JPH0615651B2 - Thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition which is excellent in impact resistance and flowability, and gives a uniform matte surface of a molded article at the time of molding.

<Prior Art> A diene rubber-modified styrene thermoplastic resin typified by an ABS resin has excellent mechanical properties such as impact resistance and rigidity and workability, as well as excellent appearance of molded products such as gloss.
It is used in a wide range of applications such as office equipment parts and sundries. However, recently, mainly for automobile interior parts, from the viewpoint of safety or to obtain a calm matte texture,
There is also an increasing demand for low-gloss matte materials.

Conventionally, as a delustering method for rubber-modified styrenic resin,
(i) Addition of inorganic filler such as calcium carbonate, (ii) Addition of rubbery polymer, (iii) Introduction by copolymerization of ethylenically unsaturated carboxylic acid, (iv) Addition of epoxy group-containing olefin copolymer Etc. have been proposed.

<Problems to be Solved by the Invention> In the above matting method, the addition of the (i) inorganic filler has a drawback that the impact resistance, which is a characteristic of the rubber-modified resin, is significantly lowered. Further, (ii) the addition of the rubbery polymer has a problem that defects such as flow marks occur on the surface of the molded product, and a uniform matte surface cannot be obtained (iii) The introduction of the ethylenically unsaturated carboxylic acid There is a problem that the flowability of the resin is greatly reduced.

(iv) The addition of the epoxy group-containing olefin copolymer is as described above.
Compared with the methods (i), (ii) and (iii), it has an advantage that a matte effect is excellent and a uniform matte surface with no defects can be obtained. There is a problem that the sex is lowered.

<Means for Solving Problems> The inventors of the present invention have conducted extensive studies to improve the above-mentioned problems, and as a result, have found that a diene rubber-modified styrene thermoplastic resin has a specific functional group together with an epoxy group-containing olefin copolymer. The present inventors have found that the addition of a polymer containing a group makes it possible to obtain a thermoplastic resin composition which gives a uniform delustered surface of a molded article with less deterioration in flowability, and has reached the present invention.

That is, the present invention relates to at least one functional group selected from the group consisting of (A) a diene rubber-modified styrene thermoplastic resin, (B) an epoxy group-containing olefin copolymer, and (C) a carboxyl group, a hydroxyl group and a nitrogen-containing base. It is obtained by copolymerizing an ethylenically unsaturated compound having OH with another unsaturated compound, or by graft-copolymerizing an ethylenically unsaturated compound having a functional group in the presence of another unsaturated compound polymer. The functional group-containing polymer is (A) 40 with the total amount of (A), (B) and (C) being 100 parts by weight.
˜99.8 parts by weight, (B) 0.1 to 10 parts by weight and (C) 0.1 to 50 parts by weight, and the amount of diene rubber contained in the composition is 5 to 40% by weight. The present invention provides a thermoplastic resin composition characterized by being mixed in a ratio.

The present invention will be described in detail below.

The diene rubber-modified styrene thermoplastic resin (A) in the present invention is obtained by polymerizing an aromatic vinyl compound in the presence of a diene rubber and optionally an ethylenically unsaturated compound copolymerizable therewith. Or a mixture of the graft copolymer with an aromatic vinyl compound and, if necessary, an aromatic vinyl polymer obtained by polymerizing an ethylenically unsaturated compound copolymerizable therewith. .

Examples of the diene rubber include polybutadiene and butadiene-
Butadiene-based rubbers such as styrene copolymers and butadiene-acrylonitrile copolymers are exemplified, and one kind or two or more kinds can be used.

As the aromatic vinyl compound, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p
-Methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene,
Vinyl naphthalene and the like are exemplified, and one kind or two or more kinds can be used.

As the ethylenically unsaturated compound copolymerizable with the aromatic vinyl compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, vinyl cyanide compounds such as fumaronitrile, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl Methacrylate, ethyl methacrylate,
Unsaturated carboxylic acid alkyl ester compounds such as propyl methacrylate and 2-ethylhexyl methacrylate,
Maleimide compounds such as maleimide, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, unsaturated amide compounds such as acrylamide and methacrylamide, and maleic anhydride, itaconic anhydride,
Unsaturated acid anhydrides such as citraconic anhydride are exemplified, and one kind or two or more kinds can be used.

Preferred examples of the diene rubber-modified styrene thermoplastic resin include a butadiene rubber-modified acrylonitrile-styrene copolymer (ABS resin), a butadiene rubber-modified styrene polymer, a butadiene rubber-modified methyl methacrylate styrene copolymer, and butadiene. -Based rubber-modified acrylonitrile-methyl methacrylate-styrene copolymer, butadiene-based rubber-modified acrylonitrile-α-methylstyrene-styrene copolymer, butadiene-based rubber-modified acrylonitrile-α-methylstyrene-methyl methacrylate-styrene copolymer, butadiene-based Rubber-modified styrene-maleic anhydride copolymer, butadiene-based rubber-modified acrylonitrile-styrene-maleic anhydride copolymer, butadiene-based rubber-modified styrene-N-phenylmaleimide copolymer, pig Diene rubber modified acrylonitrile-styrene-N-phenylmaleimide copolymer, butadiene rubber modified acrylonitrile-styrene-maleic anhydride-N-phenylmaleimide copolymer, butadiene rubber modified styrene-methylmethacrylate-maleic anhydride copolymer Examples thereof include a combination and a butadiene rubber-modified styrene-methylmethacrylate-N-phenylmaleimide copolymer, and one or two or more of them can be used.

As the method for producing the diene rubber-modified styrene thermoplastic resin, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof is used.

Next, the epoxy group-containing olefin copolymer (B) used in the present invention is a copolymer composed of an unsaturated epoxy compound and an olefin, or these and an ethylenically unsaturated compound. The composition ratio of the epoxy group-containing olefin copolymer is not particularly limited, but the epoxy compound 0.05 to
It is preferably 95% by weight.

The unsaturated epoxy compound is a compound having an unsaturated group capable of copolymerizing with an olefin and an ethylenically unsaturated compound and an epoxy group in the molecule.

For example, unsaturated glycidyl esters represented by the following general formulas (I), (II) and (III), unsaturated glycidyl ethers, epoxy alkenes, unsaturated epoxy compounds such as P-glycidyl styrenes is there.

(R is a hydrocarbon group of C ₂ -C ₁₈ having an ethylenically unsaturated bond.) (R is a hydrocarbon group of C ₂ -C ₁₈ having an ethylenically unsaturated bond.

X is -CH ₂ -O- (R is a hydrocarbon group of C ₂ -C ₁₈ having an ethylenically unsaturated bond .R 'is hydrogen or a methyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, butene Carboxylic acid esters, allyl glycidyl ether, 2-
Methylallyl glycidyl ether, styrene-P-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
1-Pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, P-glycidylstyrene and the like can be mentioned. Glycidyl acrylate or glycidyl methacrylate is particularly preferable.

As olefins, ethylene, propylene, butene,
Penten etc. are mentioned.

Examples of the ethylenically unsaturated compound include vinyl esters containing C _{2 to} C ₆ in the saturated carboxylic acid component, acrylic acid and methacrylic acid esters and maleic acid esters containing C _{1 to} C ₈ in the saturated alcohol component, halogen. Examples thereof include vinyl chlorides.

These ethylenically unsaturated compounds are added to an unsaturated epoxy compound and an olefin at the time of copolymerization with the total amount of the compound to be 5
Copolymerized up to 0% by weight, especially 0.1 to 45% by weight.

The epoxy group-containing olefin copolymer is obtained by copolymerizing an unsaturated epoxy compound with an olefin and optionally an ethylenically unsaturated compound, or in the presence of an olefin polymer or a copolymer of an olefin and an ethylenically unsaturated compound. It is produced by graft-copolymerizing an unsaturated epoxy compound.

Preferable examples of the epoxy group-containing olefin copolymer include ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl methacrylate-glycidyl methacrylate copolymer, and polyethylene, polypropylene, poly-. Examples of the copolymer include a graft reaction of glycidyl methacrylate in the presence of an olefin polymer such as 1-butene, poly-4-methyl-pentene-1, ethylene-propylene copolymer, and ethylene-propylene-diene copolymer. To be

As a method for producing the epoxy group-containing olefin copolymer, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method or a polymerization method combining these methods is used.

The functional group-containing polymer (C) used in the present invention means an ethylenically unsaturated compound having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and a nitrogen-containing base, and another unsaturated compound. It is a polymer obtained by polymerizing or graft-copolymerizing an ethylenically unsaturated compound having a functional group in the presence of another unsaturated compound polymer.

Examples of the ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and one or more can be used.

Examples of the ethylenically unsaturated compound having a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, and one kind or two or more kinds can be used.

As the ethylenically unsaturated compound having a nitrogen-containing base,
Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine,
2-Methyl-5-vinyl pyridine, N-vinyl imidazole, N-vinyl indole, N-vinyl carbazole, N-vinyl pyrrole, p-aminostyrene, p-dimethylamino styrene are exemplified, and one or two or more of them may be used. You can

Other unsaturated compounds copolymerized with the ethylenically unsaturated compound having a functional group include ethylene, propylene, 1-
Olefin compounds such as butene, aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene,
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, unsaturated carboxylic acid alkyl ester compounds such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate,
Examples include maleimide compounds such as maleimide and N-phenylmaleimide, unsaturated amide compounds such as acrylamide and methacrylamide, vinyl ester compounds such as vinyl acetate and vinyl propionate, and diene compounds such as butadiene, isoprene and chloroprene. It is possible to use more than one kind.

As the method for producing the functional group-containing polymer (C), an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or a combination of these methods is used.

Preferred examples of the functional group-containing polymer (C), styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, acrylonitrile-styrene-methacrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer, styrene -Methyl methacrylate-methacrylic acid copolymer, styrene-hydroxyethyl acrylate copolymer, acrylonitrile-styrene-hydroxyethyl acrylate copolymer, styrene-hydroxyethyl methacrylate copolymer, acrylonitrile-styrene-hydroxyethyl methacrylate copolymer, Styrene-dimethylaminoethyl acrylate copolymer, acrylonitrile-styrene-dimethylaminoethyl acrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, acrylo Tolyl - styrene - dimethylaminoethyl methacrylate copolymer, styrene - diethylaminoethyl methacrylate copolymer, acrylonitrile - styrene - diethylaminoethyl methacrylate copolymer, styrene-2-vinylpyridine copolymer,
Acrylonitrile-styrene-2-vinylpyridine copolymer, ethylene-acrylic acid copolymer and its metal salt, ethylene-methacrylic acid copolymer and its metal salt, ethylene-diethylaminoethyl methacrylate copolymer, ethylene-propylene-acrylic Acid copolymers,
Ethylene-propylene-methacrylic acid copolymer, butadiene rubber modified styrene-acrylic acid copolymer, butadiene rubber modified styrene-methacrylic acid copolymer, butadiene rubber modified acrylonitrile-styrene-acrylic acid copolymer, butadiene Rubber-modified acrylonitrile-styrene-methacrylic acid copolymer, butadiene-based rubber-modified acrylonitrile-styrene-2-vinylpyridine copolymer, butadiene-based rubber-modified acrylonitrile-styrene-hydroxyethyl acrylate copolymer, butadiene-based rubber-modified acrylonitrile-styrene -Hydroxyethyl methacrylate copolymer, butadiene rubber-modified acrylonitrile-styrene-dimethylaminoethyl acrylate copolymer, butadiene rubber-modified acrylonitrile-styrene Down - diethylaminoethyl methacrylate copolymer, butadiene rubber modified acrylonitrile - styrene-2-vinylpyridine copolymer. Can be used singly or in combination.

The mixed composition of the diene rubber modified styrene thermoplastic resin (A), the epoxy group-containing olefin copolymer (B) and the functional group-containing polymer (C) is the sum of (A), (B) and (C). Quantity 10
As 0 parts by weight, (A) 40 to 99.8 parts by weight, preferably 75 to 99 parts by weight, (B) 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, (C) 0. 1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, and the amount of the diene rubber contained in the composition is 5 to 40% by weight, preferably 10 to
It is 30% by weight.

If the diene rubber-modified styrene thermoplastic resin (A) is less than 40 parts by weight, the balance between impact strength and flowability deteriorates, and 9
If the amount exceeds 9.8 parts by weight, the matting effect becomes insufficient. If the amount of the epoxy group-containing olefin copolymer (B) is less than 0.1 parts by weight, a uniform matte surface cannot be obtained, and the matting effect is insufficient, and if it exceeds 10 parts by weight, the flowability is remarkably reduced. Become. When the amount of the functional group-containing copolymer (C) is less than 0.1 part by weight, the balance between the matting effect and the flowability is lower than that of the composition of the present invention, and when it exceeds 50 parts by weight, the flowability is deteriorated. It becomes remarkable. If the amount of the diene rubber in the composition is less than 5% by weight, the impact strength is remarkably lowered, and if it exceeds 40% by weight, the flowability and the rigidity are lowered, which is not preferable.

Diene rubber modified styrene thermoplastic resin (A), epoxy group-containing olefin copolymer (B) and functional group-containing polymer (C) is not particularly limited as to the mixing method, in the latex state, or powder, beads It can be mixed in the form of pellets. The order of mixing them is also not particularly limited, and may be a method of collectively mixing the three components or a method of premixing the two components and mixing the remaining one component. As a melt-kneading method, a known method such as a Banbury mixer, a roll or an extruder can be adopted.

At the time of mixing, if necessary, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a dye, a pigment, a plasticizer, a flame retardant,
Additives such as release agents can be added. Further, a thermoplastic resin such as polyacetal, polycarbonate, polybutylene terephthalate, polyphenylene oxide, polymethylmethacrylate, or polyvinyl chloride can be appropriately blended.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The numbers of parts and percentages are shown on a weight basis.

Reference Example 1 Production of Diene Rubber Modified Thermoplastic Resin (A) A-1 Polybutadiene latex 1 having an average particle size of 0.4 μm, a gel content of 80% and a solid content of 50% was placed in a reactor substituted with nitrogen.
After charging 00 parts, 0.3 parts of potassium persulfate and 100 parts of pure water, the temperature was raised to 65 ° C. with stirring. Thereafter, 30 parts of an emulsifier aqueous solution containing 15 parts of acrylonitrile, 35 parts of styrene and 0.2 part of t-dodecyl mercaptan and 2 parts of disproportionated potassium rosinate were continuously added over 4 hours, and then the polymerization system was added. 70 ° C
The temperature was raised to 0, and the mixture was aged for 3 hours to complete the polymerization and obtain an ABS graft copolymer latex.

A-2 A reactor purged with nitrogen was charged with 0.3 part of potassium persulfate and 120 parts of pure water, and then heated to 65 ° C. with stirring. Then 30 parts of acrylonitrile, 70 parts of styrene and 0.3 part of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of disproportionated potassium rosinate were continuously added for 4 hours each, and then the polymerization was performed. The system was heated to 70 ° C. and aged for 3 hours to complete the polymerization to obtain an acrylonitrile-styrene copolymer latex.

A-3 After charging 150 parts of pure water, 0.5 part of potassium persulfate and 2 parts of sodium lauryl sulfate into a reactor purged with nitrogen, the temperature was raised to 70 ° C. with stirring. Then, a mixed monomer solution containing 30 parts of acrylonitrile, 70 parts of α-methylstyrene and 0.2 part of t-dodecyl mercaptan was added to 5 parts of a mixed monomer solution.
After continuous addition over a period of time, the polymerization system was heated to 75 ° C. and aged for 5 hours to complete the polymerization.
An α-methylstyrene copolymer latex was obtained.

A-4 After charging 120 parts of pure water and 0.3 part of potassium persulfate to a reactor purged with nitrogen, the temperature was raised to 65 ° C with stirring. Then, 30 parts of an emulsifier aqueous solution containing 25 parts of acrylonitrile, 25 parts of N-phenylmaleimide, 50 parts of styrene and 0.3 part of t-dodecyl mercaptan and 2 parts of sodium lauryl sulfate were continuously added for 4 hours. After the addition, the polymerization system was heated to 70 ° C. and aged for 3 hours to complete the polymerization to obtain an acrylonitrile-N-phenylmaleimide-styrene copolymer latex.

Next, 100 parts of ABS graft copolymer latex (solid
Shaper) Sumilyzer as an antioxidant BBM 1st copy
And 2 parts trisnonylphenyl phosphite
After that, salting out with calcium chloride, dehydration and drying
Thus, a powdery ABS graft copolymer was obtained. In addition,
Ren Copolymer Latex A-2, A-3 and A-4
For each, salt using calcium chloride as it is.
The powder was analyzed, dehydrated and dried to obtain powder.

Reference Example 2 Production of Epoxy Group-Containing Olefin Copolymer (B) Using an autoclave-type polyethylene producing apparatus, an epoxy group-containing olefin copolymer having the following composition was produced by the bulk polymerization method according to the polymerization conditions of high-pressure polyethylene. .

B-1 Ethylene-glycidyl imethacrylate-vinyl acetate copolymer (composition ratio 90-7-3) B-2 Ethylene-glycidyl methacrylate copolymer (composition ratio 90-10) Reference Example 3 Functional group-containing polymer (C ) Preparation of C-1 A reactor purged with nitrogen was charged with 120 parts of pure water and 0.3 part of potassium persulfate, and then heated to 65 ° C with stirring. Then 30 parts of acrylonitrile, 65 parts of styrene,
Methacrylic acid 5 parts and t-dodecyl mercaptan 0.
30 parts of an emulsifier aqueous solution containing 3 parts of the mixed monomer solution and 2 parts of sodium dodecylbenzene sulfonate were continuously added for 4 hours each, and then the polymerization system was heated to 70 ° C. and aged for 3 hours for polymerization. It's complete.

C-2 An acrylonitrile-styrene-hydroxyethyl acrylate copolymer was produced in the same manner as C-1, except that 5 parts of methacrylic acid was replaced with 5 parts of hydroxyethyl acrylate.

After charging 120 parts of pure water and 0.3 part of potassium persulfate to a reactor purged with C-3 nitrogen, the temperature was raised to 65 ° C with stirring. Then, 30 parts of acrylonitrile, 65 parts of styrene
Parts, 5 parts of 2-vinylpyridine and 0.3 parts of t-dodecyl mercaptan, and 30 parts of an emulsifier aqueous solution containing 2 parts of disproportionated potassium rosinate are continuously added for 4 hours, respectively, and then polymerized. The system was heated to 70 ° C. and aged for 3 hours to complete the polymerization.

Acrylonitrile-styrene-diethylaminoethyl methacrylate copolymer was produced in the same manner as C-3 except that 5 parts of C-4 2-vinylpyridine was replaced with 5 parts of diethylaminoethyl methacrylate.

C-5 Polybutadiene latex 1 having an average particle size of 0.3 μm, a gel content of 72% and a solid content of 50% was placed in a reactor substituted with nitrogen.
After charging 00 parts, potassium persulfate 0.3 part, sodium dodecylbenzenesulfonate 0.5 part and pure water 100 parts, stirring was started and the temperature was raised to 65 ° C. Then 15 parts of acrylonitrile, 30 parts of styrene, 5 parts of methacrylic acid
And 30 parts of an emulsifier aqueous solution containing 1 part of sodium dodecylbenzenesulfonate and 30 parts of an emulsifier aqueous solution each containing 4 parts and t-dodecyl mercaptan were continuously added over 4 hours. After that, the temperature of the polymerization system was raised to 70 ° C., and 3
An ethylene-acrylic acid copolymer (composition ratio 90-1 was prepared by bulk polymerization using a C-6 autoclave-type polyethylene manufacturing apparatus that had been aged for a period of time to complete the polymerization, according to the polymerization conditions for high-pressure polyethylene.
0) was produced.

C-7 An ethylene-diethylaminoethyl methacrylate copolymer (composition ratio 90-10) was produced in the same manner as C-6.

In addition, latex-like functional group-containing polymers C-1, C-2,
Each of C-3, C-4 and C-5 was salted out with calcium chloride, dehydrated and dried to obtain a powder. However,
For C-5 only, salting out was performed after adding an antioxidant as in A-1.

Examples 1 to 7 ABS graft copolymer (A-1) produced in Reference Example,
Acrylonitrile-styrene copolymer (A-2), ethylene-glycidyl methacrylate-vinyl acetate copolymer (B-1) and functional group-containing polymer (C-1 to C-7)
Were mixed in the composition shown in Table 1 and melt-kneaded using a 40 mm single-screw extruder. The characteristics of the obtained resin composition were measured by the following methods, and the results are shown in Table 1.

Impact resistance (Izod with notch): ASTMD-256 Flowability: Enhanced flow tester Bending elastic modulus: ASTMD-790 Surface gloss and unevenness of gloss: 3.5 oz 60mm x 60mm thickness 3mm thickness using injection molding machine A test plate was molded, and the gloss of the central part of the test plate was measured at an incident angle of 60 ° using a digital variable angle gloss meter UGV-4D manufactured by Suga Test Instruments Co., Ltd. Further, the uneven gloss on the entire surface of the test plate was evaluated by visual judgment.

Comparative Examples 1 to 10 In the same manner as in Examples 1 to 7, resin compositions were produced with the composition shown in Table 2. The characteristics are shown in Table 2.

The compositions of the present invention (Examples 1 to 7) are compositions (Comparative Example 2) in which only the epoxy group-containing olefin copolymer is added.
Compared to 3), the balance between matting level and flowability is excellent. In addition, the compositions containing only the functional group-containing polymer (Comparative Examples 4 to 10) were inferior in overall matting level,
There is uneven gloss and the appearance of molded products is inferior.

Examples 8 to 15 and Comparative Examples 11 to 14 In the same manner as in Examples 1 to 7, resin compositions were prepared with the composition shown in Table 3, and the characteristics thereof were measured.

When the ratio of the epoxy group-containing olefin copolymer exceeds the range of the present invention (Comparative Example 11), the flowability is significantly reduced. Also, when the ratio of the functional group-containing polymer exceeds the range of the present invention (Comparative Examples 12, 13, and 14), the matting level is excellent, but the flowability is largely deteriorated, which is not preferable.

Examples 16 and 17 and Comparative Examples 15 and 16 In the same manner as in Examples 1 to 7, resin compositions were produced by changing the amount of diene rubber in the composition with the composition shown in Table 4.
Its properties were measured.

When the amount of rubber in the composition is less than the range of the present invention (Comparative Example 15), the impact resistance is lowered, while when the amount of rubber is more than the range of the present invention (Comparative Example 16), flowability and The rigidity (flexural modulus) is reduced, which is not preferable.

Examples 18 to 23 and Comparative Examples 17 and 18 Styrene-based copolymers, which are constituents of the diene rubber-modified thermoplastic resin, were respectively converted into acrylonitrile-α-methylstyrene copolymer and acrylonitrile-N-phenylmaleimide-styrene copolymer. A resin composition was produced in the same manner as in Examples 1 to 7 with the compounding composition shown in Table 5 instead of the polymer. The characteristics are shown in Table 5.

<Effects of the Invention> The thermoplastic resin composition of the present invention has an excellent balance between flowability and the matting level of a molded article, and has no gloss unevenness, as compared with conventionally known matting thermoplastic resin compositions. The feature is that a uniform matte surface can be obtained.

Claims (1)

[Claims] 1. A functional group selected from the group consisting of (A) diene rubber-modified styrene thermoplastic resin, (B) epoxy group-containing olefin copolymer and (C) carboxyl group, hydroxyl group and nitrogen-containing base. Or copolymerizing an ethylenically unsaturated compound having
Alternatively, a functional group-containing polymer obtained by graft-copolymerizing an ethylenically unsaturated compound having a functional group in the presence of another unsaturated compound polymer is a total of (A), (B) and (C). (A) 40 to 9 with the amount being 100 parts by weight
9.8 parts by weight, (B) 0.1 to 10 parts by weight and (C)
A thermoplastic resin composition, which is 0.1 to 50 parts by weight and is mixed in a proportion such that the amount of the diene rubber contained in the composition is 5 to 40% by weight.