JPH0718155A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Polyphenylene ether resin (I) 5-9
5% by weight and ABS resin (II) 95 to 5% by weight
And 100 parts by weight of (I) + (II), 1 to 100 parts by weight of the graft copolymer (III) having a specific multiphase structure. [Effect] This thermoplastic resin composition is a resin composition excellent in mechanical properties, heat resistance, molding processability and surface appearance, making the most of the advantages of the polyphenylene ether resin (I) and the ABS resin (II). It is a thing. Therefore, it can be widely used for automobile parts, electric / electronic parts, industrial parts and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, water resistance, etc., and is widely used in automobile parts, electric and electronic machine parts, industrial parts and the like. It is used effectively.

[0002]

2. Description of the Related Art Polyphenylene ether resin (I) and ABS resin (II) are used in many fields because of their excellent mechanical properties and heat resistance. However, although the polyphenylene ether resin (I) has relatively high heat resistance and excellent characteristics such as impact resistance, improvement in molding processability is desired. on the other hand,
Although the ABS resin (II) has excellent moldability, further improvement in heat resistance and mechanical properties is required.

Therefore, by blending the polyphenylene ether resin (I) with the ABS resin (II), the ABS resin (II) is maintained while maintaining the advantages inherent in the polyphenylene ether resin (I). It is considered that an excellent resin composition imparting the molding processability (fluidity) of 1) can be obtained, and the compatibilizing agent has been developed. For example, in a blend of a polyphenylene ether resin (I) and an ABS resin (II), as a compatibilizing agent for improving the compatibility of both resins, JP-A-60-36551 discloses a graft copolymerization of EPDM and AS. Japanese Patent Application Laid-Open No. 60-86748 discloses a graft copolymer of AS and PS. However, in each of the blended systems, the chemical structures of the blended systems were different from each other, so that the compatibility was poor, and it was insufficient to take advantage of each of the advantages.

[0004]

Therefore, the object of the present invention is to provide polyphenylene ether resins (I) and AB.
To provide a thermoplastic resin composition that effectively prevents delamination that occurs during molding of a composition comprising an S-based resin (II) and is excellent in heat resistance, mechanical properties, impact resistance and molding processability. is there.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that when a polyphenylene ether resin (I) and an ABS resin (II) are blended, By blending the graft copolymer (III) as a compatibilizer, it has been possible to complete an excellent thermoplastic resin composition having both the moldability and processability of an ABS resin while maintaining heat resistance and mechanical properties.

That is, the present invention relates to a polyphenylene ether resin (I) of 5 to 95% by weight and an ABS resin (I
I) 95 to 5% by weight, and (I) + (II) 100% by weight, based on 5 to 95% by weight of epoxy group-containing olefin polymer segment and 95 to 5% by weight of vinyl polymer segment. , One polymer segment having a particle size of 0.00 in the continuous phase formed by the other polymer segment.
The present invention relates to a thermoplastic resin composition comprising 1 to 100 parts by weight of a graft copolymer (III) having a multiphase structure forming a dispersed phase of 1 to 10 μm. The polyphenylene ether (I) used in the present invention is represented by the general formula (1)

[0007]

[Chemical 1]

(Wherein R _{1 to} R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group, or a substituted hydrocarbon group, and one of them is always a hydrogen atom). It is a polymer obtained by oxidatively polymerizing the phenol compound described above using a coupling catalyst with oxygen or an oxygen-containing gas.

Specific examples of R _{1 to} R ₅ in the above general formula (1) include hydrogen, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl and hydroxy. Methyl, carboxylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and the like can be mentioned.

Specific examples of the above general formula (1) 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 and the like.
Two or more kinds of these phenol compounds may be used.

Further, it may be a copolymer of a phenol compound other than the above general formula, for example, a bisphenol A; tetrabromobisphenol A; resorcin; a dihydric phenol such as hydroquinone and the like, and a phenol compound of the above general formula.

The polyphenylene ether resin (I) used in the present invention may be a mixture with a styrene resin, and examples of the styrene resin include polystyrene; poly-α-methylstyrene; poly-p-methylstyrene and the like. High-impact polystyrene modified by various rubbers such as homopolymers and butadiene rubber, styrene-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer; styrene-maleic anhydride copolymer; Styrene-acrylonitrile copolymer;
Examples thereof include styrene-acrylonitrile-butadiene copolymer; styrene-methyl methacrylate copolymer and the like. These styrenic resins are mixed in the range of 0 to 95% by weight with respect to the polyphenylene ether resin.

The ABS resin (II) used in the present invention is selected from the group consisting of vinyl cyanide compounds, aromatic vinyl compounds and unsaturated carboxylic acid alkyl ester compounds in the presence of butadiene rubber. Two
It is a graft copolymer (a) obtained by polymerizing one or more compounds. If necessary, it also contains a copolymer (b) obtained by polymerizing two or more compounds selected from the group consisting of vinyl cyanide compounds, aromatic vinyl compounds and unsaturated carboxylic acid alkyl ester compounds. You can Preferably, the copolymer (a) is 10 to 100.
It is a resin composed of 90% by weight and 90% by weight of the copolymer (b). If the amount of the copolymer (a) is less than 10% by weight, sufficient impact resistance cannot be obtained.

The composition ratio of the conjugated diene rubber to the above compound in the graft copolymer (a) is not particularly limited, but 5 to 70% by weight of the conjugated diene rubber and the above compound 9 are used.
A composition ratio of 5 to 30% by weight is preferable. The composition ratio of the above compounds is not particularly limited, but is 0 to 30% by weight of vinyl cyanide compound, 30 to 80% by weight of aromatic vinyl compound, and 0 to 70 of unsaturated carboxylic acid alkyl ester compound.
It is preferably in the weight%. The particle size of the conjugated diene rubber is not particularly limited, but is preferably 0.05 to 5 μm. The composition ratio of the above compound of the copolymer (b) is 0 to 30% by weight of vinyl cyanide compound, 50 to 90% by weight of aromatic vinyl compound, and 0 to 40% by weight of unsaturated carboxylic acid alkyl ester compound. Is preferred.
The intrinsic viscosity [30 ° C., dimethylformamide (DMF)] of the copolymer (b) is not particularly limited, but it is 0.25 to 0.25.
1.50 is preferable.

Examples of the conjugated diene rubber include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and the like. One kind or two or more kinds can be used. There is no limitation on the gel content of the conjugated diene rubber.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, etc., as the aromatic vinyl compound, styrene, α-methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, etc., and as the unsaturated carboxylic acid alkyl ester compound, Methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and the like can be mentioned, and one kind or two or more kinds can be used. Examples of the method for producing the ABS resin (I) include emulsion polymerization method, suspension polymerization method, solution polymerization method, bulk polymerization method and emulsion-suspension polymerization method.

In the present invention, the mixing ratio of the polyphenylene ether resin (I) and the ABS resin (II) is 5 to 95% by weight of the polyphenylene ether resin (I),
That is, the ABS resin (II) is 95 to 5% by weight.
Among them, from the viewpoint of heat resistance, the polyphenylene ether resin is 50 to 95% by weight, that is, the ABS resin (I
I) is preferably 50 to 5% by weight, and from the viewpoint of moldability, the polyphenylene ether resin is preferably 5 to 50% by weight, that is, the ABS resin is preferably 95 to 50% by weight. If the polyphenylene ether resin (I) is less than 5% by weight, the processability of forming is poor,
If the ABS resin (II) is less than 5% by weight, the heat resistance is low and it is not preferable.

The epoxy group-containing olefin polymer in the graft copolymer (III) used in the present invention is
One is a binary copolymer of an olefin and an unsaturated glycidyl group-containing monomer by high pressure radical polymerization, or a ternary or multi-element of an olefin and an unsaturated glycidyl group-containing monomer and another unsaturated monomer. Ethylene is particularly preferable as the olefin of the above copolymer, and ethylene 60 to 99.5% by weight, glycidyl group-containing monomer 0.5 to 40% by weight, other unsaturated monomer A copolymer consisting of 0 to 39.5% by weight is preferred.

Examples of the unsaturated glycidyl group-containing monomer include glycidyl acrylate; glycidyl methacrylate.
Itaconic acid monoglycidyl ester; butene tricarboxylic acid monoglycidyl ester; butene tricarboxylic acid diglycidyl ester; butene tricarboxylic acid triglycidyl ester; and α-chloroallyl, maleic acid,
Glycidyl ester acids such as crotonic acid and fumaric acid or vinyl glycidyl ethers; allyl glycidyl ethers; glycidyl oxyethyl vinyl ethers; glycidyl ethers such as styrene-p-glycidyl ethers,
Examples of p-glycidyl styrene include glycidyl methacrylate and acrylic glycidyl ether.

The other unsaturated monomer is at least one monomer selected from olefins, vinyl esters, α, β-ethylenically unsaturated carboxylic acids or their derivatives, and specifically, Is propylene; butene-1; hexene-1; decene-1; octene-1; olefins such as styrene; vinyl acetate; vinyl propyleneate; vinyl esters such as vinyl benzoate; acrylic acid; methacrylic acid; acrylic acid or Esters of methacrylic acid such as methyl-, ethyl-, propyl-, butyl-, 2-ethylhexyl-, cyclohexyl-, dodecyl-, octadecyl-; maleic acid; maleic anhydride; itaconic acid; fumaric acid; maleic acid Mono- and di-esters; vinyl chloride; vinyl methyl ether, vinyl ethyl ether, and other vinyl chloride Examples thereof include ethers and acrylic acid amide compounds, and acrylic acid esters are particularly preferable.

Specific examples of the above-mentioned epoxy group-containing olefin copolymer are ethylene-glycidyl methacrylate copolymer; ethylene-vinyl acetate-glycidyl methacrylate copolymer; 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 them, ethylene-glycidyl methacrylate copolymer is preferable. These epoxy group-containing olefin copolymers can also be used as a mixture.

The production method of the epoxy group-containing olefin copolymer by the high pressure radical polymerization method is the above-mentioned ethylene 60 to 9
9.5 wt%, 0.5 to 40 wt% of one or more unsaturated glycidyl group-containing monomers, and 0 to 39.5 wt% of at least one other ethylenically unsaturated monomer The mixture is added with 0.0001 based on the total weight of all those monomers.
Polymerization pressure of 500 to 4000 kg / cm ² , preferably 1000 to 35 in the presence of ˜1% by weight of radical polymerization initiator.
00 kg / cm ² , reaction temperature 50 to 400 ° C., preferably 1
It is a method of contacting or polymerizing the monomers simultaneously or stepwise in a tank or tube reactor in the presence of a chain transfer agent and, if necessary, an auxiliary under the condition of 00 to 350 ° C.

As the radical polymerization initiator, there may be mentioned usual initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds and oxygen. Further, as the chain transfer agent, hydrogen, propylene, butene-1, C ₁
To C ₂₀ or more saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons such as methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, C ₁ To C ₂₀ or more saturated aliphatic alcohols such as methanol, ethanol, propanol and isopropanol, C _{1 to} C ₂₀ or more saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone and aromatic compounds such as Examples thereof include compounds such as toluene, diethylbenzene and xylene.

Another example of the epoxy group-containing olefin copolymer of the present invention is a modified product obtained by addition-reacting the above-mentioned unsaturated glycidyl group-containing monomer to a conventional olefin homopolymer or copolymer.

The above olefin copolymers include low density, medium density, high density polyethylene; polypropylene; polybutene-1; homopolymers such as poly-4-methylpentene-1; ethylene-propylene copolymers; ethylene- Butene-1 copolymer; ethylene-hexene-1 copolymer; ethylene-4-methylpentene-1 copolymer; ethylene-octene-1 copolymer and other α containing ethylene as a main component
-Copolymer with olefin, copolymer with other α-olefin whose main component is propylene such as propylene-ethylene block copolymer; ethylene-vinyl acetate copolymer; ethylene-acrylic acid copolymer; Ethylene-methacrylic acid copolymer; Copolymer of ethylene and acrylic acid or methacrylic acid ester of methyl-, ethyl-, propyl-, isopropyl-, butyl-, etc .; Ethylene-
Maleic acid copolymers; ethylene-propylene copolymer rubbers; ethylene-propylene-diene-copolymer rubbers; liquid polybutadiene; ethylene-vinyl acetate-vinyl chloride copolymers and mixtures thereof, or synthetic resins different therefrom. Alternatively, a mixture with rubber is also included in the present invention.

The vinyl polymer in the graft copolymer (III) used in the present invention is specifically styrene, nucleus-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene. Vinyl aromatic monomers such as α-substituted styrenes such as α-methylstyrene and α-ethylstyrene; alkyl esters of acrylic acid or methacrylic acid having 1 to 7 carbon atoms, for example, methyl of (meth) acrylic acid, (Meth) acrylic acid ester monomers such as ethyl-, propyl-, isopropyl-, butyl-; (meth) acrylonitrile monomers such as acrylonitrile or methacrylonitrile; vinyl ester, vinyl acetate, vinyl propionate, etc. Body: (meth) acrylic acid such as acrylamide and methacrylamide Mido monomer; maleic anhydride,
It is a (co) polymer obtained by polymerizing one or more vinyl monomers such as mono- and di-esters of maleic acid. Among these, vinyl aromatic monomers, (meth) acrylic acid ester monomers, (meth) acrylonitrile monomers and vinyl ester monomers are particularly preferably used.

In particular, vinyl aromatic monomer or (meth)
A vinyl-based (co) polymer containing 50% by weight or more of an acrylic acid ester monomer is preferable because of a good compatibilizing effect,
A vinyl-based copolymer having 60 to 90% by weight of vinyl aromatic monomer and 10 to 40% by weight of (meth) acrylonitrile monomer is most preferable.

The graft copolymer (III) referred to in the present invention is a vinyl-based polymer or a vinyl-based polymer which is a component different from that in the continuous phase formed by the epoxy group-containing olefin-based polymer or vinyl-based polymer segment. It means that the epoxy group-containing olefin polymer segment is spherically and uniformly dispersed.

The particle size of the dispersed polymer is 0.001.
The thickness is -10 μm, preferably 0.01-5 μm, and most preferably 0.1-1 μm. Dispersed resin particle size is 0.00
If it is less than 1 μm or exceeds 10 μm, polyphenylene ether resin (I) and ABS resin (II)
It is not preferable because the compatibility with and becomes insufficient and, for example, the appearance is deteriorated or the effect of improving impact resistance is insufficient. The number average degree of polymerization of the vinyl polymer in the graft copolymer (III) of the present invention is 5 to 10,000, preferably 10 to 10.
It is 5000.

When the number average degree of polymerization is less than 5, the impact resistance of the thermoplastic resin composition of the present invention can be improved, but the heat resistance is lowered, which is not preferable. Also,
When the number average degree of polymerization exceeds 1,000, the melt viscosity is high,
It is not preferable because the moldability is lowered and the surface gloss is lowered.

The graft copolymer (III) of the present invention comprises an epoxy group-containing olefin polymer in an amount of 5 to 95% by weight, preferably 20 to 90% by weight, and most preferably 50 to 80% by weight. . Therefore, the vinyl polymer is 95 to 5% by weight, preferably 80 to 10% by weight, and most preferably 50 to 20% by weight. When the epoxy group-containing olefin polymer is less than 5% by weight, the impact resistance improving effect is insufficient, which is not preferable. When the epoxy group-containing olefin copolymer exceeds 95% by weight, the impact resistance improving effect is sufficiently obtained, but the heat resistance is lowered, which is not preferable.

In the present invention, the graft copolymer (III)
Is from 1 to 100 relative to 100 parts by weight of resin (I) + (II)
Parts by weight, preferably 2 to 70 parts by weight, more preferably 5 to 50 parts by weight. When the amount of the graft copolymer (III) is less than 1 part by weight, the compatibility between the resin (I) and the resin (II) is not improved, delamination occurs, and sufficient impact strength cannot be obtained. Further, if it exceeds 100 parts by weight, mechanical properties and heat resistance are deteriorated, which is not preferable.

The grafting method for producing the graft copolymer (III) of the present invention may be any of well-known methods such as chain transfer method and ionizing radiation irradiation method, but the most preferable method is Is based on the method described below. This is because the grafting efficiency is high and secondary aggregation due to heat does not occur, so that the performance is more effectively expressed and the manufacturing method is simple.

The method for producing the thermoplastic resin composition of the present invention will be described in detail below. That is, 100 parts by weight of an epoxy group-containing olefin polymer is suspended in water, and 5 to 400 parts by weight of at least one vinyl monomer is added to a radical represented by the following general formula (2) or (3). 0.1-10 parts by weight of one or a mixture of two or more polymerizable organic peroxides per 100 parts by weight of the vinyl monomer;
A radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 0 hours is 0.01 with respect to a total of 100 parts by weight of a vinyl monomer and a radically polymerizable organic peroxide.
˜5 parts by weight is added and the solution is heated under conditions where decomposition of the radical polymerization initiator does not substantially occur, and the vinyl monomer, the radical polymerizable organic peroxide and the radical polymerization initiator are mixed with an epoxy group. Impregnation of the olefin-based polymer containing content, then raising the temperature of this aqueous suspension, copolymerizing the vinyl monomer and the radically polymerizable organic peroxide in the epoxy group-containing olefin-based polymer, and grafting A chemical precursor is obtained. This grafted precursor may be directly melt mixed with the polyphenylene ether resin or polycarbonate resin (I) and the ABS resin (II).

The grafting precursor is added at 100 to 300 ° C.
It is also possible to obtain the graft copolymer (III) of the present invention by kneading while melting. At this time, the graft copolymer (III) can also be obtained by separately mixing an epoxy group-containing olefin-based polymer or vinyl-based polymer with the grafting precursor, and kneading the mixture while melting. Most preferred is a graft copolymer obtained by kneading a grafting precursor.
(III). The radical polymerizable organic peroxide represented by the general formula (2) (Chemical Formula 2) is

[0036]

[Chemical 2]

(In the formula, R ₁ is a hydrogen atom or has 1 to 1 carbon atoms.
2 alkyl group, R ₂ is hydrogen atom or methyl group, R ₃
And R ₄ are each an alkyl group having 1 to 4 carbon atoms, R ₅
Represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2. ) Is a compound represented by. The radical polymerizable organic peroxide represented by the general formula (3) (Chemical Formula 3) is

[0038]

[Chemical 3]

(In the formula, R ₆ is a hydrogen atom or a carbon number of 1 to
4 alkyl group, R ₇ is hydrogen atom or methyl group, R ₈
And R ₉ are each an alkyl group having 1 to 4 carbon atoms, R ₁₀
Represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. n is 0, 1 or 2. ) Is a compound represented by.

Specific examples of the radical-polymerizable organic peroxide represented by the general formula (2) include t-butylperoxyacryloyloxyethyl carbonate; t-amylperoxyacryloyloxyethyl carbonate; t-hexylperoxy. Acryloyloxyethyl carbonate;
1,1,3,3-Tetramethylbutylperoxyacryloyloxyethyl carbonate; Cumylperoxyacryloyloxyethyl carbonate; p-Isopropylcumylperoxyacryloyloxyethyl carbonate;
t-butyl peroxymethacryloyloxyethyl carbonate; t-amyl peroxymethacryloyloxyethyl carbonate; t-hexyl peroxymethacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxymethacryloyloxyethyl carbonate; cumyl Peroxymethacryloyloxyethyl carbonate; p-isopropyl cumyl peroxymethacryloyloxyethyl carbonate; t-butyl peroxymethacryloyloxyethyl carbonate; t-amyl peroxyacryloyloxyethoxyethyl carbonate; t-hexyl peroxyacryloyloxyethoxyethyl carbonate 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylpe Oxyacryloyloxyethoxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate; t-butylperoxymethacryloyloxyethoxyethyl carbonate; t-amylperoxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxy Ethoxyethyl carbonate; 1,
1,3,3-Tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate; cumylperoxymethacryloyloxyethoxyethyl carbonate; p
-Isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropyl carbonate; t-amylperoxyacryloyloxyisopropyl carbonate;
t-hexyl peroxyacryloyloxy isopropyl carbonate; 1,1,3,3-tetramethylbutyl peroxyacryloyloxy isopropyl carbonate;
Cumyl peroxyacryloyloxy isopropyl carbonate; p-isopropyl Cumyl peroxyacryloyloxy isopropyl carbonate; t-butyl peroxymethacryloyloxy isopropyl carbonate; t-
Amyl peroxy methacryloyloxy isopropyl carbonate; t-hexyl peroxy methacryloyloxy isopropyl carbonate; 1,1,3,3-tetramethylbutyl peroxy methacryloyloxy isopropyl carbonate; cumyl peroxy methacryloyloxy isopropyl carbonate; p-isopropyl cumyl Peroxymethacryloyloxy isopropyl carbonate etc. can be illustrated.

Further, as the compound represented by the general formula (3), t-butylperoxyallyl carbonate; t
-Amyl peroxyallyl carbonate; t-hexyl peroxyallyl carbonate; 1,1,3,3-tetramethylbutyl peroxyallyl carbonate; p-menthane peroxyallyl carbonate; cumyl peroxyallyl carbonate; t-butyl peroxymethallyl carbonate; t -Amyl peroxy methallyl carbonate; t-hexyl peroxy methallyl carbonate;
1,1,3,3-tetramethylbutyl peroxymethallyl carbonate; p-menthane peroxymethallyl carbonate; cumyl peroxymethallyl carbonate; t
-Butylperoxyallyloxyethyl carbonate; t
-Amyl peroxyallyloxyethyl carbonate; t
-Hexyl peroxyallyloxyethyl carbonate;
t-Butylperoxymetallyloxyethyl carbonate; t-Amylperoxymetallyloxyethyl carbonate; t-Hexylperoxymetallyloxyethyl carbonate; t-Butylperoxyallyloxy isopropyl carbonate; t-Amylperoxyallyloxy isopropyl carbonate; Roxy isopropyl carbonate; t-butyl peroxymetalloyloxy isopropyl carbonate; t-amyl peroxy metalloyloxy isopropyl carbonate; t-
Hexyl peroxy metalryloxy isopropyl carbonate etc. can be illustrated. Among them, preferably t
-Butyl peroxyacryloyloxy ethyl carbonate; t-butyl peroxy methacryloyloxy ethyl carbonate; t-butyl peroxy allyl carbonate; t-butyl peroxy methallyl carbonate.

In the present invention, the above (I) + (II) + (I
An inorganic filler of less than 150 parts by weight can be added to 100 parts by weight of the resin component containing II). Examples of the inorganic filler include powdery, tabular, scaly, acicular, spherical or hollow and fibrous forms, and specifically include calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand. , Glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride,
Powder and granular filler such as aluminum nitride and carbon black; mica, glass plate, sericite, pyrophyllite,
Metal foil such as aluminum flakes, flat or scale-like filler such as graphite; hollow filler such as shirasu balloon, metal balloon, glass balloon, pumice stone; glass fiber, carbon fiber, graphite fiber, whiskers, metal fiber, Examples include silicone carbide fibers, mineral fibers such as asbestos and wollastonite, and the like. If the blending amount of the filler exceeds 150 parts by weight, the impact strength of the molded article will decrease, which is not preferable.

The surface of the inorganic filler is stearic acid, oleic acid, palmitic acid or metal salts thereof,
It is preferable to perform surface treatment using paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate and the like.

The thermoplastic resin composition of the present invention has a temperature of 15
It is produced by melting and mixing at 0 to 350 ° C, preferably 180 to 330 ° C. If the temperature is lower than 150 ° C., the melting is incomplete, the melt viscosity is high, the mixing becomes insufficient, and phase separation or layered peeling appears in the molded product, which is not preferable. On the other hand, if it exceeds 350 ° C., the resin to be mixed is decomposed or gelated, which is not preferable. As a method of melting and mixing, a kneading machine which is usually used, such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll can be used.

In the present invention, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen type and phosphorus type, organic fillers such as wood powder, and the like, within the scope of the present invention. Antioxidants, UV inhibitors,
Additives such as a lubricant, a dispersant, a coupling agent, a foaming agent, a cross-linking agent and a colorant, an elastomer, and other polyolefin resins may be added.

[0046]

The present invention will be described in more detail with reference to the following examples. Reference Example 1 (Production of Graft Copolymer (IIIA)) 2500 g of pure water was placed in a stainless steel autoclave having a volume of 5 l, and 2.5 g of polyvinyl alcohol was further dissolved as a suspending agent. In this, an ethylene-glycidyl methacrylate copolymer (content of glycidyl methacrylate 15% by weight) as an epoxy group-containing olefin-based polymer "Rex Pearl R
A-3150 "[trade name, manufactured by Nippon Petrochemical Co., Ltd.] 70
0 g was added, and the mixture was stirred and dispersed. Separately, 1.5 g of benzoyl peroxide “Nyper B” [trade name, manufactured by NOF CORPORATION] as a radical polymerization initiator, and 6 g of t-butylperoxymethacryloyloxyethyl carbonate as a radically polymerizable organic peroxide are used as a vinyl monomer. It was dissolved in 300 g of styrene as a body, and this solution was put into the autoclave and stirred. Then 6 autoclaves
The temperature was raised to 0 to 65 ° C., and the mixture was stirred for 2 hours to impregnate the epoxy group-containing ethylene copolymer with a vinyl monomer containing a radical polymerization initiator and a radically polymerizable organic peroxide. Then, the temperature was raised to 80 to 85 ° C., and the temperature was maintained for 7 hours to complete the polymerization, followed by washing with water and drying to obtain a grafted precursor (IIIa). The styrene polymer in the grafted precursor (IIIa) was extracted with ethyl acetate and the number average degree of polymerization was measured by GPC.
It was 0. Next, this grafted precursor (IIIa) was used as a Labo Plastomill uniaxial extruder [manufactured by Toyo Seiki Seisakusho]
Was extruded at 200 ° C. for graft reaction to obtain a graft copolymer (IIIA).

The graft copolymer (IIIA) was observed with a scanning electron microscope "JEOL JSM T300" (manufactured by JEOL Ltd.), and the particle size was 0.3 to 0.
It had a multiphase structure in which 4 μm spherical resin was uniformly dispersed. At this time, the graft efficiency of the styrene polymer was 7
It was 7.1% by weight.

Reference Example 2 (Production of Graft Copolymer (IIIB)) In Reference Example 1, 300 g of styrene monomer as a vinyl monomer, 210 g of styrene monomer and 90 g of acrylonitrile monomer.
And mixed monomer with benzoyl peroxide 1.5
g is di-3,5,5-trimethylhexanoyl peroxide "Perloyl 355" [trade name, NOF Corporation]
3 g, and 0.3 g of α-methylstyrene dimer “Nofmer MSD” [trade name, manufactured by NOF CORPORATION] was used as a molecular weight modifier, except that 0.3 g of Reference Example 1 was repeated. (IIIb) and the graft copolymer (IIIB) were obtained. At this time, the number average degree of polymerization of the styrene-acrylonitrile polymer was 1200, and the average particle diameter of the resin dispersed in this graft copolymer (IIIB) was 0.3 to 0.4 μm.

Reference Example 3 (Production of Graft Copolymer (IIIC)) 500 g of the grafting precursor (IIIb) obtained in Reference Example 2 and an ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content) 15% by weight) "Rex Pearl RA-3150"
After dry blending 250 g of [trade name, manufactured by Nippon Petrochemical Co., Ltd.] and 250 g of styrene-based polymer “DIALEX HF-77” [trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.], Labo Plastomill uniaxial 200 in extruder
It was extruded at ℃ to obtain a graft copolymer (IIIC). The average particle size of the resin dispersed in this graft copolymer (IIIC) was 0.4 to 0.7 μm.

(Reference Example 4) (Production of Graft Copolymer (IIID)) In Reference Example 1, the ethylene-glycidyl methacrylate copolymer was replaced with an ethylene-propylene copolymer rubber "JSR EP02".
P "[trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.] and no radical-polymerizable organic peroxide was used.
Example 1 was repeated to obtain a graft copolymer (IIID). At this time, the number average degree of polymerization of the styrene polymer is 950,
The average particle size of the resin dispersed in the graft copolymer (IIID) was 1.1 to 1.4 μm.

(Reference Example 5) (Production of Graft Copolymer (IIIE)) Ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content 15% by weight) "Rex Pearl RA-3150" [trade name, Nippon Oil Co., Ltd. Manufactured by Kagaku Co., Ltd.] 900 g of dicumyl peroxide “Park Mill D” [trade name, NOF Corporation]
A solution of styrene 100 in which 20 g was dissolved was mixed and extruded with a Labo Plastomill uniaxial extruder to obtain a graft copolymer (IIIE). At this time, the number average degree of polymerization of the styrene polymer was 4.6, and the graft copolymer (IIIE)
The average particle size of the resin dispersed therein was 0.001 μm.

Reference Example 6 Production of Blend (IIIF) Ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content 1
5% by weight) "Rex Pearl RA-3150" [trade name,
700 g of Nippon Petrochemical Co., Ltd. and 300 g of styrene polymer “DIALEX HF-77” [trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.] are dry-blended and then 200 with a Labo Plastomill uniaxial extruder. The mixture was extruded at 0 ° C to obtain a blend (IIIF). This blend (III
The average particle size of the resin dispersed in F) is 12 to 15 μm.
It was m.

(Examples 1 to 10) Polyphenylene ether resin "Noryl 534J-801" [trade name, manufactured by Nippon GE Plastics Co., Ltd.] (indicated in the table as PPE), ABS resin "Styrac ABS283" Trade name, manufactured by Asahi Chemical Industry Co., Ltd.] (shown as ABS in the table) and the graft copolymers (IIIA) to (I
Cylinder temperature 280 after dry blending IIC)
The mixture was fed to a coaxial twin-screw extruder having a screw diameter of 30 mm set to 0 ° C., and extruded and granulated. Granulated resin is 150 ℃
After drying for 3 hours, the test piece was prepared by injection molding. The size of the test piece is as follows.

Izod impact test piece 13 mm × 6
5mm × 6mm (with notch) Deflection temperature test piece under load 13mm × 130mm × 6
mm Bending test piece 10mm × 130mm × 4
mm

The test method is as follows. (1) Izod impact value (with notch): JIS K7
110 (2) Deflection temperature under load: JIS K7
207 (3) Bending test: JIS K6
758 (4) Fluidity (spiral flow) At a molding temperature of 260 ° C, an injection molding machine (TS-35-FV25 type manufactured by Tabata Machine Industry Co., Ltd.) was used to form a mold having spiral grooves with a width of 4 mm and a thickness of 2 mm. Mounted, injection speed 95%, injection pressure 1000 kg / cm ² , mold temperature 60
Injection molding was carried out under the condition of ° C, and the length of the molded spiral was measured and used as an index of fluidity. (5) Appearance of molded product Regarding the appearance of the molded product, the presence or absence of flow marks was visually determined and ranked as follows. Flow mark ◎: No flow mark ○: Slight flow mark ×: Flow mark

[0056]

[Table 1]

(Examples 11 to 20) Examples using the grafting precursor (IIIa) or (IIIA) obtained in Reference Example 1,
SEBS "Clayton G1650" (IV) (trade name, manufactured by Shell Chemical Co., Ltd.), glass fiber as an inorganic filler
Table 2 shows an example in which (V) average fiber length of 0.3 mm × diameter of 10 μm) was added.

[0058]

[Table 2]

Comparative Examples 1 to 10 Graft Copolymer (III
Instead of A) to (IIIC), an epoxy group-containing olefin polymer (IIIG) "Rex Pearl RA-3150" (trade name, manufactured by Nippon Petrochemical Co., Ltd.) or the graft copolymer obtained in Reference Examples 4 to 6 Examples using the polymers (III D) to (III E) or the blend (III F) and the graft copolymer (III A) obtained in Reference Example were used, but examples outside the compounding range of the present invention are shown. 3 shows.

[0060]

[Table 3]

From these results, the resin composition of the present invention to which the graft copolymer (III) was added at the time of blending the polyphenylene ether resin (I) and the ABS resin (II) was that of the comparative example. In comparison, it is understood that the resin composition has further improved moldability (flowability) while maintaining heat resistance and mechanical properties.

[0062]

The thermoplastic resin composition of the present invention comprises a polyphenylene ether resin (I) and an ABS resin (I
A resin composition which is excellent in impact resistance, heat resistance, molding processability and surface appearance by making the best use of the advantages of I). Therefore, it can be widely used for automobile parts, electric / electronic parts, industrial parts and the like.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hiroshi Omura 5-3-1 Rokunukiyama, Taketoyo-cho, Chita-gun, Aichi

Claims (1)

[Claims] 1. A polyphenylene ether resin (I) 5
~ 95 wt% and ABS resin (II) 95-5 wt%
And (I) + (II) 100 parts by weight, based on 5 to 95% by weight of the epoxy polymer segment and 95 to 5% by weight of the vinyl polymer segment, one polymer segment is A graft copolymer (III) having a multiphase structure in which a dispersed phase having a particle size of 0.001 to 10 μm is formed in a continuous phase formed by a coalescing segment is 1 to 100.
A thermoplastic resin composition characterized by being mixed in parts by weight.