JP2000230104A - Rubber-reinforced styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition where light stability of a glycidyl (meth) acrylate-modified rubber-reinforced styrene-based resin is improved and matting property after fading test can be maintained. SOLUTION: This rubber-reinforced styrene-based resin composition is prepared by formulating (A) 100 pts.wt. glycidyl (meth)acrylatemodified rubber- reinforced styrene-based resin, (B) 1-15 pts.wt. methacrylate resin obtained by polymerizing 30-100 wt.% monomer mixture consisting of 60-100 wt.% methacrylate, 0-40 wt.% aerylate and 0-25 wt.% comonomer in the presence of 0-70 wt.% rubber and having 0.04-0.4 dl/g reduced viscosity ηred measured at 30 deg.C using a solution where the soluble part of the above methacrylate resin is dissolved in dimethylformamide in the concentration of 0.3 g/(100 ml), (C) 0.4-5 pts.wt. hindered amine and/or ultraviolet absorber and (D) 0.5-3 pts.wt. 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-based resin composition which can improve the light resistance of a glycidyl (meth) acrylate-modified rubber-reinforced styrene resin and maintain the matting 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.

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.

Japanese Patent Application Laid-Open No. 9-310004 discloses a method obtained by graft-polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a non-diene rubbery polymer. Thermoplastic polyester, melt flow rate (JIS K6
760) A technique for improving light resistance and the like by blending a high-density polyethylene and a modified polyethylene wax of 3 g / 10 minutes or more is disclosed.

[0006] However, in response to the strict requirement of light resistance, all of the above-mentioned ones are unsatisfactory because of large discoloration and change in resin gloss.

[0007]

The matte ABS resin has improved weather resistance without significantly lowering mechanical strength, moldability, low-temperature impact resistance, and color development resistance during molding, and has improved light resistance. There is also a demand for a technique that can maintain the gloss before light resistance.

[0008]

Means for Solving the Problems As a result of intensive studies in view of the above situation, the present inventors have found that a small amount of a low molecular weight methacrylate resin is added to a glycidyl (meth) acrylate-modified rubber-reinforced styrene resin. By adding a hindered amine and / or 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 light resistance is maintained even after the light resistance. They have found that the previous gloss can be maintained, and have completed the present invention.

That is, the present invention relates to (A) glycidyl (meth) acrylate-modified rubber-reinforced styrene resin 10
(B) rubber 0 to 0 parts by weight (hereinafter referred to as parts)
In the presence of 70% by weight (hereinafter referred to as%), methacrylate 60 to 100%, acrylate 0 to 4
A resin obtained by polymerizing 0% and 30 to 100% of a monomer mixture composed of 0 to 25% of a monomer copolymerizable therewith, wherein a methyl ethyl ketone (hereinafter referred to as MEK) -soluble component of the resin is 0%. The reduced viscosity [η] measured at 30 ° C. using a 0.3 g / 100 ml dimethylformamide (hereinafter referred to as DMF) solution is 0.04 to 0.4 dl / g.
1 to 15 parts of a methacrylate resin, which is (C)
Hindered amine and / or UV absorber 0.4
To 5 parts, and 0.5 to 3 parts of (D) an antioxidant, a rubber-reinforced styrene resin composition (Claim 1),
(B) The rubber contained in the methacrylate resin is
The rubber-reinforced styrene-based resin composition according to claim 1, which is a crosslinked acrylic rubber (claim 2), and the amount of (B) a methacrylate-based resin based on 100 parts of (A) a glycidyl (meth) acrylate-modified rubber-reinforced styrene-based resin. Is 2
The rubber-reinforced styrenic resin composition according to claim 1 or 2 which is 10 parts (claim 3), and wherein the (D) antioxidant is a phenolic antioxidant, a phosphite antioxidant, and a sulfur-based antioxidant. 4. The rubber-reinforced styrene-based resin composition according to claim 1, which is at least one selected from agents.

[0010]

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 a specific example, for example, (a) a diene rubbery polymer 10
~ 95%, preferably 20-80% monomer mixture 5
90%, preferably 20-80%, in which the monomer mixture is at least one selected from the group consisting of a vinyl cyanide compound, an aromatic vinyl compound, an unsaturated carboxylic acid ester compound and a maleimide compound. ~ 9
9.9%, preferably 80 to 99.5%, at least one selected from glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate 0.1 to 40
%, Preferably 0.5 to 20% and 0 to 30%, preferably 0 to 2% of other vinyl compounds copolymerizable therewith.
0% graft copolymer (hereinafter referred to as copolymer (a)
10 to 100 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, Maleimide compound 0 to 40%, preferably 0 to 30%, unsaturated carboxylic acid ester compound 0 to 40%, preferably 0 to 30% and other vinyl compounds copolymerizable therewith 0 to 30%, preferably 0
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%.
0 parts and the total amount of the copolymer (a) and the copolymer (b) is 100 parts.

The copolymer (a) is a component used for providing matting and impact resistance, and the copolymer (b) is used for improving moldability. Component.

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 is a tendency for impact resistance to decrease.

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 impact resistance tends to decrease. If it exceeds 95% (that is, the proportion of the monomer mixture is less than 5%), the moldability tends to decrease. If the proportion of at least one selected from the group consisting of the vinyl cyanide compound, the aromatic vinyl compound, the unsaturated carboxylic acid alkyl ester and the maleimide compound constituting the monomer mixture is less than 60%, the molding processability is deteriorated. When it exceeds 99.9%, the impact resistance tends to decrease. On the other hand, when the ratio of one or more selected from the glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate is less than 0.1%, the matting effect tends to be insufficient, and
%, The moldability 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.

When 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 when it exceeds 40%, thermal coloring occurs during molding. . Further, the ratio of the aromatic vinyl compound is 50%.
If it is less than 90%, the moldability tends to decrease, and 90%
When the ratio exceeds the above range, the impact resistance tends to decrease. Further, when the ratio of the maleimide compound exceeds 40%,
There is a tendency for impact resistance to decrease. If the proportion of the other vinyl compound copolymerizable with these exceeds 30%, the impact resistance tends to decrease.

Examples of the diene rubbery polymer used for producing the copolymer (a) include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-butyl acrylate copolymer, and the like. Is raised. 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) is, for example, acrylonitrile or methacrylonitrile. The aromatic vinyl compound is, for example, styrene or α. Examples of unsaturated carboxylic acid ester compounds such as methylstyrene, dimethylstyrene, and vinyltoluene include alkyl groups having 1 to 7 carbon atoms such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Unsaturated carboxylic acid hydride having a C1-6 hydroxyalkyl group such as unsaturated carboxylic acid alkyl ester, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc. Such as alkoxyalkyl esters,
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-phenylmaleimide, and N- (p-methylphenyl) maleimide. Examples of the vinyl compound include acrylic acid, 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 rubber-like polymer of the component (a), but the polymerization method at this time is not particularly limited.
For example, an emulsion polymerization method using a known emulsifier, polymerization initiator, 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.

Specific examples of the copolymer (a) include those described in Examples described later.

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

Examples of the copolymer (b) include styrene-acrylonitrile copolymer, α-methylstyrene-
Acrylonitrile copolymer, styrene-α-methylstyrene-acrylonitrile copolymer and phenylmaleimide-styrene-acrylonitrile copolymer are preferred from the viewpoint of moldability and heat resistance.

The methacrylate resin (B) used in the present invention (hereinafter also referred to as methacrylate resin (B)) is a component used for improving light resistance. 70%, preferably 10-50%
In the presence of methacrylate 60-100%, preferably 70-100%, acrylate 0-40
%, Preferably 0 to 30%, and 30 to 100%, preferably 50 to 90%, of a monomer mixture consisting of 0 to 25%, preferably 0 to 10% of a monomer copolymerizable therewith. A resin having a MEK-soluble content of 0.1%;
The reduced viscosity [η] measured at 30 ° C. using a 3 g / 100 ml DMF solution is 0.04 to 0.4 dl / g, preferably 0.1 to 0.3 dl / g.

When the proportion of the rubber used in the production of the methacrylate resin (B) exceeds 70% (that is, when the proportion of the monomer mixture is less than 30%), it was produced from the composition of the present invention. The surface properties of the molded article decrease.

Also, a methacrylate resin (B)
When the proportion of the methacrylic acid ester constituting the monomer mixture used for the production of is less than 60%, the heat resistance temperature decreases,
If the ratio of the acrylate exceeds 40%, the transferability of the plasticizer decreases. Further, when the proportion of the other monomer copolymerizable with the methacrylic acid ester and the acrylic acid ester exceeds 25%, the light resistance characteristic of the present component is reduced.

Further, when the reduced viscosity [η] of the methacrylate resin (B) is less than 0.04 dl / g, the impact strength of a molded article made from the composition of the present invention is reduced.
If it exceeds 0.4 dl / g, the effect of improving light resistance cannot be sufficiently obtained.

The M of the rubber-reinforced styrene resin (A)
The reduced viscosity [η] of the EK-soluble matter measured at 30 ° C. using a 0.3 g / 100 ml DMF solution is 0.1 dl / m less than the reduced viscosity [η] of the methacrylate resin (B).
g or more is preferable from the viewpoint of light discoloration resistance.

Examples of the rubber used for producing the methacrylate resin (B) include crosslinked acrylic rubber, ethylene-propylene rubber, silicone rubber, etc., and two or more of them may be used in combination. However, a crosslinked acrylic rubber is preferred in terms of light resistance and workability.

The crosslinked acrylic rubber contains 50 to 99.9% of an alkyl acrylate, 0 to 49.9% of a monomer copolymerizable with the above monomer, and 0.1 to 1 of a crosslinking agent.
It is obtained by polymerizing a 0% mixed monomer.

Examples of the alkyl acrylate used in the production of the crosslinked acrylic rubber include methyl acrylate, ethyl acrylate, propyl acrylate, and the like.
Examples thereof include alkyl acrylates having an alkyl group having 1 to 8 carbon atoms, such as butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These may be used alone or in combination of two or more.

Examples of the monomer copolymerizable with the alkyl acrylate include styrene, α-methylstyrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl acrylate, and the like.
Glycidyl methacrylate, phenylmaleimide, acrylonitrile and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the cross-linking agent used for producing the cross-linked acrylic rubber include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol dimethacrylate, divinyl benzene, divinyl adipate, diallyl phthalate, and the like. Diallyl maleate, allyl acrylate, allyl methacrylate, triallyl cyanurate,
Triallyl isocyanurate and the like. These may be used alone or in combination of two or more.

The particle size of the crosslinked acrylic rubber is 30 to
Preferably it is 800 nm. Examples of a method for increasing the particle diameter include methods such as seed polymerization, acid enlargement, salt enlargement, and addition of an acid group-containing latex.

The methacrylic acid ester contained in the monomer mixture to be grafted onto the rubber such as the crosslinked acrylic rubber has an alkyl group having 1 to 4 carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. And methacrylic acid alkyl esters. These may be used alone or in combination of two or more. Among them, methyl methacrylate is preferred from the viewpoint of light resistance.

Examples of the acrylate contained in the monomer mixture include carbon acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. Acrylic acid alkyl esters having an alkyl group of Formulas 1 to 8 can be mentioned. These may be used alone or in combination of two or more.

Further, the monomers copolymerizable with the methacrylic acid ester and the acrylic acid ester contained in the monomer mixture include, for example, styrene, α-methylstyrene, phenylmaleimide, acrylonitrile and the like.

If necessary, a crosslinking agent may be added to the monomer mixture. Examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate,
Diethylene glycol diacrylate, propylene glycol dimethacrylate, divinyl benzene, divinyl adipate, diallyl phthalate, diallyl malate,
Allyl acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like can be mentioned.

In grafting a rubber such as the above-mentioned crosslinked acrylic rubber, a monomer mixture containing a crosslinking agent is used in the first stage, and a monomer mixture containing no crosslinking agent is used in the second stage. Is preferred from the viewpoint of light resistance.

The methacrylic ester resin (B)
When producing 30 to 100% of the monomer mixture in the presence of 0 to 70% of rubber, a part of the monomer mixture 30 to 100%, for example, 50 to 95%
Can be separately polymerized and mixed.

The amount of the methacrylate resin (B) to be added is 1 to 15 parts, preferably 2 to 10 parts, per 100 parts of the rubber-reinforced styrene resin (A). When the addition amount is less than 1 part, the improvement in light resistance is small, and when it exceeds 15 parts, the impact resistance decreases.

The hindered amine (C) used in the present invention is used as a light stabilizer. As the hindered amine, for example, bis (2,2,
6,6-tetramethyl-4-piperidyl) sebacate,
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 succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-
Tetramethylpiperidine polycondensate, 2- (3,5-di-
Bis (1,2,2,6,6-pentamethyl-4t-butyl-4-hydroxybenzyl) -2-nbutylmalonate
-Piperidyl), 1,2,3,4-butane-tetracarboxylic acid, 1,2,2,6,6 pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl Ethyl) -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-t-butyl-4-hydroxyphenyl)
Propionyloxy] ethyl] -4- [3- (3,5-
Di-tert-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 and the like. These may be used alone or in combination of two or more.

As the ultraviolet absorber (C) used in the present invention, a benzotriazole-based one is preferred. 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 and the like can be mentioned. Can be
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, but it is preferable to use the hindered amine alone since the discoloration is less.

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

As the antioxidant of the component (D) used in the present invention, at least one of generally well-known phenolic antioxidants, phosphite antioxidants, sulfur antioxidants and the like can be used. can give.

The phenolic antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, 2,6
-Diphenyl-4octoxyphenol, stearyl-
(3,5-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4-hydroxy-3,
5-di-tert-butylphenyl) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tert-butyl-4-hydroxy) Benzylthio) 1,3,5-
Triazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, 2,2'-
Methylene bis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], Screw [3,5
-Bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 2,
2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4-tert-butyl-6
-Tert-butylphenol), 1,1,3-tris (2-
Methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-
Hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6
-Dimethyl-3-hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5- (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [ Methylene-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert-butyl ) Phenoxy-1,3,5-
Triazine, 4,4'-thiobis (6-tert-butyl-m
-Cresol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) monoacrylate, triethylene glycol bis [3- (3-tert-butyl-4-
(Hydroxy-5-methylphenyl) propionate],
3,9-bis (1,1-dimethyl-2-hydroxyethyl) 2,4,8,10-tetraoxaspiro [5,5]
And undecanebis [3- (3-tert-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, octyl-
Diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra ( Tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butanediphosphite, tetra ( _C12-15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, tetra (tridecyl)
-4,4'-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-ditert-butyl-4-hydroxyphenyl) phosphite,
Tris (mono / di mixed nonylphenyl) phosphite,
Hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,
4'-butylidenebis (3-methyl-6-tert-butylphenol) -1,6-hexanedioldiphosphitephenyl / 4,4'-isopropylidenediphenol
Pentaerythritol diphosphite, bis (2,4-
Di-tert-butylphenol) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-tert-butylphenol) Phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 4,4'-isopropiodenbis (2-tert-butylphenol) Dinonylphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylene phosphite and the like. These may be used alone or in combination of two or more.

Further, 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 the component (D) is 0.5 to 3 parts, preferably 0.5 to 2 parts, per 100 parts of the rubber-reinforced styrene resin (A). When the addition amount is less than 0.5 part, the matting property after light resistance cannot be maintained, and when it exceeds 3 parts,
Impact resistance decreases.

The rubber-reinforced styrene resin (A) and the methacrylic ester resin (B) may be produced by any polymerization method as long as the composition can be controlled within the range of the present invention.
For example, known bulk polymerization, solution polymerization, suspension polymerization,
Examples of the method include an emulsion polymerization method, an emulsion-suspended polymerization method, and an emulsion-bulk polymerization method. Among them, the production of the methacrylate resin (B) is preferable because the emulsion polymerization method can easily control the reduced viscosity. The production of the rubber-reinforced styrene resin (A) is preferably an emulsion polymerization method.

The methacrylate resin (B) may be produced by using any polymerization initiator, chain transfer agent, emulsifier and the like. As the polymerization initiator, known initiators such as a thermal decomposition initiator such as potassium persulfate and a redox initiator such as Fe-reducing agent-organic peroxide can be used. As the chain transfer agent, known t-dodecyl mercaptan, n-dodecimercaptan, α-methylstyrene dimer, terpinolene and the like can be used. Examples of the emulsifier include fatty acid metal salt-based emulsifiers such as sodium oleate, sodium palmitate and sodium rosinate, sodium dodecylbenzenesulfonate, sodium alkylsulfonate having 12 to 20 carbon atoms, and sodium alkylsulfate having 12 to 20 carbon atoms. And known ones such as dioctyl sodium succinate.

The rubber-reinforced styrenic resin (A) and the methacrylic ester resin (B) vary depending on the respective production methods. For example, they may be in the form of latex, slurry, solution, powder, pellets, or the like. Can be produced as a mixture by combining and mixing the above.

When the polymer is recovered from the latex of the rubber-reinforced styrenic resin (A) or the methacrylate ester resin (B), a conventional method is used, for example, an alkali such as calcium chloride, magnesium chloride or magnesium sulfate is added to the latex. The latex is coagulated by adding an earth metal salt, an alkali metal salt such as sodium chloride or sodium sulfate, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid such as acetic acid, formic acid or oxalic acid. After a while
Dehydration and drying can be performed. 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 latex or slurry of the rubber-reinforced styrene resin (A) or methacrylate ester resin (B) in the form of a dispersion.

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

The rubber-reinforced styrene-based resin composition of the present invention is prepared by mixing a rubber-reinforced styrene-based resin (A), a powder of a methacrylic ester-based resin (B), and a pellet.
A hindered amine and / or an ultraviolet absorber, an antioxidant, a stabilizer, an antistatic agent, a lubricant, a pigment and the like are blended if necessary, and known melting such as a Banbury mixer, a roll mill, a single-screw extruder, and a twin-screw extruder. The mixture can be kneaded by a kneading machine and molded by a known processing method such as injection molding, extrusion molding, vacuum molding, and blow molding.

The rubber-reinforced styrenic resin composition of the present invention has good molding processability and color development resistance during molding, and has excellent light resistance of molded articles, and maintains matting properties before light resistance even after light resistance. It has good mechanical strength and low-temperature impact resistance, and can be suitably used for automobile parts, building materials of profile extrusion, and the like.

[0056]

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

(Reduced Viscosity [η]) MEK-soluble portion of the obtained resin 0.3 g / 100 ml DMF solution at 30 ° C.
Was measured.

(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 and 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 12 V / 50 W 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.

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 shown 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.

[0066]

[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 gas 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, the monomers, CHP and t shown in Table 2
The amount of the mixture of DM was continuously dropped in the amount shown in Table 2 over 6 hours, and after completion of the dropping, stirring was continued at 60 ° C. for 1 hour to complete the polymerization.

[0070]

[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. After adding 0.3 part of a phenolic antioxidant, coagulating with calcium chloride, heating, dehydrating, washing with water, and drying, and powdering a rubber-reinforced styrene resin containing an antioxidant (A1) to (A5). Obtained.

[0072]

[Table 3]

Production Example 2 (Production of Methacrylic Ester Resin (B)) (d) Production of Crosslinked Acrylic Rubber (R1)-(R2) Stirrer, reflux condenser, nitrogen inlet, monomer inlet,
The following components were charged into a reaction vessel equipped with a thermometer in a nitrogen stream.

Pure water 250 parts SFS 0.5 parts Ferrous sulfate 0.003 parts EDTA 0.01 parts Sodium dioctyl sulfosuccinate (SDOSS) 2.0 parts

The reactor was stirred under a stream of nitrogen gas for 40 hours.
The temperature was raised to ° C. After the temperature reached 40 ° C., a mixture of the monomer and CHP shown in Table 4 was continuously added dropwise in the amount shown in Table 4 over 6 hours. After completion of the dropwise addition, stirring was further continued at 40 ° C. for 1 hour to complete the polymerization, and the crosslinked acrylic rubber (R
1) to (R2) were produced.

[0076]

[Table 4]

(E) Graft copolymer (RGP1)
Production of (RGP2) Stirrer, reflux condenser, nitrogen inlet, monomer inlet,
The following components were charged into a reaction vessel equipped with a thermometer in a nitrogen stream.

Pure water 250 parts SFS 0.2 parts Ferrous sulfate 0.001 parts EDTA 0.005 parts SDOSS 0.8 parts Crosslinked acrylic rubber shown in Table 5 (in solid content) Amount shown in Table 5

The reactor was stirred under a stream of nitrogen gas for 60 hours.
The temperature was raised to ° C. After the temperature reached 60 ° C., a mixture of the monomer and CHP shown in Table 5 was continuously added dropwise in an amount shown in Table 5 over 4 hours. After completion of the dropwise addition, stirring was further continued at 60 ° C. for 1 hour to complete the polymerization, and the graft copolymer (RGP
1) to (RGP2) were produced. The average particle size of the crosslinked acrylic rubber used was 60 nm.

[0080]

[Table 5]

(F) Methacrylic acid ester copolymer (M
Synthesis of FP1) to (MFP3) Stirrer, reflux condenser, nitrogen inlet, monomer inlet,
The following components were charged into a reaction vessel equipped with a thermometer in a nitrogen stream.

Pure water 250 parts SFS 0.5 parts Ferrous sulfate 0.003 parts EDTA 0.01 parts SDOSS 2.0 parts

The reactor was stirred under a nitrogen stream for 60 hours.
The temperature was raised to ° C. After the temperature reached 60 ° C., a mixture of the monomer, CHP and tDM shown in Table 6 was added dropwise in the amount shown in Table 6 continuously over 6 hours. After the completion of dropping, further 60 ° C
For 1 hour to complete the polymerization, thereby producing methacrylate copolymers (MFP1) to (MFP3).

[0084]

[Table 6]

(G) Latex blend (methacrylic acid ester resins (B1) to (B5)) The graft copolymer (R) obtained in (e) and (f) above
(GP1)-(RGP2), latexes of methacrylic acid ester copolymers (MFP1)-(MFP3) were uniformly mixed at a ratio shown in Table 7, and 0.3 part of AO-50 was added as a phenolic antioxidant. After coagulation and heat coagulation with an aqueous solution of calcium chloride, washing with water, dehydration and drying, methacrylic acid ester-based resins (B1) to (B1) containing an antioxidant
5) was obtained.

[0086]

[Table 7]

Examples 1 to 10 (Production and evaluation of rubber-reinforced styrenic resin composition) Rubber-reinforced styrenic resin (A1) produced in (c) above
To (A5), the methacrylate resin (B1) to (B5) produced in (G), hindered amine and antioxidant are added at the ratios shown in Tables 8 and 9, and titanium white (manufactured by Ishihara Sangyo Co., Ltd.) , CR-60) and 0.03 part of carbon black (# 30, manufactured by Mitsubishi Chemical Corporation), and blended with a supermixer to obtain 40 m / m
An extruder was used to produce pellets. Using these pellets, a 150 TON injection molding machine was used to rotate the screw at 1
A test piece was molded under the conditions of 00 rpm and a nozzle set temperature of 270 ° C. The light resistance was evaluated using the obtained test pieces.
The results are shown in Tables 8 and 9.

[0088]

[Table 8]

[0089]

[Table 9]

Comparative Examples 1 to 5 In the same manner as in Examples 1 to 10, the compositions shown in Table 10 were produced and evaluated. Table 10 shows the results.

[0091]

[Table 10]

[0092]

According to the present invention, a glycidyl (meth) acrylate-modified rubber-reinforced styrene resin is mixed with a low-molecular methacrylate ester resin and a hindered amine light stabilizer and / or
By blending the ultraviolet absorber and the antioxidant, it is possible to significantly improve the light resistance and maintain the matting property before the light resistance even after the light resistance test.

Claims (4)

[Claims] (A) a glycidyl (meth) acrylate-modified rubber-reinforced styrene-based resin (100 parts by weight)
(B) In the presence of 0 to 70% by weight of rubber, 60 to 100% by weight of methacrylate and 0 to 4% of acrylate
0 to 30% by weight of a monomer mixture comprising 0% by weight and 0 to 25% by weight of a monomer copolymerizable therewith, wherein the resin has a methyl ethyl ketone soluble content of 0.3 g / The reduced viscosity [η] measured at 30 ° C. using a 100 ml dimethylformamide solution is 0.0
1 to 15 parts by weight of a methacrylate resin having a weight of 4 to 0.4 dl / g, 0.4 to 5 parts by weight of (C) a hindered amine and / or an ultraviolet absorber, and (D) 0.5 to 5 parts by weight of an antioxidant. A rubber-reinforced styrene resin composition containing 3 parts by weight. 2. The rubber-reinforced styrenic resin composition according to claim 1, wherein the rubber contained in the (B) methacrylate resin is a crosslinked acrylic rubber. 3. The rubber reinforced rubber according to claim 1, wherein the amount of the methacrylate ester resin (B) is 2 to 10 parts by weight based on 100 parts by weight of the glycidyl (meth) acrylate-modified rubber reinforced styrene resin. Styrene resin composition. 4. The rubber according to claim 1, wherein the (D) antioxidant is at least one member selected from the group consisting of phenolic antioxidants, phosphite antioxidants and sulfur antioxidants. Reinforced styrene resin composition.