JP2001072826A - Rubber-reinforced styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition improved in the light resistance of the glycidyl (meth)acrylate-modified rubber-reinforced styrene-based resin as the main component and capable of retaining its delusterring property prior to light exposure even after subjected to light exposure. SOLUTION: This resin composition is obtained by compounding (A) 100 pts.wt. of a glycidyl (meth)acrylate-modified rubber-reinforced styrene-based resin with (B) 1-15 pts.wt. of a polyolefin-based copolymer produced by copolymerization between ethylene and at least one kind of monomer selected from among (meth)acrylic esters, unsaturated carboxylic acids, unsaturated carboxylic acid salts, carbon monoxide, maleic anhydride and vinyl acetate, (C) 0.4-5 pt(s).wt. of a hindered amine and (or) ultraviolet light absorber and (D) 0.5-3 pt(s).wt. of an antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-reinforced styrene resin composition capable of improving the light resistance of a glycidyl (meth) acrylate-modified rubber-reinforced styrene resin and maintaining the matte property before light resistance even after light resistance. About things.

[0002]

2. Description of the Related Art In an ABS resin, a butadiene-based polymer is used as a rubber component to impart impact resistance, but a chemically unstable carbon-carbon double bond is present in the main chain. It is well known that, since they have many, they are easily deteriorated by ultraviolet rays or the like and have poor light resistance. Also,
It is also known that the surface of a molded article changes from low gloss to high gloss after light resistance. It is also known that a high-speed surface impact test of a test piece after a light resistance test causes brittle fracture.

[0003] In order to improve such problems, various techniques for adding an ultraviolet absorber, a light stabilizer and the like have been proposed in order to improve the light resistance of ABS resins, especially matte ABS resins.

For example, Japanese Patent Publication No. 7-30251 discloses that a piperidine-based light stabilizer, a benzophenone-based light stabilizer or a benzotriazole-based light stabilizer is combined to improve the light resistance of a polymer material such as a styrene-based resin. The technique of adding the polysiloxane compound obtained together with an antioxidant and other light stabilizers, if necessary, is disclosed in Japanese Patent No. 2550474. The polymer having an imide group in the side chain has an ABS resin. A technique of adding a hindered amine compound and a hindered phenol compound in order to improve the light fastness of a compound containing such a compound is disclosed in JP-A-10-7.
No. 857 discloses a maleimide-based copolymer, an AS-based copolymer, and the like in order to impart excellent light resistance to an ABS resin.
A technique for adding a light-resistant agent such as an ABS-based graft copolymer and a hindered amine compound is disclosed. JP-A-9-310004 discloses a thermoplastic resin obtained by graft-polymerizing a monomer mainly containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a non-diene rubbery polymer. Resin, thermoplastic polyester,
Melt flow rate (JIS K 6760) 3g / 1
A technique for improving light resistance and the like by blending a high-density polyethylene and a modified polyethylene wax for 0 minutes or more is disclosed. Further, Japanese Patent Application Laid-Open No. Sho 52-1655
Japanese Unexamined Patent Publication No. 9-31294 discloses a high-impact flame-retardant ABS resin obtained by adding a flame retardant to a blend of an ABS resin and an ethylene-ethyl acrylate copolymer.
Japanese Patent Application Laid-Open Publication No. H10-150,1992 discloses a thermoplastic resin composed of a copolymer such as a rubber-containing graft copolymer or a vinyl cyanide compound, which is blended with an ethylene / (meth) acrylate / carbon monoxide copolymer to provide mechanical properties. And techniques for improving chemical resistance are disclosed.

[0005]

However, with respect to the strict requirement for light resistance, all of the above-mentioned ones are unsatisfactory because of large discoloration and change in resin gloss.

In the matte ABS resin, the weather resistance is improved without significantly lowering the mechanical strength, moldability, low-temperature impact resistance, and color development resistance during molding, and the gloss before light resistance after light resistance is improved. There is a need for a technology that can be maintained.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned circumstances, and as a result, have found that a small amount of a polyolefin-based copolymer, a hindered amine and Or) By adding an ultraviolet absorber and an antioxidant, the light resistance is improved without significantly lowering the physical properties of the glycidyl (meth) acrylate-modified rubber-reinforced styrene resin, and the gloss before and after light resistance is improved. Have been found, and the present invention has been completed.

That is, the present invention relates to (A) glycidyl (meth) acrylate-modified rubber-reinforced styrene resin 10
0 parts by weight (hereinafter referred to as "parts"), (B) one kind selected from ethylene and (meth) acrylate, unsaturated carboxylic acid, unsaturated carboxylate, carbon monoxide, maleic anhydride and vinyl acetate 0.5 to 15 parts of a polyolefin copolymer obtained by copolymerizing the above, (C) 0.4 to 5 parts of a hindered amine and / or an ultraviolet absorber,
And (D) a rubber-reinforced styrene resin composition containing 0.5 to 3 parts of an antioxidant (Claim 1), and (D) an antioxidant comprising a phenolic antioxidant and a phosphite-based oxidation The rubber-reinforced styrenic resin composition according to claim 1, which is at least one selected from an antioxidant and a sulfur-based antioxidant.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As the glycidyl (meth) acrylate-modified rubber-reinforced styrene resin (hereinafter also referred to as rubber-reinforced styrene resin (A)) as the component (A) used in the present invention, glycidyl (meth) ) Any acrylate-modified rubber-reinforced styrene resin can be used without particular limitation. As specific examples, for example, (a) 10 to 95%, preferably 20 to 80%, of the diene rubber-like polymer and 5 to 90%, preferably 2 to 90% of the monomer mixture
0 to 80% is graft-polymerized, and the monomer mixture is at least one selected from a vinyl cyanide compound, an aromatic vinyl compound, an unsaturated carboxylic acid ester compound and a maleimide compound, and 60 to 99.9%. , Preferably 8
0 to 99.5%, at least one selected from glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate 0.1 to 40%, preferably 0.5 to 2
0% and other vinylic compounds copolymerizable therewith
To 30%, preferably 0 to 19.5%, of a graft copolymer (hereinafter also referred to as copolymer (a)) 10 to 10
0 parts, preferably 20 to 95 parts, and (b) 10 to 40%, preferably 15 to 35% of a vinyl cyanide compound, 50 to 90%, preferably 60 to 85% of an aromatic vinyl compound, and 0 to 40 of a maleimide compound. %, Preferably 0 to 25%, 0 to 40%, preferably 0 to 25% of an unsaturated carboxylic acid ester compound and 0 to 30%, preferably 0 to 30% of another vinyl compound copolymerizable therewith.
0 to 90 parts, preferably 5 to 8 parts, of a vinyl copolymer (hereinafter, also referred to as a copolymer (b)) obtained by polymerizing about 20 to 20%.
And the total amount of the copolymer (a) and the copolymer (b) is 100 parts.

[0010] The copolymer (a) is a component used for matting and impact resistance, and the copolymer (b) is
It is a component used for improving moldability.

When the proportion of the copolymer (a) constituting 100 parts of the rubber-reinforced styrene resin (A) is less than 10 parts (that is, when the proportion of the copolymer (b) exceeds 90 parts),
There tends to be a lack of matting and impact resistance.

When the proportion of the diene rubbery polymer in the copolymer (a) component is less than 10% (ie, when the proportion of the monomer mixture exceeds 90%), the matting properties and impact resistance become poor. When it exceeds 95% (that is, when the proportion of the monomer mixture is less than 5%), the moldability tends to decrease. When the ratio of at least one selected from the group consisting of the vinyl cyanide compound, the aromatic vinyl compound, the unsaturated carboxylic acid ester compound and the maleimide compound is less than 60%, the moldability and impact resistance tend to decrease, If it exceeds 99.9%, the matting property and the impact resistance tend to be insufficient. When the ratio of at least one selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate is less than 0.1%, the mattability tends to be insufficient. Workability and impact resistance tend to decrease. If the ratio of the other vinyl compound copolymerizable with these exceeds 30%, the impact resistance tends to decrease.

If the proportion of the vinyl cyanide compound in the production of the copolymer (b) is less than 10%, the impact resistance tends to decrease, and if it exceeds 40%, thermal coloring tends to occur during molding. There is a tendency. When the proportion of the aromatic vinyl compound is less than 50%, the moldability tends to decrease, and when it exceeds 90%, the impact resistance tends to decrease. Further, the ratio of the maleimide compound is 40
%, The impact resistance tends to decrease. And, the ratio of the unsaturated carboxylic acid ester compound is 40
%, The impact resistance tends to decrease. If the proportion of the other vinyl compound copolymerizable with these exceeds 30%, the impact resistance tends to decrease.

The diene rubbery polymer used for producing the copolymer (a) includes, for example, 20 to 100% of a diene monomer such as butadiene and isoprene, and styrene having copolymerizability with the diene monomer. (Co) polymers with 0 to 80% of monomers such as acrylonitrile, butyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate and butyl methacrylate, for example, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer Polymers, butadiene-butyl acrylate copolymer and the like. These may be used alone or in combination of two or more.

The vinyl cyanide compound constituting the monomer mixture used in the production of the copolymer (a) includes:
For example, acrylonitrile, methacrylonitrile,
Examples of the aromatic vinyl compound include styrene and α-
Examples of unsaturated carboxylic acid ester compounds such as methyl styrene, dimethyl styrene and vinyl toluene include compounds having an alkyl group having 1 to 7 carbon atoms such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. Maleimide compounds such as unsaturated carboxylic acid hydroxyalkyl esters having a hydroxyalkyl group having 1 to 6 carbon atoms such as saturated carboxylic acid alkyl esters, hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate include maleimide and N-methylmaleimide. , N
-Ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (p-
Other vinyl compounds copolymerizable with these, such as methylphenyl) maleimide, include, for example, acrylic acid,
Examples include methacrylic acid, maleic anhydride, vinyl acetate, vinyl ether, and isobutylene. These may be used alone or in combination of two or more.

The copolymer (a) is obtained by graft-polymerizing a monomer mixture to the diene rubbery polymer.
The polymerization method at this time is not particularly limited, and for example, a known emulsion polymerization method using an emulsifier, a polymerization initiator, a chain transfer agent, or the like can be used. The average particle size of the copolymer (a) obtained by emulsion polymerization is not particularly limited, but is usually about 0.05 to 2 μm.

Further, specific examples of vinyl cyanide compounds, aromatic vinyl compounds, maleimide compounds, unsaturated carboxylic acid ester compounds and other vinyl compounds copolymerizable therewith, which are used for producing the copolymer (b) The same one as in the case of the copolymer (a) is used.

Specific examples of the copolymer (b) include, for example, styrene-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, styrene-α-methylstyrene-acrylonitrile copolymer, phenylmaleimide-styrene- Acrylonitrile copolymers can be mentioned, and these are preferable from the viewpoint of moldability and heat resistance.

The component (A) has a reduced viscosity of 0.25 to 1.5 dl / g, preferably 0.4 to 1 d.
1 / g is preferred. If it is less than 0.25 dl / g, mechanical strength such as impact resistance decreases, and if it exceeds 1.5 dl / g, the moldability tends to decrease.

The ethylene (B) used in the present invention, a (meth) acrylate, an unsaturated carboxylic acid,
Polyolefin copolymer obtained by copolymerizing at least one selected from unsaturated carboxylate, carbon monoxide, maleic anhydride and vinyl acetate (hereinafter also referred to as polyolefin copolymer (B)) Means chemical resistance, impact resistance,
It is a component used for improving fluidity and light resistance, and a component having a functional group such as an acrylate ester is preferably used. Such a polymer can be produced by a known method such as a high-pressure radical polymerization method, a solution polymerization method, or an emulsion polymerization method.

Ethylene in the polyolefin copolymer (B) and at least one selected from (meth) acrylates, unsaturated carboxylic acids, unsaturated carboxylate salts, carbon monoxide, maleic anhydride and vinyl acetate The content ratio of ethylene is 60 to 95% by weight (hereinafter, referred to as%), preferably 65 to 90%, (meth) acrylic acid ester, unsaturated carboxylic acid, unsaturated carboxylate, carbon monoxide, The content of one or more selected from maleic anhydride and vinyl acetate is preferably 5 to 40%, more preferably 10 to 30%. If the ethylene content is less than 60%, the impact resistance tends to decrease, and if it exceeds 95%, there is a tendency to peel when melt-kneaded with the component (A).

Examples of the (meth) acrylate include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. As, for example, acrylic acid, methacrylic acid,
As unsaturated carboxylate salts such as fumaric acid, monomethyl maleate, monoethyl maleate, and maleic anhydride, sodium (meth) acrylate,
Examples thereof include potassium (meth) acrylate and rubidium (meth) acrylate.

Specific examples of the polyolefin copolymer (B) include ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene- (meth) acrylate copolymer, and ethylene-vinyl acetate copolymer. Polymer,
Examples include an ethylene-vinyl acetate-carbon monoxide copolymer, an ethylene-maleic anhydride-ethyl acrylate copolymer, and an ethylene-methacrylic acid-acrylate copolymer. These may be used alone or in combination of two or more.

JIS of polyolefin copolymer (B)
-6730 (test temperature 190 ° C, test load 21.18N
(2.16 kg)), the melt flow rate (MFR) is 0.5 to 800 dg / min.
500 dg / min is preferred. If the MFR is less than 0.5 dg / min, the fluidity during molding tends to be too low, and if it exceeds 800 dg / min, the delamination tends to occur.

The amount of the polyolefin copolymer (B) is based on 100 parts of the rubber-reinforced styrene resin (A).
0.5 to 15 parts, preferably 1 to 10 parts. When the amount is less than 0.5 part, the effect of improving chemical resistance, fluidity, impact resistance and light resistance is small, and when it exceeds 15 parts, delamination tends to occur.

The hindered amine of the component (C) used in the present invention is used as a light stabilizer. Examples of the hindered amine include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-).
4-piperidyl) sebacate, 1,2,3,4-tetrakis (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butane, 1,2,3,4-tetrakis (1,2,2 , 6,6-pentamethyl-4-piperidyloxycarbonyl) butane, dimethyl-1-succinate
(2-hydroxyethyl) -4-hydroxy-2,2,
6,6-tetramethylpiperidine polycondensate, 2- (3,
5-di-t-butyl-4-hydroxybenzyl) -2-
bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butylmalonate, 1,2,3,4-butane-
Tetracarboxylic acid and 1,2,2,6,6 pentamethyl-
4-piperidinol and 3,9-bis (2-hydroxy-
1,1-dimethylethyl) -2,4,8,10-tetraoxospiro [5,5] undecane polycondensate, 1-
(3,5-di-tert-butyl-4-hydroxyphenyl) -1,1-bis (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) pentane, 1-
[2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, N, N'-bis (3-aminopropyl) ethylenediamine.2.4 -Bis [N-butyl-N
-(1,2,2,6,6-pentamethyl-4piperidyl) amino] -6-chloro-1,3,5-triazine condensate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine , Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-
2,4-diyl {(2,2,6,6-tetramethyl-
4-piperidyl) imino {hexamethylene} (2,2
6,6-tetramethyl-4-piperidyl) imino}],
Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate; These may be used alone or in combination of two or more.

As the ultraviolet absorber of the component (C) used in the present invention, a benzotriazole-based one is preferable. Specifically, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] 2H-benzotriazole, 2- ( 3,5-di-t
-Butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
-5-chlorobenzotriazole, 2- (3,5-di-
t-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t
-Octylphenyl) benzotriazole, 2- (4,
6-diphenyl-1,3,5-triazin-2-yl)
-5- (hexyl) -oxy-phenol, 2- (4,
6-bis-2,4-dimethylphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxy-phenol and the like. These may be used alone or in combination of two or more.

The hindered amine and the ultraviolet absorber may be used alone or in combination. However, it is preferable to use the hindered amine alone because the discoloration is less.

The amount of component (C) is 0.4 to 5 parts, preferably 0.4 to 3 parts, per 100 parts of rubber-reinforced styrene resin (A). If the amount is less than 0.4 part, the improvement in light resistance is insufficient, and if it exceeds 5 parts, the impact resistance is reduced.

Examples of the antioxidant (D) used in the present invention include well-known phenolic antioxidants, phosphite antioxidants and sulfur antioxidants. These may be used alone,
More than one species may be used in combination.

Examples of the phenolic antioxidants include 2,6-di-t-butyl-p-cresol,
6-diphenyl-4octoxyphenol, stearyl- (3,5-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4-hydroxy-
3,5-di-t-butylphenyl) propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ′,
5'-di-t-butyl-4-hydroxybenzylthio)
1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzylmalonate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4 '-Methylenebis (2,6-
Di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5-bis (4-hydroxy-3-t-
Butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-t-butyl-m-
Cresol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-t-butylphenol),
1,1,3-tris (2-methyl-4-hydroxy-5
-T-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate,
1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butyl) benzyl isocyanurate,
3,5- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate] methane, 1,3
5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, 2
-Octylthio-4,6-di (4-hydroxy-3,5
-Di-t-butyl) phenoxy-1,3,5-triazine, 4,4'-thiobis (6-t-butyl-m-cresol), 2,2'-methylenebis (6-t-butyl-4
-Methylphenol) monoacrylate, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-
Bis (1,1-dimethyl-2-hydroxyethyl) 2
4,8,10-tetraoxaspiro [5,5] undecanebis [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionate].
These may be used alone or in combination of two or more.

The phosphite-based antioxidants include, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite and octyl phosphite.
Diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (Tridecyl)
-1,1,3-tris (2-methyl-5-t-butyl-
4-hydroxyphenyl) butane diphosphite, tetra (C _{12 ~ 15} mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl)
-4,4'-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono-di-mixed nonylphenyl) phosphite Phyte, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) .bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol) .1,6-hexanediol Diphosphite phenyl / 4,4'-isopropylidene diphenol pentaerythritol diphosphite, bis (2,4-di-t-butylphenol) pentaerythritol diphosphite, bis (2,6-di-t-butyl) -4-methylphenyl) pentaerythritol diphosphite, tris [4,4 ' Isopropylidene-bis (2
-T-butylphenol)] phosphite, phenyl.
Diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 4,
4'-isopropiodenbis (2-t-butylphenol) dinonylphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di- (t-butylphenyl) -4,4'-biphenylenediphosphite and the like. These may be used alone,
More than one species may be used in combination.

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl-, dimyristyl- and distearyl- and alkylthiopropionic acids such as butyl-, octyl-, lauryl- and stearyl-. Esters of polyhydric alcohols (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralauryl thiopropionate). These may be used alone or in combination of two or more.

The amount of component (D) is 0.5 to 3 parts, preferably 0.5 to 2 parts, per 100 parts of rubber-reinforced styrene resin (A). If the compounding amount is less than 0.5 part, the matte property before light resistance cannot be maintained after light resistance, and if it exceeds 3 parts, the impact resistance decreases.

The rubber-reinforced styrenic resin (A) may be produced by any polymerization method. For example, there are known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, emulsion-suspension polymerization, and emulsion-bulk polymerization.

When the polymer is recovered from the latex of the rubber-reinforced styrenic resin (A), calcium chloride, magnesium chloride,
Alkaline earth metal salts such as magnesium sulfate, alkali metal salts such as sodium chloride, sodium sulfate, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, or acetic acid, formic acid,
After coagulation of the latex by adding an organic acid such as oxalic acid, it can be carried out by a method of dehydrating and drying. Spray drying can also be used.

Also, hindered amines and / or
An ultraviolet absorber, an antioxidant, and the like can also be added to the rubber-reinforced styrene-based resin (A) latex or slurry in the form of a dispersion.

The rubber-reinforced styrenic resin composition of the present invention may contain, if necessary, a pigment, an antistatic agent, and a well-known pigment.
A lubricant and the like can be appropriately compounded. In particular, organosiloxanes, aliphatic hydrocarbons, esters and amides of higher fatty acids and higher alcohols used in styrene resins,
Lubricants such as tallow can be used to provide higher performance as molding resins. These may be used alone or in combination of two or more.

The rubber-reinforced styrenic resin composition of the present invention can be used for a mixture of a rubber-reinforced styrenic resin (A), a polyolefin copolymer (B) powder and pellets, with a hindered amine and / or an ultraviolet absorber. , An antioxidant, and if necessary, an antistatic agent, a lubricant, a pigment, etc., and a Banbury mixer, a roll mill, a single screw extruder,
It can be manufactured by kneading with a known melt kneader such as a shaft extruder. Further, the produced composition can be formed by a known processing method such as injection molding, extrusion molding, vacuum molding, blow molding and the like.

The rubber-reinforced styrenic resin composition of the present invention has good moldability and colorfastness during molding, and has excellent lightfastness of the molded product, and maintains the matte property before lightfastness even after lightfastness. Can have good mechanical strength, low temperature impact resistance,
It can be suitably used for automotive parts, profile extrusion building materials, and the like.

[0041]

EXAMPLES Hereinafter, the composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

The measurement in the examples and comparative examples was performed by the following method.

As the (average particle diameter) measuring device, Pacific Scientific (PACIFIC SCIE) was used.
NTIFIC) NICOMP MODEL370
The volume average particle diameter was measured by a dynamic light scattering method using a particle diameter analyzer.

(Reduced viscosity [η]) MEK of the obtained resin
30 g of soluble matter 0.3 g / 100 ml DMF solution
Measured in ° C.

(Light fastness) Using a strong energy xenon weather meter manufactured by Suga Test Instruments Co., Ltd., the obtained test piece was irradiated with irradiance of 150 W / m ² , black panel temperature of 8
After irradiation at 3 ° C. and an integrated irradiance of 150 MJ / m ² , the discoloration degree (ΔE) and gloss value (gloss (%)) of the test piece were measured.

As a device for measuring the degree of discoloration, a Z-SENSOR colorimetric colorimeter manufactured by Nippon Denshoku Industries Co., Ltd. was used. The measuring light source was a 12V / 50W halogen lamp, and the light receiving element was a silicon photocell high-speed response type. , Standard light: C2 degree field of view, illumination / light receiving conditions: in accordance with JIS Z-8722.

As a device for measuring the gloss value, a VGS-300A variable-angle gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. was used. The measurement light source was a 5V / 8W halogen lamp, and the light receiving element was a silicon photocell high-speed response type. , Deflection range: incident angle 0 to 85 °
・ Light receiving angle 0 to 85 °, illumination and light receiving conditions: JIS Z-8
741.

The abbreviations in the following table indicate the following contents. GMA: glycidyl methacrylate AN: acrylonitrile St: styrene αMSt: α-methylstyrene MMA: methyl methacrylate PMI: phenylmaleimide Polyolefin-based resin 1: ethylene-ethyl acrylate copolymer manufactured by Mitsui / Dupont Polychemical Co., Ltd.
Brand name EVAFLEX A709 (MFR: 25dg
/ Min, ethylene content: 65%) Polyolefin-based resin 2: Ethylene-methacrylic acid copolymer manufactured by Mitsui-DuPont Polychemical Co., Ltd., trade name
NUCREL N1560 (MFR: 60 dg / min, ethylene content: 85%) Polyolefin resin 3: ethylene-maleic anhydride-ethyl acrylate copolymer manufactured by Sumitomo Chemical Co., Ltd.
Product name BONDINE A8700 (MFR: 125
dg / min, ethylene content: 70%) Hindered amine 1: bis (2,2,6,6-tetramethyl-4-pipedyl) sebacate hindered amine 2: 1,2,3,4-tetrakis (2,2,6) , 6-Pentamethyl-4-pipedyloxycarbonyl) butane Antioxidant 1: 1,3,5-tris (3,5-di-t-
Butyl-4-hydrobenzyl) -s-triazine-2,
4,6-trione antioxidant 2: n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butyl) propionate

Production Example 1 (Rubber reinforced styrene resin (A)
(A) Production of copolymers (a1) to (a4) Stirrer, reflux condenser, nitrogen inlet, monomer inlet,
The reactor described below was charged into a reactor equipped with a thermometer.

Pure water 250 parts Polybutadiene (average particle size 0.1 μm) The amount described in Table 1 Sodium formaldehyde sulfoxylate (SFS) 0.3 parts Ferrous sulfate 0.0025 parts Disodium ethylenediaminetetraacetate (EDTA) 0.01 parts

The reactor was stirred for 60 hours under a nitrogen stream.
The temperature was raised to ° C. After reaching 60 ° C., the monomer mixture shown in Table 1, cumene hydroxyperoxide (CH
A mixture of P) and t-dodecylmercaptan (t-DM) was continuously added dropwise in the amount shown in Table 1 over 5 hours, and after completion of the addition, stirring was continued at 60 ° C. for 1 hour to complete the polymerization.

[0052]

[Table 1]

(B) Production of copolymers (b1) to (b4) Stirrer, reflux condenser, nitrogen inlet, monomer inlet,
The reactor described below was charged into a reactor equipped with a thermometer.

Pure water 250 parts Sodium dodecylbenzenesulfonate (SDBS) 3 parts SFS 0.4 parts Ferrous sulfate 0.0025 parts EDTA 0.01 parts

The reactor was stirred under a stream of nitrogen for 60 hours.
The temperature was raised to ° C. After reaching 60 ° C., the amount of α-methylstyrene (αMSt) shown in Table 2 was charged.
After sufficient emulsification, a mixture of the monomer, CHP and tDM shown in Table 2 was continuously added dropwise in the amount shown in Table 2 over 6 hours, and after completion of the addition, stirring was continued at 60 ° C. for 1 hour to complete the polymerization. did.

[0056]

[Table 2]

(C) Rubber-reinforced styrene resin (A1)
Production of (A5) The copolymer (a) and the copolymer (b) produced above were each mixed in a latex state at a ratio (solid content) shown in Table 3, and this mixed latex was used as an antioxidant. 0.3 parts of a phenolic antioxidant (n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butyl) propionate) is added, coagulated with calcium chloride, and then heated. After dehydration, washing and drying, powders of rubber-reinforced styrene resins (A1) to (A5) containing an antioxidant were obtained.

[0058]

[Table 3]

Examples 1 to 10 (Production and evaluation of rubber-reinforced styrenic resin composition) Rubber-reinforced styrenic resin (A1) produced in (c) above
To (A5), a polyolefin resin, a hindered amine, and an antioxidant in the proportions shown in Table 4, 3 parts of titanium white (CR-60, manufactured by Ishihara Sangyo Co., Ltd.) and carbon black (manufactured by Mitsubishi Chemical Corporation) , # 30) Add 0.03 parts, blend with super mixer, 40m
/ M extruder to produce pellets. A test piece (a flat plate with a grain size of 150 mm × 150 mm × 3 mm) was formed from the pellets by a 150TON injection molding machine under the conditions of a screw rotation speed of 100 rpm and a nozzle set temperature of 270 ° C. Further, the obtained test piece was 70 mm ×
After cutting to a size of 40 mm, light resistance was evaluated. Table 4 shows the results.

[0060]

[Table 4]

Comparative Examples 1 to 5 In the same manner as in Examples 1 to 11, compositions having the main compositions shown in Table 5 were produced and evaluated. Table 5 shows the results.

[0062]

[Table 5]

Since the gloss of the matte ABS resin molded article is very low in the initial stage (before light resistance), a slight increase in gloss impairs the mattability and results in poor appearance. In order to prevent appearance defects, the gloss difference between before and after light fastness is 2
%. All examples are 2%
Although it is before and after, it is 3% or more in the comparative example.

[0064]

The glycidyl (meth) acrylate-modified rubber-reinforced styrenic resin is modified from ethylene and (meth) acrylate, unsaturated carboxylic acid, unsaturated carboxylate, carbon monoxide, maleic anhydride and vinyl acetate. By using a composition containing a polyolefin-based copolymer obtained by copolymerizing with one or more selected kinds, a hindered amine and / or an ultraviolet absorber and an antioxidant, light resistance is greatly improved, It is possible to obtain a molded article that maintains the matte property before light resistance even after light resistance.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/524 C08K 5/524 // (C08L 51/04 23:08)

Claims (2)

[Claims] 1. A glycidyl (meth) acrylate-modified rubber-reinforced styrene resin (100 parts by weight), (B) ethylene, (meth) acrylate, unsaturated carboxylic acid, unsaturated carboxylate, carbon monoxide. , 0.5 to 15 parts by weight of a polyolefin copolymer obtained by copolymerizing at least one selected from maleic anhydride and vinyl acetate, (C) a hindered amine and / or an ultraviolet absorber 0.4 to 5 parts by weight, and (D) an antioxidant.
A rubber-reinforced styrene resin composition containing 5 to 3 parts by weight. 2. The rubber-reinforced styrene resin according to claim 1, wherein (D) the antioxidant is at least one member selected from the group consisting of a phenolic antioxidant, a phosphite antioxidant and a sulfur antioxidant. Composition.