TWI572659B - Rubber modified styrene-based resin composition and molding product made therefrom - Google Patents

Description

Rubber modified styrene resin composition and formed molded article thereof

The present invention relates to a resin composition, and more particularly to a rubber-modified styrene-based resin composition and a molded article formed therefrom.

Thermoplastic resins have been widely used in various fields such as household appliances, mechanical parts, office supplies, electronic components, and the automotive industry. The raw material used for the plastic molded article for electrical equipment or household goods may be a rubber-modified styrene resin or a polycarbonate resin. Among them, a rubber-modified styrene-based resin such as a diene-based rubber-modified styrene-based resin or an acrylate-based rubber-modified styrene-based resin, and a diene-based rubber-modified styrene-based resin such as styrene- Acrylonitrile-Butadiene-Styrene Resin (ABS) has excellent characteristics such as high surface hardness, good chemical resistance, good impact resistance and easy molding.

However, the diene rubber in the styrene-acrylonitrile-butadiene resin is easily broken by ultraviolet irradiation, resulting in poor weather resistance. In order to solve the above problems, the olefinic rubber is often used in the industry to improve the weather resistance of the rubber-modified styrene resin.

The acrylate-based rubber-modified styrene-based resin is a ternary graft copolymer comprising acrylonitrile, styrene, and an acrylate-based rubber. Compared with the diene rubber-modified styrene resin, the acrylate-based rubber-modified styrene-based resin is more difficult to replace the diene-based rubber with an acrylate-based rubber having a small double bond content, thereby greatly improving weather resistance. Cracked by light or heat. Further, since the weather resistance of the acrylate-based rubber-modified styrene-based resin is about 10 times higher than that of the diene-based rubber-modified styrene-based resin, it can be directly used outdoors.

However, the impact resistance of the acrylate-based rubber-modified styrene-based resin is inferior to that of the diene-based rubber-modified styrene-based resin, so when the acrylate-based rubber and the diene-based rubber are used in combination, the rubber is modified into benzene. The impact resistance of the entire vinyl resin is lowered.

Therefore, the use of the acrylate-based rubber to improve the weather resistance of the rubber-modified styrene-based resin and how to achieve the impact resistance of the rubber-modified styrene-based resin as a whole have become a problem that those skilled in the art are eager to break through.

The present invention provides a rubber-modified styrene-based resin composition and a molded article formed from the above-mentioned composition, which can improve not only weather resistance but also impact resistance, and the impact resistance has a multiplying effect.

The rubber-modified styrene-based resin composition of the present invention comprises a continuous phase formed of 77% by weight to 84% by weight of a styrene-based copolymer and a dispersed phase formed by 16% by weight to 23% by weight of rubber particles, wherein The rubber particles include a diene rubber and an acrylate rubber, and the content of the diene rubber is 24% by weight to 90% by weight based on the total content of the rubber particles of 100% by weight, the acrylate rubber The content of the acrylate rubber particles is from 0.2 μm to 0.2 μm and a bimodal distribution of from 0.35 μm to 0.5 μm, and the diene rubber particles are contained in an amount of from 10% by weight to 76% by weight. The weight average particle size is a bimodal distribution.

In an embodiment of the invention, the particles of the acrylate rubber have a weight average particle diameter of from 0.1 μm to 0.2 μm and a bimodal distribution of from 0.4 μm to 0.48 μm.

In an embodiment of the invention, the weight average particle diameter of the particles is from 0.1 μm to 0.2 μm, based on 100% by weight of the acrylate rubber, of 60% by weight to 80% by weight, based on the weight of the particles. The content of the average particle diameter of from 0.35 μm to 0.5 μm is from 20% by weight to 40% by weight.

In an embodiment of the invention, the particles of the diene rubber have a weight average particle diameter of 0.2 μm to 0.4 μm and 0.8 μm to 1.2 μm.

In an embodiment of the invention, the content of the diene rubber is 24% by weight to 76% by weight based on the total content of the rubber particles of 100% by weight, and the content of the acrylate rubber is 24% by weight. % to 76% by weight.

In an embodiment of the invention, the content of the diene rubber is 24% by weight to 64% by weight based on the total content of the rubber particles of 100% by weight, and the content of the acrylate rubber is 36% by weight. % to 76% by weight.

In an embodiment of the invention, the weight average particle diameter of the particles of the diene rubber is 0.05 μm to 0.15 μm and 0.2 μm to 0.4 μm.

In an embodiment of the invention, the content of the diene rubber is 60% by weight to 90% by weight based on the total content of the rubber particles, and the content of the acrylate rubber is 10% by weight. Up to 40% by weight.

The molded article of the present invention is formed of the rubber-modified styrene resin composition as described above.

Based on the above, the rubber-modified styrene resin composition of the present invention includes a diene rubber and an acrylate rubber, and the particles of the acrylate rubber have a bimodal distribution of a specific weight average particle diameter range, and The particles of the diene rubber also have a bimodal distribution of weight average particle diameters, so that the molded article obtained by the resin composition is excellent in weather resistance and impact resistance.

The above described features and advantages of the present invention will become more apparent and understood.

Hereinafter, embodiments of the invention will be described in detail. However, these embodiments are illustrative, and the disclosure of the present invention is not limited thereto.

In an embodiment of the invention, the rubber-modified styrene resin composition comprises a continuous phase formed of a styrene copolymer and a dispersed phase formed by rubber particles, wherein 77% by weight to 84% by weight is a styrene system The continuous phase formed by the copolymer, 16% by weight to 23% by weight, is a dispersed phase formed by rubber particles. The rubber particles include a diene rubber and an acrylate rubber. The content of the diene rubber is from 24% by weight to 90% by weight based on the total content of the rubber particles of 100% by weight, and the content of the acrylate-based rubber is from 10% by weight to 76% by weight. Wherein the weight average particle diameter of the particles of the acrylate rubber is a bimodal distribution of 0.1 μm to 0.2 μm and 0.35 μm to 0.5 μm, and the weight average particle diameter of the particles of the diene rubber is also a double peak. distributed. The invention will be described in detail below.

Source of acrylate rubber

The source of the acrylate-based rubber in the present embodiment may be an acrylate-based rubber-modified styrene-based resin, for example, a dispersion formed of a styrene-based copolymer and a dispersion of an acrylate-based rubber graft copolymer. The composition of the phase.

For example, an acrylonitrile-styrene-acrylate rubber (ASA) resin may include 55% by weight to 80% by weight of a styrene-acrylonitrile-based copolymer, and 20% by weight to 45% by weight of an acrylate. A rubber graft copolymer. From another viewpoint, the acrylate-based rubber-modified styrene-based resin includes, for example, 15% by weight to 25% by weight of the acrylonitrile-based monomer unit, and 55% by weight to 65% by weight of the styrene-based monomer unit and 15 From 5% by weight to 25% by weight of the acrylate monomer unit.

The styrene-acrylonitrile-based copolymer may be obtained by polymerization of 60% by weight to 74% by weight of a styrene-based monomer and 26% by weight to 40% by weight of an acrylonitrile-based monomer. The polymerization reaction can be carried out by a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method, and a bulk polymerization method or a solution polymerization method is preferred. Specific examples of the styrene-based monomer include: styrene, α-methylstyrene, p-t-butylstyrene, p-methylstyrene, o-methylstyrene, m-methylbenzene Ethylene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene or bromostyrene, among which styrene or α-methylstyrene is preferred. Specific examples of the acrylonitrile-based monomer include acrylonitrile or α-methyl acrylonitrile, and the like, with acrylonitrile being preferred.

The acrylate monomer unit, the styrene monomer unit, and the acrylonitrile monomer unit are respectively referred to as an acrylate monomer, a styrene monomer, and an acrylonitrile monomer after polymerization and graft reaction. A repeating structural unit in an acrylate-based rubber graft copolymer or in a styrene-acrylonitrile-based copolymer.

Further, the method for producing the styrene-acrylonitrile-based copolymer preferably comprises carrying out a polymerization reaction using a reactor which can be subjected to continuous bulk or solution polymerization. The reactor comprises a columnar flow reactor, a fully mixed reactor (CSTR), or a tube reactor containing a static mixing element, etc., wherein a fully mixed reactor is preferred. The reactor may be used in one or two or more in combination.

The solvent used in the solution polymerization reaction is, for example, toluene, ethylbenzene, methyl ethyl ketone or the like. Preferably, the solution polymerization has an operating temperature in the range of from 70 ° C to 140 ° C; more preferably, the solution polymerization has an operating temperature in the range of from 90 ° C to 130 ° C.

In the preparation of the styrene-acrylonitrile-based copolymer, a thermal polymerization method may be employed or a polymerization initiator may be added to the reaction, wherein the polymerization initiator is, for example but not limited to, a hydrogenoperoxide compound, for example: Tert-butyl hydroperoxide, Isopropylcumyl hydroperoxide, etc.; Peroxyketal compounds, for example: 1,1-double- Tributylperoxy-3,3,5-trimethylcyclohexane (1,1-Di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane), 2,2-di(4,4- Di(1,2-di(tert-butylperoxycyclohexyl)propane); etc.; Diacyl peroxides, for example: Dilauroyl peroxide, Decanoyl peroxide, Dibenzoyl peroxide (BPO), etc.; Peroxyesters compounds, for example, Third Ding T-butylperoxypivalate, 2,5-dimethyl-2,5-di(2-B 1,5-Dimethyl-2,5-di(2-ethylhexanoylperoxyhexane), etc.; peroxy ketals, for example, 4,4-diperoxylated tert-butyl-pentanoic acid -4,4-di-t-butyl peroxy valeric acid n-butyl ester (TX-17); peroxycarbonates, for example: 2-ethylhexyl third pentyl Tert-Amylperoxy 2-ethylhexyl carbonate, tert-Butylperoxy 2-ethylhexyl carbonate, etc.; and azo with nitro and cyclohexane Compounds, etc. The polymerization initiator may be added in an amount ranging from 0.01 part by weight to 2.0 parts by weight, preferably 0.01 part by weight to 1.0, based on 100 parts by total of the styrene monomer and the acrylonitrile monomer. Parts by weight.

The molecular weight of the prepared styrene-acrylonitrile-based copolymer is preferably from 60,000 to 400,000.

The above acrylate rubber graft copolymer may be obtained by graft polymerization of 100 parts by weight of an acrylate rubber emulsion with 50 parts by weight to 100 parts by weight of a monomer mixture, wherein the monomer mixture may comprise 65% by weight to 75 wt% of a styrene monomer and 25 wt% to 35 wt% of an acrylic monomer. The foregoing monomer mixture may be added in a single addition, in portions, continuously, or in portions of various monomers in the monomer mixture. Further, the acrylate-based rubber graft copolymer may include two or more acrylate-based rubber graft copolymers having different weight average particle diameters.

The method for preparing the acrylate rubber emulsion preferably comprises directly polymerizing the acrylate monomer as a main component by an emulsion polymerization method. The acrylate monomer is, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate. , 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, acrylic acid A dialkyl ester or the like, wherein n-butyl acrylate is preferred.

In addition, the method for preparing the acrylate rubber emulsion may further include adding a bridging agent when the polymerization reaction is carried out. The bridging agent is, for example but not limited to, ethylene diacrylate, butylene diacrylate, divinyl benzene, butylene glycol dimethacrylate, dimethacrylate, trimethylolpropane tris(meth)acrylate Ester, allyl methacrylate (AMA), diallyl methacrylate, diallyl maleate, diallyl fumarate, diallyl citrate, methacrylic acid Allyl ester, triallyl cyanurate, triallyl cyanurate, acrylate of tricyclodecenol, diacrylate of polyalkylene glycol, etc., wherein the aforementioned bridging agent can be used alone Use two or more types together. In one embodiment, the bridging agent is preferably used in an amount of from 0.1% by weight to 10% by weight based on the total amount of the acrylate monomer and the bridging agent and 100% by weight.

The average particle diameter of the above acrylate rubber emulsion can be controlled by polymerization conditions, for example, polymerization temperature, initiator, emulsifier, amount and type of activator, and method of adding monomers.

The initiator may be various known radical polymerization initiators, and the initiator may be added in a single addition or continuously or incrementally. In detail, specific examples of the initiator include: Di-tert-butyl peroxide, layroyl peroxide, octadecane-based peroxide (oleyl peroxide), ditoluoyl peroxide, dicumyl peroxide, tert-butyl peroxide, diperic acid Di-tert-butyl diperphthalate, tert-butyl peracetate, tert-butyl perbenzoate, isopropyl peroxycarbonate (isopropyl peroxy dicarbonate), 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, Tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di(tributylperoxy)-hexyl-3-tert-butyl hydroperoxide (2, 5-dimethyl-2,5-di(tert-butyl peroxy)hexane-3-tert-butyl hydroperoxide), cumene hydroperoxide, p-menthane peroxidation Hydrogen (p-menthane hydroperoxide), cyclopentane hydroperoxide, diisopropylbenzene hydroperoxide, p-tert-butylcumene Hydroperoxide), pinane hydroperoxide, 2,5-dimethyl-hexane-2,5-dihydroperoxide or mixtures thereof .

The starting agent is preferably used in an amount of from 0.01 part by weight to 5 parts by weight based on 100 parts by total of the total of the monomer mixture.

Specific examples of the emulsifier preferably include: various carboxylic acid salts of sodium succinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, rose acid soap, etc.; sodium dihexyl sulfosuccinate Any of various sulfonates such as alkyl sulfate or sodium alkylbenzenesulfonate; and an anionic emulsifier such as sodium polysulfonate. The emulsifier is preferably used in an amount of from 1 part by weight to 10 parts by weight based on 100 parts by total of the total of the monomer mixture.

Specific examples of the activator include ferrous sulfate, sodium formaldehyde sulfoxylate, disodium edetate, sodium tetrasodium pyrophosphate, and the like. The activator is preferably used in an amount of from 1 part by weight to 10 parts by weight based on 100 parts by total of the total of the monomer mixture.

The graft molecular weight of the above acrylate rubber graft copolymer can also be changed by polymerization temperature, initiator, emulsifier, activator, type and amount of chain transfer agent, monomer addition method and the like. The adjustment wherein the reaction temperature of the graft polymerization is below 90 ° C, especially between 25 ° C and 40 ° C is preferred. The types and amounts of the initiator, emulsifier and activator are as described above. Specific examples of the chain transfer agent include: n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan (n-dodecyl mercaptan) Or tert-dodecyl mercaptan. The chain transfer agent is preferably used in an amount of from 0.01 part by weight to 0.1 part by weight based on 100 parts by total of the total of the monomer mixture.

While carrying out a graft reaction to form an acrylate-based rubber graft copolymer, styrene is polymerized with acrylonitrile to produce a second styrene-acrylonitrile-based copolymer. The molecular weight of the second styrene-acrylonitrile-based copolymer is preferably from 10,000 to 100,000.

Further, specific examples of the styrene monomer and the acrylonitrile monomer contained in the above monomer mixture are the same as those of the styrene monomer and the acrylonitrile monomer in which the styrene-acrylonitrile copolymer is prepared. , will not repeat them here.

The method for producing the acrylate-based rubber-modified styrene-based resin of the present embodiment is not particularly limited, and a general mixing method such as styrene-acrylonitrile-based copolymer and acrylate-based rubber graft copolymer can be used. Mix it. In one embodiment, the general mixing method comprises: dry blending with a commonly used Hanschel mixer, followed by melt mixing with a mixer such as an extrusion mixer, a kneader or a Banbury mixer.

In one embodiment, the particles of the acrylate rubber have a weight average particle diameter of from 0.1 μm to 0.2 μm and a bimodal distribution of from 0.35 μm to 0.5 μm.

In another embodiment, the particles of the acrylate-based rubber have a weight average particle diameter of from 0.1 μm to 0.2 μm, and the content is from 60% by weight to 80% by weight based on 100% by weight of the acrylate rubber. The particles have a weight average particle diameter of from 0.35 μm to 0.5 μm in an amount of from 20% by weight to 40% by weight.

Source of diene rubber

The source of the diene rubber in the present embodiment may be a diene rubber modified styrene resin, for example, a continuous phase formed of a styrene copolymer and a dispersion of a diene rubber graft copolymer. The composition of the phase.

The method for producing the diene rubber-modified styrene resin may be a simultaneous grafting method or a grafting and kneading method. The simultaneous grafting method comprises the steps of: adding a rubber component to a polymerization process of a styrene copolymer to participate in a polymerization reaction to obtain a diene rubber modified styrene resin; and the grafting and kneading method is a rubber group A part (for example, a general rubber or rubber graft copolymer, particularly a rubber graft copolymer) is directly mixed with a styrene copolymer to obtain a diene rubber modified styrene resin.

The polymerization reaction in the method for producing the diene rubber-modified styrene resin is, for example, not limited to, a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a bulk suspension polymerization method, or the like. For example, graft polymerization can be carried out by a known method (for example, emulsion polymerization) by using a monomer component containing a styrene monomer and other copolymerizable monomers copolymerizable with the styrene monomer. It is obtained on a diene rubber polymer.

More specifically, the diene rubber modified styrene resin may be a diene rubber polymer (solid content), a monomer component containing a styrene monomer and an acrylonitrile monomer, and a selectivity. Additives such as an emulsifier, a polymerization initiator or a chain transfer agent are added by graft polymerization.

The above diene rubber polymer is obtained, for example, by an emulsion polymerization method from a rubber component and other copolymerizable monomers which are selectively added, or may be further subjected to a hypertrophy treatment after the emulsion polymerization reaction. Other copolymerizable monomers such as, but not limited to, styrene or acrylonitrile, and the like. The diene rubber polymer may be used singly or in combination, and examples thereof include, but not limited to, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-diene rubber, acrylonitrile rubber, and the like. A preferred diene rubber polymer is a butadiene rubber.

The styrenic monomers may be used singly or in combination, such as, but not limited to, styrene, α-methylstyrene, α-chlorostyrene, p-tert-butylstyrene, p-methylstyrene, o-chloro Styrene, p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-trichlorostyrene or 2,5-dibromostyrene. Preferred styrenic monomers may be selected from the group consisting of styrene, alpha-methyl styrene or combinations of the foregoing.

The acrylonitrile-based monomers may be used singly or in combination, such as, but not limited to, acrylonitrile, α-methacrylonitrile, and the like. A preferred acrylonitrile monomer is acrylonitrile.

Other copolymerizable monomers may be used singly or in combination, such as, but not limited to, acrylate monomers, methacrylate monomers, and monofunctional maleimide monomers.

Specific examples of the acrylate-based monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, polyethylene glycol diacrylate, and the like. A preferred acrylate monomer is butyl acrylate.

Specific examples of the methacrylate monomer include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, Cyclohexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, ethylene dimethacrylate (ethylene Dimethacrylate), neopentyl dimethacrylate, and the like. Preferred methacrylate monomers are methyl methacrylate and butyl methacrylate.

Specific examples of the monofunctional maleimide-based monomer include: maleic imine, N-methyl maleimide, N-isopropyl maleimide, N-butyl mala Yttrium, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenyl horse醯imine, N-2-methylphenylmaleimide, N-2,3-dimethylphenylmaleimide, N-2,4-dimethylphenyl mala Imine, N-2,3-diethylphenylmaleimide, N-2,4-diethylphenylmaleimide, N-2,3-dibutylphenyl Malay Yttrium, N-2,4-dibutylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-2,3-dichlorophenylmale Yttrium, N-2,4-dichlorophenylmaleimide, N-2,3-dibromophenylmaleimide or N-2,4-dibromophenylmalazone Amines, etc. A preferred monofunctional maleimide monomer is N-phenylmaleimide.

In addition, other copolymerizable monomers, such as acrylic monomers (eg, acrylic acid, methacrylic acid), anhydrous maleic acid, anhydrous methyl maleic acid, anhydrous methyl fumaric acid, fumaric acid (fumaric acid), an unsaturated carboxylic acid compound such as itaconic acid, and an esterification monomer thereof (for example, dimethyl fumarate, dibutyl itaconate), ethylene, propylene, 1-butyl Alkene, 1-pentene, 4-methyl 1-pentene, ethylene chloride, vinyl chloride fork, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, butadiene, propenylamine, Isobutenylamine, vinyl acetate, ethyl vinyl ether, methyl vinyl ketone, triallyl isocyanate, and the like.

The diene rubber modified styrene resin in the present embodiment is, for example, selected from an acrylonitrile-butadiene-styrene copolymer (ABS) or a methyl methacrylate-butadiene-styrene copolymer. (MBS). Preferably, the diene rubber modified styrene resin is an acrylonitrile-butadiene-styrene copolymer.

Rubber modified styrene resin composition

The method for preparing the rubber-modified styrene-based resin composition in the present embodiment is not particularly limited, and a general mixing method can be employed, for example, the acryl-based rubber-modified styrene-based resin and the diene-based rubber are modified. The styrene-based resin is uniformly mixed or obtained by uniformly mixing a styrene-based copolymer, an acrylate-based rubber graft copolymer, and a diene rubber graft copolymer. The general mixing method includes dry mixing by a generally used Hanschel mixer, followed by melt mixing by a mixer such as an extrusion mixer, a kneader or a Banbury mixer.

In one embodiment, the particles of the acrylate rubber have a weight average particle diameter of 0.1 μm to 0.2 μm and a bimodal distribution of 0.35 μm to 0.5 μm; the weight average particles of the particles of the diene rubber The diameters range from 0.2 μm to 0.4 μm and from 0.8 μm to 1.2 μm. Moreover, the content of the diene rubber is from 24% by weight to 76% by weight based on the total content of the rubber particles of 100% by weight, and the content of the acrylate-based rubber is from 24% by weight to 76% by weight; preferably, based on The total content of the rubber particles is 100% by weight, the content of the diene rubber is 24% by weight to 64% by weight, and the content of the acrylate-based rubber is 36% by weight to 76% by weight.

In another embodiment, the particles of the acrylate rubber have a weight average particle diameter of from 0.1 μm to 0.2 μm and a bimodal distribution of from 0.35 μm to 0.5 μm; the average weight of the particles of the diene rubber The particle size ranges from 0.05 μm to 0.15 μm and from 0.2 μm to 0.4 μm. Further, the content of the diene rubber is from 60% by weight to 90% by weight based on the total content of the rubber particles of 100% by weight, and the content of the acrylate-based rubber is from 10% by weight to 40% by weight.

additive

The rubber-modified styrene-based resin composition of the present embodiment can selectively add various additives depending on the subsequent demand. The additive may be used singly or in combination, such as, but not limited to, an antioxidant, a plasticizer, a processing aid, an ultraviolet stabilizer, a UV absorber, a filler, a fortifier, a colorant, a slip agent, a charge inhibitor, and a flame retardant. Agent, flame retardant, heat stabilizer, coupling agent, etc.

The antioxidant may be used singly or in combination, and the antioxidant is, for example but not limited to, a phenol-based antioxidant, a thioether-based antioxidant, or a phosphorus-based antioxidant. The phenolic antioxidant may be used singly or in combination, and the phenolic antioxidant such as, but not limited to, octadecyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate (3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, type: antioxidant IX-1076), triethylene glycol bis[3-(3-tert-butyl-5-methyl) 4-hydroxyphenyl)propionate], tetrakis[methylene-3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl- 6-(3-Tertibutyl-2-hydroxy-6-methylbenzyl)-4-methylphenyl acrylate, 2,2'-methylene-bis(4-methyl-6- (2,2'-methylenebis(4-methyl-6-tert-butylphenol), type: antioxidant 2246), 2,2'-thiobis(4-methyl-6-third Phenol), 2,2'-thio-diethylene-bis[3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate], or 2,2'-B Diamine-bis[ethyl-3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate] and the like. The thioether-based antioxidants may be used singly or in combination, and the thioether-based antioxidants such as, but not limited to, distearyl thiodipropionate, dipalmitosulfur dipropionate, pentaerythritol-tetra-( --dodecyl-thiopropionate, or dioctadecyl sulfide, and the like. The phosphorus-based antioxidant may be used singly or in combination, and the phosphorus-based antioxidant is selected from a phosphite-containing phosphorus-based antioxidant or a phosphate-containing phosphorus-based antioxidant. The phosphite-containing phosphorus-based antioxidants such as, but not limited to, tris(nonylphenyl) phosphite, dodecyl phosphite, 4,4'-butylene bis(3-methyl-6- Tert-butylphenyl-bistridecylphosphite) or tris(2,4-t-butylphenyl)phosphite, and the like. The phosphate-containing phosphorus-based antioxidant such as, but not limited to, tetrakis(2,4-t-butylphenyl)-4,4'-extended biphenyl phosphate, or 9,10-dihydro-9- Oxygen-10-phosphate phenoxy-10-oxygen and the like.

The slip agent may be used singly or in combination, and a slip agent such as, but not limited to, a metal soap such as calcium stearate, magnesium stearate, lithium stearate or the like, ethylene bis-stearamide (abbreviation) EBA), pentaerythritol stearate (PETS), methylene distearylamine, palmitate, butyl stearate, palmitate stearate, pentaerythritol tetra-fatty acid ester, polyacrylic acid A compound such as an acid alcohol tristearate, n-docosic acid or stearic acid, a polyethylene wax, a octadecanoic acid wax, a carnuba wax or a petroleum wax.

The content of the additive is preferably in the range of 0.01 part by weight to 20 parts by weight based on 100 parts by weight of the rubber-modified styrene resin composition.

The additive may be added during the graft polymerization reaction, after the graft polymerization reaction, before the coagulation, or during the preparation of the acrylate rubber modified styrene resin and the diene rubber modified styrene resin. .

A molded article according to another embodiment of the present invention is formed of the rubber-modified styrene resin composition as described above. The method for producing the molded article is not particularly limited herein, and may be kneading, processing, or a combination of the above processes. The kneading and processing can be carried out in a known manner and will not be described again.

The rubber-modified styrene-based resin composition of the present invention will be more specifically described below with reference to several experiments. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively based on the experiments described below.

<Materials used in the examples and comparative examples>

1. PW-997S (ASA resin produced by Chi Mei Industrial Co., Ltd.): the acrylate rubber content is 21% by weight, and the weight average particle diameter of the acrylate rubber particles is 0.12 μm and 0.46 μm; wherein, based on the acrylate rubber The content is 100% by weight, the weight average particle diameter of the particles is 0.12 μm, the content is 70% by weight, and the weight average particle diameter of the particles is 0.46 μm, and the content is 30% by weight.

2. PA-747H (ABS resin produced by Chi Mei Industrial Co., Ltd.): the diene rubber content is 16% by weight, and the weight average particle diameter of the diene rubber particles is 0.3 μm and 1.0 μm; wherein, based on the diene rubber The content is 100% by weight, the content of the particles having a weight average particle diameter of 0.3 μm is 95% by weight, and the content of the particles having a weight average particle diameter of 1.0 μm is 5% by weight.

3. PA-709 (ABS resin produced by Chi Mei Industrial Co., Ltd.): the diene rubber content is 21% by weight, and the weight average particle diameter of the diene rubber particles is 0.1 μm and 0.3 μm; wherein, based on the diene rubber The content is 100% by weight, the content of the particles having a weight average particle diameter of 0.1 μm is 52% by weight, and the content of the particles having a weight average particle diameter of 0.3 μm is 48% by weight.

4. ASA-1 represents an acrylate-based rubber-modified styrene-based resin in which the acrylate-based rubber content is 21% by weight, and the acrylate-based rubber particles have a weight average particle diameter of 0.46 μm.

4-1. Preparation of ASA-1

68 parts by weight of styrene, 32 parts by weight of acrylonitrile, 8 parts by weight of ethylbenzene, 0.01 parts by weight of 1,1-bis-tert-butylperoxy-3,3,5-trimethylcyclohexane The alkane and 0.15 parts by weight of the raw material of the third-dodecyl mercaptan are mixed and continuously supplied to two series-type fully mixed continuous reactors each having a volume of 40 liters in two reactors. The temperature was maintained at 110 ° C and 115 ° C, respectively, and the pressure of the reactor was maintained at 4 kg / cm ² , fed into the reactor at 35 kg / hr, the overall conversion rate was about 50%. After the end of the polymerization, the obtained copolymer solution is heated by a preheater, and then the unreacted monomer and other volatiles are removed by devolatilization in a vacuum degassing tank, and then granulated and granulated to obtain a desired one. Styrene-acrylonitrile copolymer (AS-1).

Next, 99.0 parts by weight of n-butyl acrylate, 1.0 part by weight of allyl methacrylate, 3.0 parts by weight of dioctyl sulfosuccinate, and 1.0 part by weight of a third butyl hydroperoxide solution (concentration) 70 wt%), 3.0 parts by weight of a ferrous sulfate solution (concentration: 0.2 wt%), 3.0 parts by weight of a sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), and 4000.0 parts by weight of distilled water at a reaction temperature of 65 ° C The reaction was carried out for 7 hours to obtain an acrylate rubber emulsion having a weight average particle diameter of 0.4 μm (conversion ratio of about 99%, solid content of about 38%).

100.0 parts by weight of the above acrylate rubber emulsion (dry weight) having a weight average particle diameter of 0.4 μm, 37.6 parts by weight of styrene, 16.1 parts by weight of acrylonitrile, and 4.0 parts by weight of dioctyl sulfosuccinate 1.0 part by weight of cumene hydroperoxide, 3.0 parts by weight of a ferrous sulfate solution (concentration: 0.2 wt%), 3.0 parts by weight of a sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), and 2000.0 parts by weight of distilled water are mixed. Graft polymerization was carried out in which styrene and acrylonitrile were added to the reaction system in a continuous manner over 5 hours. After completion of the graft polymerization, an acrylate-based rubber graft emulsion having a weight average particle diameter of 0.46 μm was obtained. After the calcium chloride is coagulated, dehydrated, and then dried to a moisture content of 2% or less, the desired acrylate rubber graft copolymer can be obtained. (Rubber content: 65% by weight, rubber weight average particle diameter: 0.46 μm)

In a dry state, 67.5 wt% of the above styrene-acrylonitrile copolymer (AS-1), 32.5 wt%, was used as a biaxial extruder (Model: ZPT-25, manufacturer: Zeji Industry Co., Ltd.). The acrylate-based rubber graft copolymer having a weight average particle diameter of 0.46 μm and 2.0% by weight of a slip agent were kneaded at a kneading temperature of 220 °C. Then, after extruding by a twin-axis extruder, the desired acrylate-based rubber-modified styrene-based resin (ASA-1) was obtained.

5. ASA-2 represents an acrylate-based rubber-modified styrene-based resin in which the acrylate-based rubber content is 21% by weight, and the acrylate-based rubber particles have a weight average particle diameter of 0.12 μm.

5-1. Preparation of ASA-2

99.0 parts by weight of n-butyl acrylate, 1.0 part by weight of allyl methacrylate, 5.0 parts by weight of dioctyl sulfosuccinate, 2.0 parts by weight of a solution of a third butyl hydroperoxide (concentration 70 wt) %), 3.0 parts by weight of a ferrous sulfate solution (concentration: 0.2 wt%), 3.0 parts by weight of a sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), and 4000.0 parts by weight of distilled water are reacted at a reaction temperature of 60 ° C. The acrylate rubber emulsion having a weight average particle diameter of 0.1 μm was obtained in an hour (conversion ratio: about 99%, solid content: about 38%).

100.0 parts by weight of the above acrylate rubber emulsion (dry weight) having a weight average particle diameter of 0.1 μm, 70.0 parts by weight of styrene, 30.0 parts by weight of acrylonitrile, and 6.0 parts by weight of dioctyl sulfosuccinate 1.0 part by weight of cumene hydroperoxide, 3.0 parts by weight of a ferrous sulfate solution (concentration: 0.2 wt%), 3.0 parts by weight of a sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), and 3000.0 parts by weight of distilled water are mixed. Graft polymerization was carried out in which styrene and acrylonitrile were added to the reaction system in a continuous manner over 5 hours. After completion of the graft polymerization, an acrylate-based rubber graft emulsion having a weight average particle diameter of 0.12 μm can be obtained. After the calcium chloride is coagulated, dehydrated, and then dried to a moisture content of 2% or less, the desired acrylate rubber graft copolymer can be obtained. (The rubber content is 50% by weight, and the rubber weight average particle diameter is 0.12 μm)

In a dry state, 60% by weight of the aforementioned styrene-acrylonitrile copolymer (AS-1), 40% by weight, of a biaxial extruder (Model: ZPT-25, manufacturer: Zeji Industry Co., Ltd.) The acrylate-based rubber graft copolymer having a weight average particle diameter of 0.12 μm and 2.0% by weight of a slip agent were kneaded at a kneading temperature of 220 °C. Then, after extrusion by a biaxial extruder, the desired acrylate-based rubber modified styrene resin (ASA-2) can be obtained.

6. ABS-1 represents a diene rubber modified styrene resin in which the content of the diene rubber is 16% by weight, and the weight average particle diameter of the diene rubber particles is 0.3 μm.

6-1. Preparation of ABS-1

150.00 parts by weight of 1,3-butadiene, 15.00 parts by weight of potassium persulfate solution (concentration 1 wt%), 2.00 parts by weight of potassium oleate, 0.13 parts by weight of ethylene glycol dimethacrylate and 190.00 The parts by weight of distilled water was reacted at a reaction temperature of 65 ° C for 14 hours to obtain a diene rubber emulsion having a weight average particle diameter of 0.1 μm (conversion ratio of about 94%, solid content of about 36%).

90.00 parts by weight of n-butyl acrylate, 10.00 parts by weight of methacrylic acid, 0.50 parts by weight of potassium persulfate solution (concentration: 1 wt%), 0.50 parts by weight of sodium lauryl sulfate solution (concentration: 10 wt%) 1.00 parts by weight of n-dodecyl mercaptan and 200.00 parts by weight of distilled water were reacted at a reaction temperature of 75 ° C for 5 hours to obtain a carboxylic acid group-containing polymer flocculant emulsion having a conversion of about 95% and a pH of 6.0. .

Thereafter, 3 parts by weight (dry weight) of a carboxylic acid group-containing polymer flocculant was used to ferment 100 parts by weight of the diene rubber latex, and the obtained rubber emulsion had a pH of 8.5, and the rubber weight average particle diameter thereof. It is about 0.3 μm.

Further, 300.0 parts by weight of the above-mentioned enlarged rubber emulsion (dry weight), 75.0 parts by weight of styrene, 25.0 parts by weight of acrylonitrile, 2.0 parts by weight of thirteen-dodecyl mercaptan, and 3.0 parts by weight of isopropyl Benzene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 0.9 parts by weight of sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), and 3.0 parts by weight of ethylenediaminetetraacetic acid solution (concentration 0.25) Gt%), the above-mentioned hypertrophized rubber emulsion is graft-polymerized with a styrene acrylonitrile copolymer to produce a diene rubber graft copolymer. The prepared diene rubber graft copolymer emulsion is coagulated with calcium chloride, and then dehydrated and dried to less than 2% to obtain a desired diene rubber graft copolymer (rubber content: 75% by weight) , rubber weight average particle size of 0.3 μm).

In a dry state, 78.625% by weight of the aforementioned styrene-acrylonitrile copolymer (AS-1) and 21.375% by weight were obtained by a two-axis extruder (Model: ZPT-25, manufacturer: Zeji Industry Co., Ltd.). The diene rubber graft copolymer having a weight average particle diameter of 0.3 μm and 2.0% by weight of a slip agent were kneaded at a kneading temperature of 220 °C. Then, after extruding by a biaxial extruder, the desired diene rubber modified styrene resin (ABS-1) can be obtained.

7. ABS-2 (manufactured by Shanghai Takahashi, model ABS 8434): The content of the diene rubber is 16% by weight, and the weight average particle diameter of the diene rubber particles is 1.0 μm.

8. ABS-3 represents a diene rubber modified styrene resin in which the content of the diene rubber is 21% by weight, and the weight average particle diameter of the diene rubber particles is 0.1 μm.

8-1. Preparation of ABS-3

150.00 parts by weight of 1,3-butadiene, 15.00 parts by weight of potassium persulfate solution (concentration 1 wt%), 2.00 parts by weight of potassium oleate, 0.13 parts by weight of ethylene glycol dimethacrylate and 190.00 The parts by weight of distilled water was reacted at a reaction temperature of 65 ° C for 14 hours to obtain a diene rubber emulsion having a weight average particle diameter of 0.1 μm (conversion ratio of about 94%, solid content of about 36%).

Further, 100.0 parts by weight of the aforementioned diene rubber emulsion (dry weight), 75.0 parts by weight of styrene, 25.0 parts by weight of acrylonitrile, 2.0 parts by weight of thirteen-dodecylmercaptan, and 3.0 parts by weight of Propylene benzene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration: 0.2 wt%), 0.9 parts by weight of sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), and 3.0 parts by weight of ethylenediaminetetraacetic acid solution (concentration) 0.25 wt%), the aforementioned diene rubber emulsion was graft-polymerized with a styrene acrylonitrile copolymer to produce a diene rubber graft copolymer. The prepared diene rubber graft copolymer emulsion is coagulated with calcium chloride, and then dehydrated and dried to less than 2% to obtain a desired diene rubber graft copolymer (the rubber content is 50% by weight). , rubber weight average particle size of 0.1 μm).

In a dry state, 58% by weight of the aforementioned styrene-acrylonitrile copolymer (AS-1), 42% by weight, of a biaxial extruder (Model: ZPT-25, manufacturer: Zeji Industry Co., Ltd.) The diene rubber graft copolymer having a weight average particle diameter of 0.1 μm and 2.0% by weight of a slip agent were kneaded at a kneading temperature of 220 °C. Then, after extruding by a biaxial extruder, the desired diene rubber modified styrene resin (ABS-3) can be obtained.

<Single beam impact strength>

First, according to the preparation method of each example and each comparative example, a test sample having a size of 80×10 mm and a thickness of 4 mm (the test piece has a V-shaped score) is prepared, and the test sample prepared according to the Charpy Impact test method of ISO179 is measured. Impact strength. The measurement results are listed in Tables 1 and 2.

<Examples 1 to 10>

Examples 1 to 10 are rubber modified styrene resin compositions prepared by mixing two resin pellets in a biaxial extruder according to the distribution ratios listed in Table 1, respectively, and impacting them. The test results of the strength are shown in Table 1.

Table 1         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Instance 1 </td><td> Instance 2 </td ><td> Instance 3 </td><td> Instance 4 </td><td> Instance 5 </td><td> Instance 6 </td><td> Instance 7 </td><td> Instance 8 </td><td> Instance 9 </td><td> Instance 10 </td></tr><tr><td> PW-997S (RC-21%) </td><td> Weight </td><td> 70 </td><td> 60 </td><td> 50 </td><td> 40 </td><td> 40 </td><td> 30 < /td><td> 30 </td><td> 20 </td><td> 20 </td><td> 10 </td></tr><tr><td> PA-747H (RC -16%) </td><td> parts by weight </td><td> 30 </td><td> 40 </td><td> 50 </td><td> 60 </td>< Td> — </td><td> 70 </td><td> — </td><td> 80 </td><td> — </td><td> — </td></tr ><tr><td> PA-709 (RC-21%) </td><td> Parts by weight</td><td> — </td><td> — </td><td> — < /td><td> — </td><td> 60 </td><td> — </td><td> 70 </td><td> — </td><td> 80 </td ><td> 90 </td></tr><tr><td> AP </td><td> parts by weight</td><td> 14.7 </td><td> 12.6 </td>< Td> 10.5 </td><td> 8.4 </td><td> 8.4 </td><td> 6.3 </td><td> 6.3 </td><td> 4.2 </td><td> 4.2 </td><td> 2.1 </td></tr><tr><td> BP </td><td> parts by weight</td><td> 4.8 </td><td> 6.4 </ Td><td> 8.0 </td><td> 9.6 </td><td> 12.6 </td><td> 11.2 </td><td> 14.7 </td><td> 12.8 </td> <td> 16.8 </td><td> 18.9 </td></tr><tr><td> RC(total) </td><td> parts by weight</td><td> 19.5 </td ><td> 19.0 </td><td> 18.5 </td><td> 18.0 </td><td> 21.0 </td><td> 17.5 </td><td> 21.0 </td>< Td> 17.0 </td><td> 21.0 </td><td> 21.0 </td></tr><tr><td> AP </td><td> % by weight </td><td> 75.4 </td><td> 66.3 </td><td> 56.8 </td><td> 46.7 </td><td> 40.0 </td><td> 36.0 </td><td> 30.0 < /td><td> 24.7 </td><td> 20.0 </td><td> 10.0 </td></tr><tr><td> BP </td><td> % by weight </td ><td> 24.6 </td><td> 33.7 </td><td> 43.2 </td><td> 53.3 </td><td> 60.0 </td><td> 64.0 </td>< Td> 70.0 </td><td> 75.3 </td><td> 80.0 </td><td> 90.0 </td></tr><tr><td> Physicality-Charpy (Notched) </td ><td> KJ/m²</td><td> 44.8 </td><td> 45.6 </td><td> 43.7 </td><td> 42.9 </td ><td> 44 </td><td> 42.5 </td><td> 45.6 </td><td> 39 </td><td> 44.6 </td><td> 43.8 </t d></tr></TBODY></TABLE>AP: Acrylate rubber BP: Diene rubber R.C: Total rubber content       

In the results of Table 1, Examples 1 to 10 contained 16% by weight to 23% by weight of rubber particles (RC (total)); wherein, based on the total content of the rubber particles (AP + BP) was 100% by weight, The content (BP) of the diene rubber is from about 24% by weight to 90% by weight, the content (AP) of the acrylate rubber is from 10% by weight to about 76% by weight, and due to the acrylate rubber particles The weight average particle diameter is a bimodal distribution, and the weight average particle diameter of the particles of the diene rubber is also bimodal, thereby making the rubber-modified styrene resin composition of Examples 1 to 10 excellent in resistance. Impact characteristics.

Specifically, the weight average particle diameter of the diene rubber particles contained in Examples 1 to 4, 6, and 8 is a bimodal distribution of 0.3 μm and 1.0 μm; based on the total content of the rubber particles (AP+BP) 100% by weight, the content (BP) of the diene rubber contained in Examples 1 to 4, 6, and 8 is limited to the range of 24% by weight to 76% by weight, and the content of the acrylate-based rubber to be contained (AP) ) is limited to the range of 24% by weight to 76% by weight, wherein Examples 1 to 4, 6 further limit the content (BP) of the diene rubber contained in the range of 24% by weight to 64% by weight, The content of the acrylate-based rubber (AP) was limited to the range of 36% by weight to 76% by weight, and exhibited higher impact strength than the impact strength measured in Example 8.

<Comparative Examples 1 to 8>

The preparation methods of the rubber-modified styrene-based resin compositions of Comparative Examples 1 to 8 were the same as those of Examples 1 to 10 except that Comparative Examples 1 to 8 were prepared in accordance with the ratios of the components listed in Table 2, The impact strength test results are shown in Table 2.

Table 2         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Comparative Example 1 </td><td> Comparative Example 2 < /td><td> Comparative Example 3 </td><td> Comparative Example 4 </td><td> Comparative Example 5 </td><td> Comparative Example 6 </td><td> Comparative Example 7 < /td><td> Comparative Example 8 </td></tr><tr><td> PW-997S (RC-21%) </td><td> Parts by weight</td><td> 100 < /td><td> 80 </td><td> — </td><td> — </td><td> — </td><td> 20 </td><td> 20 </td ><td> 20 </td></tr><tr><td> PA-747H (RC-16%) </td><td> parts by weight</td><td> — </td>< Td> 20 </td><td> 100 </td><td> 80 </td><td> 80 </td><td> — </td><td> — </td><td> — </td></tr><tr><td> ASA-1 (RC-21%) </td><td> Parts by weight</td><td> — </td><td> — < /td><td> — </td><td> 20 </td><td> — </td><td> — </td><td> — </td><td> — </td ></tr><tr><td> ASA-2 (RC-21%) </td><td> Parts by weight</td><td> — </td><td> — </td>< Td> — </td><td> — </td><td> 20 </td><td> — </td><td> — </td><td> — </td></tr ><tr><td> ABS-1 (RC-16%) </td><td> Parts by weight</td><td> — </td><td> — </td><td> — < /td>< Td> — </td><td> — </td><td> 80 </td><td> — </td><td> — </td></tr><tr><td> ABS -2 (RC-16%) </td><td> Parts by weight</td><td> — </td><td> — </td><td> — </td><td> — < /td><td> — </td><td> — </td><td> 80 </td><td> — </td></tr><tr><td> ABS-3 (RC -21%) </td><td> parts by weight</td><td> — </td><td> — </td><td> — </td><td> — </td>< Td> — </td><td> — </td><td> — </td><td> 80 </td></tr><tr><td> AP </td><td> Weight </td><td> 21.0 </td><td> 16.8 </td><td> 0.0 </td><td> 4.2 </td><td> 4.2 </td><td> 4.2 < /td><td> 4.2 </td><td> 4.2 </td></tr><tr><td> BP </td><td> parts by weight</td><td> 0.0 </td ><td> 3.2 </td><td> 16.0 </td><td> 12.8 </td><td> 12.8 </td><td> 12.8 </td><td> 12.8 </td>< Td> 16.8 </td></tr><tr><td> RC(total) </td><td> parts by weight</td><td> 21.0 </td><td> 20.0 </td> <td> 16.0 </td><td> 17.0 </td><td> 17.0 </td><td> 17.0 </td><td> 17.0 </td><td> 21.0 </td></ Tr><tr><td> AP </td><td> wt% </td><td> 100.0 </td><td> 84.0 </td><td> 0.0 </td><td> 24.7 </td><td> 24.7 </td>< Td> 24.7 </td><td> 24.7 </td><td> 20.0 </td></tr><tr><td> BP </td><td> wt% </td><td> 0.0 </td><td> 16.0 </td><td> 100.0 </td><td> 75.3 </td><td> 75.3 </td><td> 75.3 </td><td> 75.3 < /td><td> 80.0 </td></tr><tr><td> Physicality-Charpy (Notched) </td><td> KJ/m²</td>< Td> 18.3 </td><td> 31.2 </td><td> 37.3 </td><td> 33 </td><td> 36.3 </td><td> 32.7 </td><td> 19.6 </td><td> 4.8 </td></tr></TBODY></TABLE>

In the results of Table 2, Comparative Examples 1 to 8 also contained 16% by weight to 23% by weight of rubber particles (RC (total)) in the rubber-modified styrene-based resin composition, but the impact strength test results were compared. For Examples 1 through 10, it was significantly worse. For example, Comparative Examples 1 and 3 have only a single resin, and since the acrylate-based rubber particles of Comparative Example 1 have a disadvantage of poor impact resistance, even if the weight average particle diameter thereof has a bimodal distribution, the measured impact strength is obtained. Still very low. Although the impact resistance characteristics of Comparative Example 3 were superior to those of Comparative Example 1, the impact strength test results of the two were significantly inferior to those of Examples 1 to 10.

The rubber-modified styrene-based resin composition of Comparative Example 2 contains the two resin compositions as in Example 1, but the content (BP) of the diene rubber therein is less than 24% by weight, and the content of the acrylate-based rubber ( Since AP) is more than 76% by weight, the impact strength of the rubber-modified styrene-based resin composition of Comparative Example 2 as a whole is rather inferior.

Comparative Examples 4 to 8 each contained a resin composition having a diene rubber and an acrylate rubber, but none of the rubber compositions in the two resin compositions had a bimodal distribution, so even rubber The content ratio was within the range of the above examples, and the impact strengths exhibited by Comparative Examples 4 to 8 were still poor.

In summary, the rubber-modified styrenic resin composition of the present invention comprises a continuous phase formed by 77% by weight to 84% by weight of a styrene-based copolymer and 16% by weight to 23% by weight of rubber particles. a dispersed phase in which the content of the diene rubber is from 24% by weight to 90% by weight based on the total content of the rubber particles, and the content of the acrylate rubber is from 10% by weight to 76% by weight, and the acrylate system is The weight average particle diameter of the rubber particles is a bimodal distribution of 0.1 μm to 0.2 μm and 0.35 μm to 0.5 μm, and the weight average particle diameter of the particles of the diene rubber is also a bimodal distribution. The rubber-modified styrene resin composition of the present invention is improved in weather resistance by the above-described rubber-modified styrene-based resin having a bimodal distribution and having a weight average particle diameter, and the resin composition as a whole is also considered. It has excellent impact resistance and impact resistance, and it has a multiplier effect.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

no.

Claims (8)

A rubber-modified styrene-based resin composition comprising: a continuous phase formed by 77% by weight to 84% by weight of a styrene-based copolymer; and a dispersed phase formed by 16% by weight to 23% by weight of rubber particles, wherein The rubber particles include diene rubber particles and acrylate rubber particles, and the content of the diene rubber particles is 24% by weight to 90% by weight based on 100% by weight of the total content of the rubber particles, and the acrylic acid The content of the ester rubber particles is 10% by weight to 76% by weight, and the weight average particle diameter of the acrylate rubber particles is a bimodal distribution of 0.1 μm to 0.2 μm and 0.35 μm to 0.5 μm, and the diene system The weight average particle diameter of the rubber particles is a bimodal distribution of 0.2 μm to 0.4 μm and 0.8 μm to 1.2 μm. A rubber-modified styrene-based resin composition comprising: a continuous phase formed by 77% by weight to 84% by weight of a styrene-based copolymer; and a dispersed phase formed by 16% by weight to 23% by weight of rubber particles, wherein The rubber particles include diene rubber particles and acrylate rubber particles, and the content of the diene rubber particles is 24% by weight to 90% by weight based on 100% by weight of the total content of the rubber particles, and the acrylic acid The content of the ester rubber particles is from 10% by weight to 76% by weight, and the weight average particle diameter of the acrylate rubber particles is from 0.1 μm to 0.2 μm. And a bimodal distribution of 0.35 μm to 0.5 μm, and the weight average particle diameter of the diene rubber particles is a bimodal distribution of 0.05 μm to 0.15 μm and 0.2 μm to 0.4 μm. The rubber-modified styrene-based resin composition according to the above item 1, wherein the particles of the acrylate-based rubber have a weight average particle diameter of 0.1 μm to 0.2 μm and 0.4 μm to 0.48 μm. The bimodal distribution. The rubber-modified styrene-based resin composition according to the first or second aspect of the invention, wherein the weight average particle diameter is from 0.1 μm to 0.2 μm based on 100% by weight of the acrylate rubber particles. The content of the acrylate-based rubber particles is from 60% by weight to 80% by weight, and the content of the acrylate-based rubber particles having a weight average particle diameter of from 0.35 μm to 0.5 μm is from 20% by weight to 40% by weight. The rubber-modified styrene-based resin composition according to claim 1, wherein the content of the diene rubber particles is from 24% by weight to 76% by weight based on 100% by weight of the total content of the rubber particles. And the content of the acrylate rubber particles is from 24% by weight to 76% by weight. The rubber-modified styrene-based resin composition according to claim 5, wherein the content of the diene rubber particles is 24% by weight to 64% by weight based on 100% by weight of the total content of the rubber particles. And the content of the acrylate rubber particles is from 36% by weight to 76% by weight. The rubber-modified styrene-based resin composition according to claim 2, wherein the diene-based rubber is based on 100% by weight of the total content of the rubber particles. The content of the gum particles is from 60% by weight to 90% by weight, and the content of the acrylate-based rubber particles is from 10% by weight to 40% by weight. A molded article is formed from the rubber-modified styrene resin composition according to any one of claims 1 to 7.