JPH073169A - Thermoplastic resin composition with improved mattness - Google Patents

Abstract

(57) [Summary] [Object] To provide a thermoplastic resin composition capable of obtaining a molded product whose surface is uniformly and densely matt. [Structure] (A) 100 parts by weight of a non-crystalline resin (excluding a rubber-reinforced resin composed of a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound and / or another compound capable of copolymerization) On the other hand, (B) 0.01 to 20 parts by weight of an epoxy group-containing ethylene copolymer, and
(C) Polyfunctional compound and / or (D) 0.01 to 20 parts by weight of a metal salt of a carboxylic acid, and a thermoplastic resin composition having improved matting properties.

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 capable of providing a molded and processed product having a uniformly and densely matt surface.

[0002]

2. Description of the Related Art Non-crystalline materials such as polystyrene resins (aromatic vinyl polymers), AS resins (vinyl cyanide-aromatic vinyl copolymers), polycarbonate resins and polyphenylene ether resins. Resins are used in various fields such as vehicles, low-voltage electric appliances, and sundries because of their excellent moldability, impact resistance, rigidity and good surface gloss. However, not all of these physical properties are required depending on the application. For example, automotive interior parts, office or household electrical equipment parts, etc., without lowering other mechanical and chemical properties, reduce the surface gloss of the molded product and modify it to a homogeneous and dense matte state. Materials such as polystyrene resin and polycarbonate resin are demanded. The purpose thereof is to prevent the reflection of light at night in the interior parts of automobiles for safety, and in the electrical equipment parts, a high-grade appearance is required due to the high-class orientation.

As a conventional method for matting a molded article, for example, an amorphous resin such as a polystyrene resin or a polycarbonate resin, a crystalline resin such as polypropylene or a saturated polyester resin, or an oxide or carbonic acid such as titanium, magnesium or calcium is used. A method of adding a filler such as a salt is known, but with this method, the matte surface of the molded article was not satisfactory.

Further, a method in which a rubber-like elastic material is added or grafted to these resins, or a composition obtained by adding a crosslinkable ethylene copolymer (Japanese Patent Laid-Open No. 59-8934).
No. 6) is also well known, but even with these methods, matting is still insufficient, and there is a drawback that uneven matting occurs due to poor dispersion of these materials.

[0005]

SUMMARY OF THE INVENTION In order to solve the heretofore known technical problems, the present inventors have found that non-crystalline resins such as polystyrene resins, AS resins, polycarbonate resins and polyphenylene ether resins ( However, as a result of diligent study on a resin composition effective for modifying a rubber-based polymer, an aromatic vinyl compound and a vinyl cyanide compound or / and a rubber-reinforced resin comprising another compound capable of copolymerization), The present invention has been completed by finding a thermoplastic resin composition that can provide a molded article having a matt surface by blending a specific compound.

That is, the present invention provides (A) a non-crystalline resin (provided that a rubber-reinforced resin comprising a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound or / and another compound capable of copolymerization). (Excluding) 100 parts by weight of (B) epoxy group-containing ethylene copolymer 0.01 to
20 parts by weight and (C) a carboxyl group, an amino group,
The same or different selected from a carboxylic acid anhydride group and a unit of the following formula (1) (in the formula, X and Y represent an oxygen atom or a sulfur atom, or one represents an oxygen atom and the other represents a sulfur atom) Thermoplastic with improved mattness, which comprises 0.01 to 20 parts by weight of a polyfunctional compound containing at least two functional groups in one molecule and / or (D) a metal salt of a carboxylic acid. A resin composition is provided.

The present invention will be described in detail below. The (A) non-crystalline resin used in the present invention means that the temperature is raised to a temperature at which the resin is melted by a differential scanning calorimeter (DSC) and then 10 ° C. /
A resin in which no exothermic peak due to crystallization is observed when the temperature is lowered in minutes. The (A) non-crystalline resin used in the present invention is, for example, a polystyrene resin (provided that it is a rubber-reinforced polymer composed of a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound, and / or other copolymerizable compound). Resin), AS resin (vinyl cyanide-aromatic vinyl copolymer), polycarbonate resin, polyphenylene ether resin, and mixtures thereof, such as polyphenylene ether resin and polystyrene resin, polyphenylene ether resin and rubber-modified polystyrene resin. Etc. Of these, polystyrene resin, AS resin, and polycarbonate resin are particularly preferable. However, as the non-crystalline resin, a rubber-reinforced resin composed of a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound and / or another compound which is copolymerizable is excluded.
The rubber-reinforced resin is a rubber-reinforced resin (i) composed of (a) a rubber-like polymer, (b) an aromatic vinyl compound and (c) a vinyl cyanide compound, (a) a rubber-like polymer, (b).
A rubber-reinforced resin (ii) comprising an aromatic vinyl compound and (d) another copolymerizable compound, or (a) a rubbery polymer, (b) an aromatic vinyl compound, (c) a vinyl cyanide compound, and (D) A rubber-reinforced resin (iii) comprising another copolymerizable compound. Generally, it is a polymer obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound or / and another compound capable of copolymerization in the presence of a rubbery polymer. Examples of the rubbery polymer (a) include polybutadiene,
Polyisoprene, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-isoprene-styrene copolymer, diene rubber such as polychloroprene, ethylene-propylene copolymer, ethylene- Examples thereof include ethylene-propylene rubbers such as propylene-non-conjugated diene (ethylidene norbornene, dicyclopentadiene) copolymers and acrylic rubbers such as polybutyl acrylate. Examples of the (b) aromatic vinyl compound include styrene,
Examples thereof include α-methylstyrene, α-ethylstyrene, dimethylstyrene, chlorostyrene, paramethylstyrene and the like. Examples of the vinyl cyanide compound (c) include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and (d) other copolymerizable compounds include (meth) methacrylate such as methyl methacrylate and methyl acrylate.
Acrylic ester compound, N-phenylmaleimide,
Maleimide compounds such as N-cyclohexylmaleimide are mentioned. Specific examples of the rubber-reinforced resin include acrylonitrile-butadiene rubber-styrene polymer (ABS), acrylonitrile-ethylene / propylene rubber-styrene polymer (AES), methyl methacrylate-butadiene rubber-styrene polymer (MBS). , Rubber-reinforced resins such as acrylonitrile-butadiene rubber-styrene-methyl methacrylate polymer (ABSM) and acrylonitrile-acrylic ester rubber-styrene polymer (AAS).

The polystyrene resin used in the present invention is a polymer composed of an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene and 2,4.
-Alkyl-substituted styrenes such as dimethyl styrene, ethyl styrene and p-tert-butyl styrene, α-alkyl substituted styrenes such as α-methyl styrene and α-methyl-p-methyl styrene, and halogen-substituted styrenes such as chlorostyrene. And a copolymer composed of two or more kinds of these monomers is also included. If necessary, other copolymerizable compounds such as an ethylenically unsaturated carboxylic acid ester and a vinyl compound having an amide group can be copolymerized and used. Specific examples of polystyrene resins include polystyrene (PS) and styrene-α-
Methyl styrene copolymer etc. are mentioned. In addition, a non-crystalline resin such as the above-mentioned polystyrene resin may be copolymerized or graft polymerized with a rubbery polymer, if necessary. As the rubbery polymer described here, a diene rubbery polymer and a non-diene rubbery polymer can be used. As the diene rubbery polymer,
Examples thereof include polybutadiene, polyisoprene, and natural rubber. Examples of the non-diene rubbery polymer include ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, acrylic rubber and the like. These rubbery polymers can be used alone or in admixture of two or more. Further, a conjugated diene rubbery polymer and a non-conjugated diene rubbery polymer may be mixed and used. Specific examples thereof include rubber-modified polystyrene-based resins such as polybutadiene rubber-modified polystyrene-based resin (HIPS).

The AS resin used in the present invention is a copolymer obtained by polymerizing a vinyl cyanide compound and an aromatic vinyl compound. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the aromatic vinyl compound, the same ones as those used in the above-mentioned polystyrene resin can be mentioned. If necessary, two or more vinyl cyanide compounds, 2
One or more aromatic vinyl compounds may be copolymerized at the same time. Specific examples of the AS resin include an acrylonitrile-styrene copolymer, a methacrylonitrile-styrene copolymer, and an acrylonitrile-styrene-α-methylstyrene terpolymer.

Polycarbonate resin (P
C) is the following general formula (5) (where X is a carbon number of 1 to 1).
0 alkylene group, C1-10 alkylidene group,
A cycloalkylene group having 4 to 8 carbon atoms, -O-, -S-,
A group selected from the group consisting of —SO ₂ —, R ₁ and R ₂
Is halogen and an alkyl group having 1 to 12 carbon atoms,
It may be the same or different. m and n represent an integer of 0 to 4, and p represents an integer of 0 or 1. The main structure is obtained by condensing a dihydric phenol and a carbonic acid derivative represented by (4). Specific compounds of the general formula (5) include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (3 ', 5'-dibromo-4'-hydroxyphenyl) propane, resorcin, hydroquinone and the like can be mentioned. Of these, bisphenol A is preferred. Examples of the carbonic acid derivative include phosgene, diphenyl carbonate, haloformate of bisphenol A, and the like.

Next, the (B) epoxy group-containing ethylene copolymer used in the present invention may be any epoxy group-containing ethylene copolymer, for example, (a) ethylene unit is 5
0 to 99% by weight, and (b) the unsaturated carboxylic acid glycidyl ester unit or unsaturated glycidyl ether unit is 0.
1 to 30% by weight, preferably 0.5 to 20% by weight,
(C) An epoxy group-containing ethylene copolymer having an ethylenically unsaturated compound unit of 0 to 50% by weight is preferable.
(B) In the epoxy group-containing ethylene copolymer (b)
The unsaturated glycidyl ester unit and the unsaturated glycidyl ether unit are represented by the following general formulas (2) and (3). (In the formula, R is 2 to 2 carbon atoms having an ethylenically unsaturated bond.
18 hydrocarbon groups. ) (In the formula, R is 2 to 2 carbon atoms having an ethylenically unsaturated bond.
18 is a hydrocarbon group, and X is CH ₂ —O— or the following formula (4). )

Specific examples include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

The (B) epoxy group-containing ethylene copolymer used in the present invention includes (a) ethylene and (b)
3 of unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether and (c) ethylenically unsaturated compound
It is also possible to use multi-component copolymers of one or more. Examples of the (c) ethylenically unsaturated compound include α, β-unsaturated carboxylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, vinyl acetate, vinyl propionate, Carboxylic acid vinyl esters such as vinyl butanoate and vinyl benzoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, ethyl vinyl ether and phenyl vinyl ether, styrene, methyl styrene,
Examples thereof include styrenes such as ethylstyrene and dimethylstyrene.

(B) Epoxy group-containing ethylene copolymers include, for example, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-methyl acrylate terpolymer, ethylene-glycidyl methacrylate-ethyl acrylate terpolymer. Examples include a combination, an ethylene-glycidyl methacrylate-vinyl acetate terpolymer, and the like. Among them, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-methyl acrylate terpolymer and ethylene-
A glycidyl methacrylate-vinyl acetate terpolymer is preferred.

The melt index (JIS K6760) of the epoxy group-containing ethylene copolymer is not particularly limited, but is 0.5 to 100 g / 10.
Minutes are preferred.

The method for producing the epoxy group-containing ethylene copolymer is not particularly limited, and examples thereof include a random copolymerization method in which an unsaturated epoxy compound is introduced into the main chain of the copolymer and an unsaturated epoxy compound. Any of the graft copolymerization methods introduced as a side chain of the copolymer is possible. As a specific production method, an unsaturated epoxy compound and ethylene are added in the presence of a radical generator at 500 to 400.
A method of copolymerizing in the presence or absence of a suitable solvent or chain transfer agent at 0 atm and 100 to 300 ° C., an unsaturated epoxy compound and a radical generator are mixed with polyethylene or an ethylene copolymer, and an extruder is used. Among them, a method of performing melt graft copolymerization and the like can be mentioned.

The amount of the (B) epoxy group-containing ethylene copolymer added is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the (A) amorphous resin. is there. If the addition amount is less than 0.01 parts by weight, a satisfactory matting effect on the surface of the molded product cannot be obtained, and conversely, if it exceeds 20 parts by weight, favorable results such as deterioration of molding processability and deterioration of mechanical properties are obtained. I can't.

The polyfunctional compound (C) used in the present invention includes, in one molecule, the same or different functional groups selected from the group consisting of a carboxyl group, an amino group, a carboxylic acid anhydride group and the unit represented by the above formula (1). And those containing at least two of them. The molecular weight of the polyfunctional compound is not particularly limited and includes a high molecular compound.

At least 2 carboxyl groups per molecule
Examples of the (C) polyfunctional compound contained include aliphatic polyvalent compounds such as oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid. Carboxylic acid, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid-acrylic acid methyl ester copolymer, ethylene-acrylic acid-acrylic acid ethyl ester copolymer, ethylene-acrylic acid -Acrylic acid butyl ester copolymer, ethylene-acrylic acid-vinyl acetate ester copolymer, ethylene-methacrylic acid-methacrylic acid methyl ester copolymer, ethylene-methacrylic acid-methacrylic acid ethyl ester copolymer, ethylene-methacrylic Acid-butyl methacrylate Polymer type polycarboxylic acids such as stell copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, etc. An aromatic polycarboxylic acid is mentioned. Among these polyvalent carboxylic acids, aliphatic polycarboxylic acids and polymer type polycarboxylic acids are particularly preferable.

Examples of the (C) polyfunctional compound containing at least two amino groups in one molecule include 1,6-hexamethylenediamine, trimethylhexamethylenediamine, 1,4-diaminobutane and 1,3-. Aliphatic diamines such as diaminopropane, ethylenediamine, polyetherdiamine, hexamethylenediaminecarbamate, aliphaticdiaminecarbamate such as ethylenediaminecarbamate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethylaminoethylamine, methyl Aminopropylamine, 2-hydroxyethylaminopropylamine, aminoethylethanolamine, 1,3-
Aliphatic polyamines such as bis (3-aminopropoxy) -2,2-dimethylpropane, 1,3,6-trisaminomethylhexane, iminobispropylamine, methyliminobispropylamine and bis (hexamethylene) triamine, Alicyclic polyamines such as menthenediamine, N-aminoethylpiperazine, 1,3-diaminocyclohexane, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, m-xylylenediamine, tetrachloro-p- Aliphatic polyamines having an aromatic ring such as xylylenediamine, m-phenylenediamine, o-phenylenediamine, diaminodiphenyl ether, 4,4′-methylenedianiline, diaminodiphenylsulfone, benzidine, 4,4′-bis (o −
Toluidine), 4,4′-thiodianiline, dianisidine, methylenebis (o-chloroaniline), 2,4-toluenediamine, bis (3,4-diaminophenyl) sulfone, diaminoditolyl sulfone, 4-chloro-o-
Phenylenediamine, 4-methoxy-6-methyl-m-
Aromatic amines such as phenylenediamine and m-aminobenzylamine, 1,3-bis (γ-aminopropyl)
Examples thereof include silicon-containing polyamines such as -1,1,3,3-tetramethyldicycloxane. In addition, amine-modified silicone oil, butadiene-acrylonitrile copolymer whose terminal functional group is amine, N, N, N ′,
N'-tetramethylhexamethylenediamine, N, N,
Tertiary amine compounds such as N ′, N ″, N ″ -pentamethyldiethylenetriamine, ethylene units such as copolymers of ethylene and N, N-dimethylaminoethyl methacrylate, and α, β-unsaturated carboxylic acids N, N From ethylene units such as ethylene copolymers composed of dialkylaminoalkyl ester units, copolymers of ethylene and N, N-dimethylaminopropylacrylamide and N, N-dialkylaminoalkyl α, β-unsaturated carboxylic acid amide units Other dihydrazide compounds such as ethylene copolymers, succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, eicosane diacid dihydrazide, diaminomaleonitrile, melamine and the like can also be mentioned. further,
Examples also include compounds generally used as curing agents for epoxy resins, such as imidazoles such as 2,4,6-tris (dimethylaminomethyl) phenyl and 2-ethyl-4-methylimidazole.

The polyfunctional compound (C) containing at least two carboxylic acid anhydride groups in one molecule is, for example, an ethylene copolymer comprising ethylene units and maleic anhydride units, or a copolymer of isobutene and maleic anhydride. Examples thereof include polymers and copolymers of styrene and maleic anhydride. These copolymers may further contain α, β-unsaturated carboxylic acid alkyl ester or carboxylic acid vinyl ester as a copolymerization component. For example, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, methacrylic acid methyl ester,
Acrylic acid alkyl esters such as methacrylic acid ethyl ester and methacrylic acid butyl ester, methacrylic acid alkyl esters, and vinyl esters such as vinyl acetate and vinyl propionate may be contained as a copolymer component. Further, trimellitic anhydride, pyromellitic dianhydride, ethylene glycol bis (anhydrotrimellitate) and the like can be mentioned.

Examples of the polyfunctional compound (C) containing at least two units of the formula (1) in one molecule include heterocyclic compounds, aliphatic compounds and aromatic compounds. Examples of the heterocyclic compound include parabanic acid,
Isocyanuric acid, alloxan, alloxanthin, alloxan-5-oxime, barbituric acid, 5,5-diethylbarbituric acid, 5-ethyl-5-phenylbarbituric acid, 5- (1-methyl-butyl) -5-allyl Barbituric acid, 5,5-diallylbarbituric acid and the like and compounds obtained by substituting the oxygen atom of —C═O of these compounds with a sulfur atom, for example, 2,4-dithiobarbituric acid and 2-thiobarbituric acid are Can be mentioned. Examples of the aliphatic compound include triuret, 1-methyltriuret, 1,1-
Examples thereof include thiouret such as diethyl triuret and tetrauret. Examples of the aromatic compound include thioimides such as pyromellitic acid diimide, meritic acid triimide, and 1,4,5,8-naphthalic acid diimide.

Further, as (C) a polyfunctional compound, one or more carboxyl group and amino group, respectively, in one molecule,
Those having one or more functional groups selected from the carboxylic acid anhydride group and the unit of the above formula (1) are also included. For example, 4
-Aminobutyric acid, 6-aminohexanoic acid, 12-aminododecanoic acid, hydantoic acid and the like can be mentioned. The above-mentioned (C) polyfunctional compounds may be used in combination.

The (D) carboxylic acid metal salt used in the present invention refers to a neutralized product of a compound having at least one carboxyl group, and is, for example, acetic acid, capric acid, lauric acid, tridecylic acid, mistyric acid, stearin. Acid, nonadecanoic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, oleic acid,
Metal salts of aliphatic carboxylic acids such as linoleic acid and tetrahydrophthalic acid, benzoic acid, toluic acid, naphthoic acid, anthracenecarboxylic acid, biphenylcarboxylic acid, aromatic carboxylic acids such as trimesic acid, trimellitic acid and cinnamic acid Salt etc. are mentioned. Further, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid-acrylic acid methyl ester copolymer, ethylene-acrylic acid-acrylic acid ethyl ester copolymer, ethylene-acrylic acid-acrylic acid Butyl ester copolymer, ethylene-acrylic acid-vinyl acetate copolymer, ethylene-methacrylic acid-methacrylic acid methyl ester copolymer, ethylene-methacrylic acid-methacrylic acid ethyl ester copolymer, ethylene-methacrylic acid-methacrylic Acid butyl ester copolymer, ethylene-
A metal salt of a polyvalent carboxylic acid-containing polymer such as a methacrylic acid-vinyl acetate copolymer can also be used.
Examples of the metal of the metal salt include alkali metals such as lithium, sodium and potassium, magnesium, calcium, alkaline earth metals such as strontium,
Alternatively, zinc, aluminum, etc. may be mentioned. In particular,
The (D) carboxylic acid metal salt is preferably an alkali metal salt or alkaline earth metal salt of an aliphatic carboxylic acid such as sodium stearate, magnesium stearate, calcium stearate, sodium acetate and sodium oleate.

Further, in the present invention, (C) or (D)
The components may be used individually or as a mixture, and the mixing ratio thereof is not particularly limited. Further, when the component (D) is used, it is also effective to add a carboxylic acid such as stearic acid, oleic acid or benzoic acid together.

The addition amount of the (C) polyfunctional compound and / or (D) carboxylic acid metal salt used in the present invention is
0.01 to 100 parts by weight of the (A) amorphous resin
20 parts by weight, preferably 0.1 to 10 parts by weight.
If the addition amount is less than 0.01 parts by weight, the matte effect on the surface of the molded product is insufficient. On the contrary, if it exceeds 20 parts by weight, the moldability deteriorates and flow marks are generated on the surface of the molded product, resulting in poor appearance. cause.

In producing the thermoplastic resin composition of the present invention, there is no particular limitation on the mixing method of each component,
It can be carried out by melt-kneading. For the melt-kneading, for example, commonly used kneading devices such as a single-screw or twin-screw extruder, a Banbury mixer, a roll, and various kneaders can be used. The order of mixing is also not particularly limited, and may be a method of mixing the respective components at once or a method of preliminarily mixing the two components and then mixing the remaining one component. Further, an epoxy group-containing ethylene copolymer, a polyfunctional compound and / or a metal salt of a carboxylic acid are melt-kneaded in advance with a part of the non-crystalline resin to produce a high-concentration master batch, and an appropriate amount of the remaining amount is used for the rest. Examples thereof include a method of adding it to the amorphous resin.

The thermoplastic resin composition of the present invention contains other components such as pigments, dyes, reinforcing agents, fillers, heat resistance stabilizers, antioxidants, weathering agents, and cores as long as the moldability and physical properties are not impaired. Agents, lubricants, antistatic agents, release agents, flame retardants, plasticizers and the like can be added. In addition, the thermoplastic resin composition of the present invention contains ABS resin, A
ES resin, AAS resin, polyethylene terephthalate,
Other thermoplastic resins such as polybutylene terephthalate, polyethylene and polypropylene can be blended.

The thermoplastic resin composition of the present invention is not particularly limited to a molding method, and may be molded by, for example, injection molding, extrusion molding or other various molding processing methods.

[0030]

Industrial Applicability As described above in detail, the thermoplastic resin composition of the present invention can provide a processed molded product whose surface is uniformly and densely matt. Furthermore, the thermoplastic resin composition of the present invention can be easily processed into a molded product, a film, a sheet, etc. by a molding processing method used for a usual thermoplastic resin composition, for example, a molding processing method such as injection molding or extrusion molding. .

[0031]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. The physical properties in the examples were measured by the following methods. (1) Surface Matte Degree (Gloss) It was carried out under the condition of 60 ° by a gloss meter GM-3D (manufactured by Murakami Color Research Laboratory).

In Examples and Comparative Examples, the following were used as the (A) non-crystalline resin and (B) the epoxy group-containing ethylene copolymer. (A) Amorphous resin PS: Sumibright E183 (Sumitomo Chemical Co., Ltd.)
(Manufactured) (MI = 2.3 g / 10 min, measured at 200 ° C., 5 kg load) HIPS: Sumibright M540 (manufactured by Sumitomo Chemical Co., Ltd.) (MI = 11 g / 10 min, measured at 200 ° C., 5 kg load) AS: 28% by weight of acrylonitrile, 72 styrene
Weight% (MI = 39 g / 10 min, measured at 220 ° C., 10 kg load) PC: Caliber 200-13 (manufactured by Sumitomo Dow Co., Ltd.) (MI = 13 g / 10 min, measured at 300 ° C., 1.2 kg load) (B) Epoxy group-containing ethylene copolymer Copolymer (1) E / MA / GMA = 65/15 /
20% by weight, MI = 10 g / 10 minutes Copolymer (2) E / VA / GMA = 83/5/1
2% by weight, MI = 3 g / 10 minutes Copolymer (3) E / GMA = 88/12% by weight,
MI = 3 g / 10 minutes Here, E: ethylene, GMA: glycidyl methacrylate, VA: vinyl acetate, MA: methyl acrylate,
MI: Shows the melt flow rate measured under the conditions of 190 ° C. and 2.16 kg load.

Examples 1 to 13 Using a 30 mmφ single screw extruder, (A) an amorphous resin shown in Tables 1 and 2 (B) an epoxy group-containing ethylene copolymer and (C) a polyfunctional resin. The compound or (D) carboxylic acid metal salt was added at a mixing ratio shown in Tables 1 and 2 at 250 ° C.
Was melt-kneaded to obtain a thermoplastic resin composition. For each composition, PS and HIPS at a molding temperature of 25 using a 5 ounce injection molding machine after drying at 110 ° C. for 3 hours.
0 ℃, injection pressure Minimum filling pressure in mold + 10kgf /
cm ² , mold temperature 50 ° C, AS molding temperature 250 ° C, injection pressure minimum filling pressure in mold + 10kgf / cm ² , mold temperature 50 ° C, PC molding temperature 280 ° C, injection pressure
Minimum filling pressure in mold +10 kgf / cm ² , mold temperature 9
Test pieces for measuring physical properties were prepared at 0 ° C. The measurement results of the obtained test pieces are shown in Tables 1 and 2.

Comparative Examples 1, 5, 9 and 13 (A) Amorphous resins and (B) shown in Tables 1 and 2
The epoxy group-containing ethylene copolymer was melt-kneaded in the same manner as in Example 1 to obtain a thermoplastic resin composition. Further, using the composition, a test piece for measuring physical properties was prepared in the same manner as in Example 1. The measurement results of the obtained test pieces are shown in Tables 1 and 2.

Comparative Examples 2, 3, 6, 7, 10, 11, 14 and 15 (A) amorphous resins shown in Tables 1 and 2 and (C) polyfunctional compounds shown in Tables 1 and 2 Alternatively, (D) carboxylic acid metal salt was added and melt-kneaded in the same manner as in Example 1 to obtain a thermoplastic resin composition. Further, using the composition, a test piece for measuring physical properties was prepared in the same manner as in Example 1. The measurement results of the obtained test pieces are shown in Tables 1 and 2.

Comparative Examples 4, 8, 12 and 16 Test pieces were prepared in the same manner as in Example 1 using only the (A) non-crystalline resin shown in Tables 1 and 2. The measurement results of the obtained test pieces are shown in Tables 1 and 2.

[0037]

[Table 1]

[0038]

[Table 2]

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Claims (8)

[Claims] 1. A weight of (A) non-crystalline resin (excluding a rubber-reinforced resin comprising a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound and / or another compound capable of copolymerization) 100 weight 0.01 to 20 parts by weight of (B) epoxy group-containing ethylene copolymer, and
(C) a carboxyl group, an amino group, a carboxylic acid anhydride group, a unit of the following formula (1) (in the formula, X and Y represent an oxygen atom or a sulfur atom, or one is an oxygen atom and the other is a sulfur atom) A) a polyfunctional compound containing at least two identical or different functional groups selected from the above) in one molecule and / or (D) carboxylic acid metal salt.
A thermoplastic resin composition having an improved matting property, characterized in that the thermoplastic resin composition contains 01 to 20 parts by weight. 2. A rubber-reinforced resin in which the non-crystalline resin (A) is a polystyrene resin (provided that it is a rubber-like polymer, an aromatic vinyl compound and a vinyl cyanide compound or / and another compound copolymerizable therewith). Is excluded)
A thermoplastic resin composition having improved mattness as described. 3. A non-crystalline resin (A) is vinyl cyanide.
The thermoplastic resin composition according to claim 1, which is an aromatic vinyl copolymer. 4. The thermoplastic resin composition according to claim 1, wherein the non-crystalline resin (A) is a polycarbonate resin. 5. The epoxy group-containing ethylene copolymer (B), wherein (a) the ethylene unit is 50 to 99% by weight, and (b) the unsaturated carboxylic acid glycidyl ester unit or the unsaturated glycidyl ether unit is 0.1 to 0.1% by weight. The thermoplastic resin with improved matting properties according to claim 1, which is an epoxy group-containing ethylene copolymer comprising 30% by weight and (c) an ester unit selected from the ethylenically unsaturated compound unit of 0 to 50% by weight. Composition. 6. The thermoplastic resin composition according to claim 1, wherein the polyfunctional compound (C) is a polyvalent carboxylic acid. 7. The polyfunctional compound (C) has a unit of the following formula (1) (wherein X and Y represent an oxygen atom or a sulfur atom, or one of them is an oxygen atom and the other is a sulfur atom). The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a heterocyclic compound having 8. The thermoplastic resin composition according to claim 1, wherein the (D) carboxylic acid metal salt is an aliphatic carboxylic acid metal salt.