobbins, distributor caps/housings, rotors, carburetors, and safety belts. Parts (spools, etc.), gears, exhaust valves, gear cases, outer handles,
Examples include connectors, bumpers, automobile exterior products, and motorcycle exterior products.

Applications in various industries include clock parts, clock base plates, watch base plates, camera parts (aperture rings), office equipment, key tops, copying machine fusing covers, cooling fans, agricultural equipment, and powder dusting. Examples of machine housings and leisure goods include ski pecks and fishing gear spools. Applications related to building piping include gas burner parts, water meter chambers, pumps (impellers and housings), flow control equipment, pressure vessels, and chemical waste treatment equipment.

[0062]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Examples 1 to 8 (A) was an aromatic polyester with an intrinsic viscosity of 3.5.
dl/g of polybutylene terephthalate (indicated as PBT in the table) and ethylene-glycidyl methacrylate copolymer (B) as the epoxy group-containing ethylene copolymer (B).
(abbreviated as E-GMA (1)) "Product name: Nisseki Rexpar RA4100" [manufactured by Nippon Petrochemicals Co., Ltd.], as the acid group-containing olefin (co)polymer of (C), maleic anhydride-modified polypropylene ( PP-gr.MAH) "Product name: Nisseki N Polymer P4201" (manufactured by Nippon Petrochemical Co., Ltd.) were melt-mixed in the proportions shown in Table 1. In the melt-mixing method, the materials were supplied to a co-directional twin-screw extruder (manufactured by Plastic Engineering Research Institute Co., Ltd.) with a screw diameter of 30 mm and set at a cylinder temperature of 250° C., and melt-mixed within the cylinder. The mixed resin was granulated, dried at 150° C. for 3 hours, and then injection molded into test pieces.

[0063] The size of the test piece and the test method are as follows. Izod impact value (with notch) (JIS K7110
): 13mm x 65mm x 6mm load deflection temperature (JI
S K7207): 13m
m x 130mm x 6mm bending strength (JIS K720
3) :10mm
x 130 mm x 4 mm Layer peeling state: The layer peeling state was determined by observing the fractured surface of the molded product and ranking it as follows. ◎: No peeling at all ○: Slight peeling ×: Peeling

Examples 9 to 16 As (D), a propylene homopolymer with an MFR of 4.0 was used.
Product name: Nisseki Polypropylene J130G" [manufactured by Nippon Petrochemicals Co., Ltd.] was further added, and polybutylene terephthalate (indicated as PBT in the table) with an intrinsic viscosity of 3.5 dl/g as aromatic polyester (A) and ( As the epoxy group-containing ethylene copolymer of B), ethylene-glycidyl methacrylate copolymer (abbreviated as E-GMA (1)) "
Product name: Nisseki Rexpar RA4100'' [manufactured by Nippon Petrochemicals Co., Ltd.] Maleic anhydride-modified polypropylene (PP-
gr. (abbreviated as MAH) “Product name: Nisseki N Polymer P42
01'' [manufactured by Nippon Petrochemicals Co., Ltd.] was melt-mixed in the proportions shown in Table 2.

Examples 17 to 24 In Examples 1 to 8 above, maleic anhydride-modified polypropylene (P
Maleic anhydride-modified ethylene-propylene copolymer (EPR-gr.MAH) was used instead of
Table 3 shows an example using "Product name: MEP4105" (manufactured by JSR Corporation). "It wasn't damaged.

Examples 25 to 34 Examples of inorganic fillers include examples in which glass fibers having an average fiber length of 5.0 mm and a diameter of 10 μm are blended into the compositions of Examples 9 to 16 (Examples 25 to 32), and polypropylene. Examples using 100 parts by weight and 100 parts by weight of PBT (Examples 33 to 34)
) are shown in Table 4. *Amount of polypropylene: (PBT+EGMA (1)
+PP-gr. MAH) Parts by weight per 100 parts by weight*
*Blend amount of glass fiber: [PBT+EGMA(
1) +PP-gr. MAH) + polypropylene)] 10
Parts by weight relative to 0 parts by weight

[0067]

[Effects of the Invention] As described above, the present invention can be applied to aromatic polyester resins, polycarbonate resins, polyamide resins, polyphenylene resins, etc. while maintaining the excellent properties such as polyolefins' moldability and chemical resistance, and their low cost. Mechanical properties, heat resistance, rigidity, and impact resistance of engineering plastics (A) such as ether resin alone or a mixture of it and styrene polymer, polyacetal resin, polyarylene sulfide resin, polyarylate resin, ABS resin, etc. , thermoplastic resin compositions that minimize deterioration in properties such as paintability, and thermoplastic resin compositions containing olefin (co)polymers such as polypropylene, which are useful for reducing the weight of automobiles. Yes, a thermoplastic resin composition in which engineering plastic (A) is blended with a specific amount of (B) an epoxy group-containing ethylene copolymer and (C) an acid group-containing olefin (co)polymer, or further (D) This objective can be achieved by using a thermoplastic resin composition blended with an olefin (co)polymer such as polypropylene. The thermoplastic resin composition of the present invention includes:
connectors, plugs, sockets, coil bobbins, relays,
Electronic and electrical parts such as switches, IC (integrated circuit) carriers, outer handles, connectors, bumpers,
Automotive related parts such as automobile exterior parts, watch parts, camera parts, office equipment parts, key tops, duster housings,
Various industrial applications such as leisure goods, gas burner parts,
Widely used in construction piping-related applications such as water meter chambers, pumps (impellers and housings), flow rate control equipment, pressure vessels, and chemical waste treatment equipment.

Claims (3)

[Claims] Claim 1: (A) Aromatic polyester resin, polycarbonate resin, polyamide resin, polyphenylene ether resin alone or a mixture of these and a styrene polymer, polyacetal resin, polyarylene sulfide resin, polyarylate resin, ABS resin 100 parts by weight of at least one resin selected from the group consisting of (B
) Epoxy group-containing ethylene copolymer consisting of the following (a) to (c): (a) 80 to 99.9 mol% of olefin monomer units:
(b) 0.1 to 20.0 mol% of glycidyl ester monomer units of α,β-unsaturated acid: (c) 0 to 19.9 mol% of vinyl monomer units radically copolymerizable with ethylene: 1 to 100% by weight Department and (C)
Acid group-containing olefin (co)polymer
A thermoplastic resin composition comprising 1 to 100 parts by weight. (A) Aromatic polyester resin, polycarbonate resin, polyamide resin, polyphenylene ether resin alone or a mixture of these and a styrene polymer, polyacetal resin, polyarylene sulfide resin, polyarylate resin, ABS resin 95-5% by weight of at least one resin selected from the group consisting of (D
) At least one olefin (co)polymer 5 to 95
Resin composition consisting of wt%

100 parts by weight, and (B) an epoxy group-containing ethylene copolymer consisting of the following (a) to (c): (a) 80 to 99.9 mol% of olefin monomer units:
(b) 0.1 to 20.0 mol% of glycidyl ester monomer units of α,β-unsaturated acid: (c) 0 to 19.9 mol% of vinyl monomer units radically copolymerizable with ethylene: 1 to 100% by weight Department and (C)
Acid group-containing olefin (co)polymer
A thermoplastic resin composition characterized in that it contains 1 to 100 parts by weight. 3. (E) inorganic filler and/or (F) rubber-like elastic body 1 per 100 parts by weight of the thermoplastic resin composition according to claim 1 or 2.
A thermoplastic resin composition characterized in that it contains ~200 parts by weight.