KR101445089B1 - Polycarbonate Resin Composition With Excellent Colorability, Impact Resistance and Scratch Resistance - Google Patents

Abstract

The polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a modified acrylic copolymer; And (C) a transparent rubber-modified aromatic vinyl-based copolymer, and is excellent in coloring property, impact resistance and scratch resistance.

Description

[0001] The present invention relates to a polycarbonate resin composition excellent in coloring property, impact resistance and scratch resistance,

The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a polycarbonate resin composition excellent in coloring property, impact resistance and scratch resistance.

Recently, there have been increasing instances of using differentiated designs in the housing of electric / electronic products, household appliances, office automation products, or mobile phone products or automobile materials. Especially, there have been many attempts to show a high quality product using a high-gloss texture. However, it has been difficult to realize such a characteristic only by the material itself, and thus, such characteristics have been implemented using a paint.

However, in the case of using a coating, it is required to undergo various processes such as a base coat, a top coat, a middle coat, and a bottom coat, and since the defect rate due to the process itself is high, manufacturing costs are increased and it is difficult to recycle the defective product. In addition, the coating process is a typical carbon dioxide generating process, and the amount of harmful volatile components (VOC) generated is high, and efforts have been made to reduce it.

As a result, there is a steady increase in demand for materials that can be applied to unpainted materials, but materials that satisfy both deep color rendering, scratch resistance, and impact resistance have not been developed to date.

On the other hand, scratch resistance and impact resistance are mutually interchangeable, and when one is improved, the other is necessarily lowered. Particularly, when an impact modifier is used for improving impact resistance, the scratch resistance is reduced and the coloring property is also reduced.

In order to solve such a problem of unbalance between physical properties, the prior arts such as Patent Publication 10-2010-0073548 and Patent Publication No. 10-2011-0063091 disclose a resin composition in which a polycarbonate resin and an acrylic resin are alloyed Have been disclosed. However, in the case of the compositions prepared from these, the effect of improving the coloring property for the high-gloss texture was not large. The present inventors have developed a polycarbonate resin composition which is excellent in coloring property, impact resistance and scratch resistance by adding a modified acrylic copolymer and a transparent rubber modified aromatic vinyl copolymer to a polycarbonate resin It is early.

It is an object of the present invention to provide a polycarbonate resin composition for non-coating.

Another object of the present invention is to provide a polycarbonate resin composition excellent in coloring property.

It is still another object of the present invention to provide a polycarbonate resin composition excellent in impact resistance.

It is still another object of the present invention to provide a polycarbonate resin composition excellent in scratch resistance.

It is still another object of the present invention to provide a polycarbonate resin composition excellent in coloring property, impact resistance and scratch resistance.

The above and other objects of the present invention can be achieved by the present invention described below.

The polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a modified acrylic copolymer; And (C) a transparent rubber-modified aromatic vinyl-based copolymer.

In one embodiment of the present invention, the polycarbonate resin (A) is contained in an amount of 25 to 94% by weight, the modified acrylic copolymer (B) is contained in an amount of 1 to 70% by weight, The copolymer (C) is contained in an amount of 5 to 20% by weight.

In one embodiment of the present invention, the modified acrylic copolymer (B) includes a unit derived from an acrylate or methacrylate containing an aliphatic cyclic or aromatic hydrocarbon group.

In one embodiment of the present invention, the modified acrylic copolymer (B) is obtained by polymerizing (b1) an acrylate or methacrylate containing an aliphatic cyclic or aromatic hydrocarbon group, and (b2) a monofunctional unsaturated monomer.

In one embodiment of the present invention, 5 to 95% by weight of the acrylate or methacrylate (b1) containing the aliphatic cyclic or aromatic hydrocarbon group is used, and the monofunctional unsaturated monomer (b2) is used in an amount of 5 to 95% Is used.

In one embodiment of the present invention, the acrylate or methacrylate (b1) comprising the aliphatic cyclic or aromatic hydrocarbon group is represented by the following formula (2), (3) or combinations thereof:

(2)

Wherein m is an integer from 0 to 10; X is a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group or a substituted or unsubstituted C6 to C30 aryl group; Y is hydrogen or a methyl group;

(3)

Wherein m is an integer from 0 to 10; X is a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group or a substituted or unsubstituted C6 to C30 aryl group; Y is hydrogen or a methyl group; Z is oxygen (O) or sulfur (S).

In one embodiment of the present invention, the acrylate or methacrylate (b1) comprising the aliphatic cyclic or aromatic hydrocarbon group is selected from the group consisting of cyclohexyl acrylate or methacrylate, ethyl phenoxy acrylate or methacrylate, Phenyl acrylate or methacrylate, 2-ethylaminophenyl acrylate or methacrylate, phenyl acrylate or methacrylate, benzyl acrylate or methacrylate, 2-phenylethyl acrylate or methacrylate, 3-phenyl Propyl acrylate or methacrylate, 4-phenylbutyl acrylate or methacrylate, 2-2-methylphenyl ethyl acrylate or methacrylate, 2-3-methylphenyl ethyl acrylate or methacrylate, 2-4-methylphenyl Ethyl acrylate or methacrylate, 2- (4-propylphenyl) ethyl acrylate Ethyl acrylate or methacrylate, 2- (4-methoxyphenyl) ethyl acrylate or methacrylate, 2- (4-cyclohexylphenyl) ethyl acrylate or methacrylate, 2- 2- (3-chlorophenyl) ethyl acrylate or methacrylate, 2- (4-chlorophenyl) ethyl acrylate or methacrylate, 2- ) Ethyl acrylate or methacrylate, 2- (4-bromophenyl) ethyl acrylate or methacrylate, 2- (3-phenylphenyl) ethyl acrylate or methacrylate, 2- Ethyl acrylate or methacrylate, and mixtures thereof.

In one embodiment of the present invention, the monofunctional unsaturated monomer (b2) is selected from the group consisting of an acrylate or methacrylate containing an aliphatic cyclic hydrocarbon group, an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, an unsaturated monomer including a hydroxyl group, Unsaturated amide-based monomers, unsaturated imide-based monomers, unsaturated nitrile-based monomers, aromatic vinyl-based monomers, and mixtures thereof.

In one embodiment of the present invention, the refractive index of the modified acrylic copolymer (B) is 1.495 to 1.590.

In one embodiment of the present invention, the modified acrylic copolymer (B) has a weight average molecular weight of 5,000 to 50,000 g / mol.

In one embodiment of the present invention, the transparent rubber-modified aromatic vinyl-based copolymer (C) comprises a core comprising a rubbery polymer and a core comprising an acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer, (C1) a graft copolymer comprising a shell formed by graft polymerization of an aromatic vinyl monomer and an aromatic vinyl monomer; And a (c2) non-graft copolymer including a unit derived from an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer.

In one embodiment of the present invention, the graft copolymer (c1) is contained in an amount of 5 to 50% by weight, and the graft copolymer (c2) is contained in an amount of 50 to 95% by weight.

In one embodiment of the present invention, the graft copolymer (c1) has an average particle size of the rubbery polymer of 0.10 to 0.30 m.

In one embodiment of the present invention, the rubbery polymer is at least one selected from the group consisting of butadiene rubber, acrylic rubber, ethylene-propylene copolymer rubber, butadiene-styrene copolymer rubber, acrylonitrile-butadiene copolymer rubber, isoprene rubber, ethylene- Copolymer rubbers, polyorganosiloxane-polyalkyl (meth) acrylate rubber composites, and mixtures thereof.

In one embodiment of the present invention, the shell includes an inner shell and an outer shell, and the outer shell includes a unit derived from an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer.

In one embodiment of the present invention, the inner shell is obtained by polymerizing the unsaturated nitrile monomer and the aromatic vinyl monomer, and the outer shell comprises the acrylic acid alkyl ester monomer, the methacrylic alkyl ester monomer, The mixture was polymerized.

In one embodiment of the present invention, the inner shell is obtained by polymerizing the acrylic acid alkyl ester monomer or the methacrylic acid alkyl ester monomer, the unsaturated nitrile monomer and the aromatic vinyl monomer, and the outer shell comprises the acrylic acid An alkyl ester monomer or the methacrylic acid alkyl ester monomer, the unsaturated nitrile monomer and the aromatic vinyl monomer.

In one embodiment of the present invention, the graft copolymer (c1) comprises 30 to 70% by weight of the core, 15 to 55% by weight of a unit derived from the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer, 1 to 5% by weight of a unit derived from an unsaturated nitrile-based monomer, and 5 to 35% by weight of a unit derived from the aromatic vinyl-based monomer.

In one embodiment of the present invention, the polycarbonate resin composition is prepared by mixing 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber-modified aromatic vinyl copolymer (C) D) 0 to 5 parts by weight of syndiotactic polystyrene.

In one embodiment of the present invention, the polycarbonate resin composition is prepared by mixing 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber-modified aromatic vinyl copolymer (C) e1) 0.1 to 10 parts by weight of a siloxane-based surface modifier, (e2) 0.1 to 5 parts by weight of a fatty acid amide-based surface modifier, or a mixture thereof.

In one embodiment of the present invention, the polycarbonate resin composition may contain at least one of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a compatibilizer, a lubricant, an antistatic agent, An additive selected from the group consisting of dyes, flame retardants, flame retardant adjuvants, anti-drip agents, weathering stabilizers, ultraviolet absorbers, ultraviolet screening agents and mixtures thereof.

In one embodiment of the present invention, the polycarbonate resin composition further contains carbon black as a pigment, and has an L value of 26.5 to 28.0 as measured under a D65 light source using CCM (Computer Color Matching) equipment according to ASTM D1925.

In one embodiment of the present invention, the polycarbonate resin composition has a notched Izod impact strength of from 40 to 65 kgf · cm / cm in a 3.175 mm thick specimen measured according to ASTM D256.

In one embodiment of the present invention, the polycarbonate resin composition is prepared by injection molding a 2 mm thick specimen in a pin point gate mold, placing a metal tip with a diameter of 10 mm on the gate of the specimen, Is measured at free fall from a height of 70 cm and the rate of gate breakage is less than 50%.

In one embodiment of the present invention, the polycarbonate resin composition has a scratch width of 275 to 300 m measured according to the BSP test, and a pencil hardness of not less than HB measured at a load of 500 g according to ASTM D3362.

The polycarbonate resin composition according to the present invention is excellent in coloring property, impact resistance and scratch resistance.

FIG. 1 is a photograph of a specimen prepared according to Example 2 and Comparative Example 2, in which a weight of 2 kg was dropped free from a height of 70 cm, and a gate breakage rate was measured.

Hereinafter, the present invention will be described in detail.

The polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a modified acrylic copolymer; And (C) a transparent rubber-modified aromatic vinyl-based copolymer.

(A) Polycarbonate resin

In the present invention, the polycarbonate resin is not limited. For example, an aliphatic polycarbonate resin, an aromatic polycarbonate resin, a copolycarbonate resin, a copolyester carbonate resin, a polycarbonate-polysiloxane copolymer resin, or a mixture thereof may be used as the polycarbonate resin. The polycarbonate resin may have a linear or branched structure.

In one embodiment of the present invention, the polycarbonate resin can be prepared by reacting (a1) an aromatic dihydroxy compound with (a2) carbonate precursor.

(a1) an aromatic dihydroxy compound

The aromatic dihydroxy compound is a compound represented by the following formula (1) or a mixture thereof.

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, halogen, or a C 1 to C 8 alkyl group; a and b are each independently an integer of 0 to 4; Z is a single bond, a C1 to C8 alkylene group, a C2 to C8 alkylidene group, a C5 to C15 cycloalkylene group, a C5 to C15 cycloalkyl Denote -S-, -SO-, SO ₂ -, -O-, or -CO-.

Examples of the aromatic dihydroxy compound represented by Formula 1 include bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis Methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1- 3-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2- (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (2-tertiary- (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro- Hydroxyphenyl) propane, 2,2-bis (3,5-dibromo (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Methane, 2,2-bis (4-hydroxy-1- methylphenyl) propane, 1,1-bis (4-hydroxy- tertiary- 3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, Bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy- Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (3-bromo- ) Propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2- Butane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,1- Methylphenyl) butane, 1,1-bis (2-tertiary-butyl-4-hydroxy-5-methylphenyl) isobutane, Bis (3,5-dibromo-4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) heptane, 1,1-bis (2-tertiary-butyl-4-hydroxy-5-methylphenyl) heptane, 2,2- Phenyl) octane, or 1,1- (4-hydroxyphenyl) ethane; Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, Bis (3-phenyl-4-hydroxyphenyl) cyclohexane, or 1,1-bis (4-hydroxyphenyl) cyclohexane, ) -3,5,5-trimethylcyclohexane, and other bis (hydroxyaryl) cycloalkanes; Bis (hydroxyaryl) ether such as bis (4-hydroxyphenyl) ether or bis (4-hydroxy-3-methylphenyl) ether; Bis (hydroxyaryl) sulfide such as bis (4-hydroxyphenyl) sulfide or bis (3-methyl-4-hydroxyphenyl) sulfide; Bis (hydroxyaryl) sulfoxide such as bis (hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide or bis (3-phenyl-4-hydroxyphenyl) sulfoxide; Bis (hydroxyaryl) sulfone such as bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, or bis Dihydroxybiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'- Biphenyl compounds such as dihydroxy-3,3'-dicyclobiphenyl and 3,3-difluoro-4,4'-dihydroxybiphenyl, but are not limited thereto. These compounds may be used singly or in a mixture of two or more.

Examples of the aromatic dihydroxy compound that can be used in addition to the compound represented by Formula 1 include dihydroxybenzene, halogen or alkyl-substituted dihydroxybenzene, and examples thereof include resorcinol, 3-methylresorcinol, But are not limited to, 3-ethyl resorcinol, 3-propyl resorcinol, 3-butyl resorcinol, 3-tertiary-butyl resorcinol, 3-phenyl resorcinol, 2,3,4,6-tetrafluororesor Methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-methylhydroquinone, 3- Butyl hydroquinone, 3-phenyl hydroquinone, 3-silyl hydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra- Tertiary-butyl hydroquinone, 2,3,5,6-tetraprourohydroquinone, or 2,3,5,6-tetrabromohydroquinone.

In one embodiment of the present invention, it is preferable that 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is used as the aromatic dihydroxy compound.

(a2) a carbonate precursor

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis Diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, bishaloformate, and the like, but are not limited thereto. These compounds may be used singly or in a mixture of two or more. It is preferable that carbonyl chloride (phosgene) is used when the polycarbonate resin is produced by the interfacial polymerization method.

In one embodiment of the present invention, the carbonate precursor may be used in a molar ratio of 0.9 to 1.5 based on 1 mol of the aromatic dihydroxy compound.

In one embodiment of the present invention, the polycarbonate resin has a weight average molecular weight of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol.

In one embodiment of the present invention, the polycarbonate resin has a melt flow index (MI) of 3 to 120 g / 10 min measured at a temperature of 310 DEG C and a load of 1.2 kg in accordance with ASTM D1238.

In one embodiment of the present invention, the polycarbonate resin (A) is added to 100% by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber modified aromatic vinyl copolymer (C) By weight, and 25 to 94% by weight. In this case, the colorability, impact resistance and scratch resistance of the polycarbonate resin composition can be kept excellent.

(B) a modified acrylic copolymer

In the present invention, the modified acrylic copolymer serves to improve the colorability and scratch resistance of the polycarbonate resin composition.

In one embodiment of the present invention, the modified acrylic copolymer includes a unit derived from an acrylate or methacrylate containing an aliphatic cyclic or aromatic hydrocarbon group. Specific examples of the aliphatic cyclic hydrocarbon group include a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, and a C3 to C30 cycloalkynyl group. Specific examples of the aromatic hydrocarbon group include C6 to C30 aryl groups.

In one embodiment of the present invention, the aliphatic cyclic hydrocarbon group, the aromatic hydrocarbon group, or both include C1 to C10 linear, branched or cyclic alkyl groups, C1 to C10 linear, branched or cyclic alkoxy groups, C1 to C10 linear, Branched or cyclic alkylamine group, a C6 to C18 aryl group, a C6 to C18 aryloxy group, a C6 to C18 arylthio group, a C6 to C18 arylamine group, a halogen, etc. May be substituted.

In one embodiment of the present invention, the aliphatic cyclic hydrocarbon group, the aromatic hydrocarbon group, or both of them, and the acrylate or methacrylate, a C1 to C10 alkylene group, a C2 to C10 alkylidene group, a C15 cycloalkylene group, C5 to C15 cycloalkyl alkylidene group _{of, -S-, -SO-, SO 2 -} , can be a bond -O-, -CO-, or a combination thereof.

In one embodiment of the present invention, the modified acrylic copolymer is obtained by polymerizing (b1) an acrylate or methacrylate containing an aliphatic cyclic or aromatic hydrocarbon group, and (b2) a monofunctional unsaturated monomer. The monofunctionally unsaturated monomer (b2) means all compounds having one unsaturated group, and does not contain an acrylate or methacrylate (b1) containing the aliphatic cyclic or aromatic hydrocarbon group.

In one embodiment of the present invention, 5 to 95% by weight of the acrylate or methacrylate (b1) containing the aliphatic cyclic or aromatic hydrocarbon group is used, and the monofunctional unsaturated monomer (b2) is used in an amount of 5 to 95% Is used.

In one embodiment of the present invention, the acrylate or methacrylate (b1) comprising the aliphatic cyclic or aromatic hydrocarbon group is represented by the following formula (2), (3) or combinations thereof:

(2)

Wherein m is an integer from 0 to 10; X is a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group or a substituted or unsubstituted C6 to C30 aryl group; Y is hydrogen or a methyl group;

(3)

Wherein m is an integer from 0 to 10; X is a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group or a substituted or unsubstituted C6 to C30 aryl group; Y is hydrogen or a methyl group; Z is oxygen (O) or sulfur (S).

In one embodiment of the present invention, the acrylate or methacrylate (b1) comprising the aliphatic cyclic or aromatic hydrocarbon group is selected from the group consisting of cyclohexyl acrylate or methacrylate, ethyl phenoxy acrylate or methacrylate, Phenyl acrylate or methacrylate, 2-ethylaminophenyl acrylate or methacrylate, phenyl acrylate or methacrylate, benzyl acrylate or methacrylate, 2-phenylethyl acrylate or methacrylate, 3-phenyl Propyl acrylate or methacrylate, 4-phenylbutyl acrylate or methacrylate, 2-2-methylphenyl ethyl acrylate or methacrylate, 2-3-methylphenyl ethyl acrylate or methacrylate, 2-4-methylphenyl Ethyl acrylate or methacrylate, 2- (4-propylphenyl) ethyl acrylate Ethyl acrylate or methacrylate, 2- (4-methoxyphenyl) ethyl acrylate or methacrylate, 2- (4-cyclohexylphenyl) ethyl acrylate or methacrylate, 2- 2- (3-chlorophenyl) ethyl acrylate or methacrylate, 2- (4-chlorophenyl) ethyl acrylate or methacrylate, 2- ) Ethyl acrylate or methacrylate, 2- (4-bromophenyl) ethyl acrylate or methacrylate, 2- (3-phenylphenyl) ethyl acrylate or methacrylate, 2- Ethyl acrylate or methacrylate, and mixtures thereof.

In one embodiment of the present invention, the monofunctional unsaturated monomer (b2) is selected from the group consisting of an acrylate or methacrylate containing an aliphatic cyclic hydrocarbon group, an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, an unsaturated monomer including a hydroxyl group, Unsaturated amide-based monomers, unsaturated imide-based monomers, unsaturated nitrile-based monomers, aromatic vinyl-based monomers, and mixtures thereof.

Examples of the acrylate or methacrylate containing the aliphatic cyclic hydrocarbon group include methyl acrylate or methacrylate, ethyl acrylate or methacrylate, propyl acrylate or methacrylate, butyl acrylate or methacrylate, and the like. have.

Examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid.

Examples of the unsaturated carboxylic acid anhydride include maleic anhydride and the like.

Examples of the unsaturated monomer containing a hydroxy group include 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, monoglycerol acrylate or methacrylate, and the like.

Examples of the unsaturated monomer containing an epoxy group include allyl glycidyl ether, glycidyl acrylate, and methacrylate.

Examples of the unsaturated amide-based monomer include acrylamide and methacrylamide.

Examples of the unsaturated imide-based monomer include maleimide and the like.

Examples of the unsaturated nitrile-based monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile.

Examples of the aromatic vinyl-based monomer include styrene, C1 to C10 alkyl substituted styrene substituted with hydrogen of vinyl group, C1 to C10 alkyl substituted styrene substituted with hydrogen of benzene group, halogen substituted styrene substituted with hydrogen of vinyl group, Substituted halogen-substituted styrene, vinylnaphthalene, and the like.

In one embodiment of the present invention, the refractive index of the modified acrylic copolymer is from 1.495 to 1.590. In this case, the compatibility with the polycarbonate resin (A) is maintained to be excellent, and the transparency and colorability of the polycarbonate resin composition can be maintained to be excellent.

In one embodiment of the present invention, the modified acrylic copolymer has a weight average molecular weight of 5,000 to 50,000 g / mol, preferably 10,000 to 40,000 g / mol. In this case, there is no problem that the modified acrylic copolymer is decomposed during the production of the polycarbonate resin composition or a molded article thereof, and compatibility with the polycarbonate resin (A) can be maintained to be excellent.

In one embodiment of the present invention, the modified acrylic copolymer (B) is obtained by copolymerizing 100% by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber modified aromatic vinyl copolymer (C) By weight, preferably 1 to 70% by weight. In this case, the colorability, impact resistance and scratch resistance of the polycarbonate resin composition can be kept excellent.

(C) a transparent rubber-modified aromatic vinyl copolymer

In the present invention, the transparent rubber-modified aromatic vinyl-based copolymer serves to improve the impact resistance without lowering the other physical properties of the polycarbonate resin composition.

In one embodiment of the present invention, the transparent rubber-modified aromatic vinyl-based copolymer includes a core comprising a rubbery polymer, and a core comprising an acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer, an unsaturated nitrile monomer, And (c1) a graft copolymer comprising a shell formed by graft polymerizing an aromatic vinyl monomer; And a (c2) non-graft copolymer including a unit derived from an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer.

(c1) graft copolymer

The graft copolymer (c1) comprises a core; And a shell formed by graft polymerization on the surface of the core. The core comprises a rubbery polymer, and the shell is formed by graft polymerization of an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer.

Examples of the rubbery polymer include butadiene rubber, acrylic rubber, ethylene-propylene copolymer rubber, butadiene-styrene copolymer rubber, acrylonitrile-butadiene copolymer rubber, isoprene rubber, ethylene-propylene-diene terpolymer rubber, Siloxane-polyalkyl (meth) acrylate rubber composites, and the like, which may be used alone or as a mixture. As the rubbery polymer, a butadiene rubber or a butadiene-styrene copolymer rubber may preferably be used. When the butadiene-styrene copolymer rubber is used, it is preferable that the styrene content is less than 30% by weight.

In one embodiment of the present invention, the graft copolymer (c1) has an average particle size of the rubbery polymer of 0.10 to 0.30 m. When the average particle size of the rubbery polymer is within the above range, an appropriate balance of colorability, impact resistance and glossiness can be maintained.

The specific kind of the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer is not particularly limited.

In one embodiment of the present invention, the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer may be selected from the group consisting of C1 to C10 alkyl acrylates, C1 to C10 alkyl methacrylates, and mixtures thereof .

Examples of the C1 to C10 alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, t-butyl acrylate, n-butyl acrylate, n-octyl acrylate, And examples of the C1 to C10 alkyl methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, n-butyl methacrylate , n-octyl methacrylate, 2-ethylhexyl methacrylate, and the like. Preferably, methyl methacrylate can be used.

The unsaturated nitrile monomer is a compound containing an unsaturated hydrocarbon capable of radical polymerization and a cyanating group, and the specific kind thereof is not particularly limited.

Examples of the unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile. These monomers may be used alone or as a mixture. Preferably, acrylonitrile can be used.

The specific kind of the aromatic vinyl-based monomer is not particularly limited.

Examples of the aromatic vinyl monomer include styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, vinyl naphthalene, etc. These may be used alone or as a mixture.

In one embodiment of the present invention, the aromatic vinyl monomer is at least one selected from the group consisting of styrene, C1 to C10 alkyl substituted styrene substituted with hydrogen of vinyl group, C1 to C10 alkyl substituted styrene substituted with hydrogen of benzene group, Substituted halogenated styrene, halogen substituted styrene substituted with hydrogen of a benzene group, vinyl naphthalene, and mixtures thereof.

In one embodiment of the present invention, the aromatic vinyl-based monomer is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, , p-ethylstyrene, propylstyrene, butylstyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, and mixtures thereof.

It is preferable to use styrene as the aromatic vinyl monomer.

In one embodiment of the present invention, the shell may be further polymerized with maleic anhydride, C1 to C4 alkyl or phenyl substituted maleimide, or a mixture thereof.

In one embodiment of the invention, the shell may include an inner shell and an outer shell. In addition, the outer shell may include a unit derived from an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer. In this case, the inner shell may serve to improve impact resistance, and the outer shell may improve scratch resistance.

In one embodiment of the present invention, the inner shell is obtained by polymerizing the unsaturated nitrile-based monomer and the aromatic vinyl-based monomer (for example, styrene-acrylonitrile copolymer (SAN)), Alkyl ester monomer, the above-mentioned methacrylic acid alkyl ester monomer and a mixture thereof (for example, polymethyl methacrylate (PMMA)). In this case, the graft copolymer (c1) is prepared by the following method.

An aromatic vinyl monomer and an unsaturated nitrile monomer are graft-polymerized on the surface of the core to form an inner shell (first step), and an acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer is added thereto to wrap the inner shell Thereby forming an outer shell (second step). It is preferred that the first step proceeds under a lipid soluble redox initiator system and the second step proceeds under a water soluble initiator system. The graft copolymer (c1) produced by the second step may be prepared into a powder state through a post-treatment such as solidification, washing, dehydration and the like.

In one embodiment of the present invention, the inner shell is obtained by polymerizing the acrylic acid alkyl ester monomer or the methacrylic acid alkyl ester monomer, the unsaturated nitrile monomer and the aromatic vinyl monomer (for example, methyl methacrylate Acrylonitrile-styrene copolymer (MSAN)), and the outer shell is obtained by polymerizing the acrylic acid alkyl ester monomer or the methacrylic acid alkyl ester monomer, the unsaturated nitrile monomer, and the aromatic vinyl monomer (For example, methyl methacrylate-acrylonitrile-styrene copolymer (MSAN)). In this case, the graft copolymer (c1) is prepared by the following method.

A part of a mixture of an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer, an aromatic vinyl monomer and an unsaturated nitrile monomer is graft-polymerized on the surface of the core to form an inner shell (first step) To form an outer shell surrounding the inner shell (second step). It is preferred that the first step proceeds under a lipid soluble redox initiator system and the second step proceeds under a water soluble initiator system. The graft copolymer (c1) produced by the second step may be prepared into a powder state through a post-treatment such as solidification, washing, dehydration and the like.

In one embodiment of the present invention, the graft copolymer (c1) can improve the coloring property due to a small refractive index difference between the core and the shell. In the production of the graft copolymer (c1), the acrylic acid alkyl ester monomer or methacryl The scratch resistance can be improved by placing the acid alkyl ester monomer at the end of the chain and the weather resistance can be improved by wrapping the outermost portion of the core with the acrylic acid alkyl ester monomer or the methacrylic acid alkyl ester monomer have.

In one embodiment of the present invention, the graft copolymer (c1) comprises 30 to 70% by weight of the core, 15 to 55% by weight of a unit derived from the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer, 1 to 5% by weight of a unit derived from an unsaturated nitrile-based monomer, and 5 to 35% by weight of a unit derived from the aromatic vinyl-based monomer.

In one embodiment of the present invention, the graft copolymer (c1) is a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS).

In one embodiment of the present invention, the graft ratio of the graft copolymer (c1) is 30 to 70%. In this case, it is possible to obtain a white powder having a uniform particle size distribution during solidification and drying, and there is no problem that the surface state or the surface gloss of the molded article is lowered by unextracted particles during extrusion or injection. Also, excellent impact resistance, moldability and surface gloss can be maintained.

In one embodiment of the present invention, the graft copolymer (c1) may be contained in an amount of 5 to 50% by weight based on 100% by weight of the graft copolymer (c1) and the graft copolymer (c2).

(c2) Vigreft copolymer

In the present invention, the Vigreft copolymer (c2) means a copolymer excluding the graft copolymer (c1), and examples of the Vigreft copolymer include alternating copolymers, random copolymers, block copolymers and the like. The above-mentioned non-graft copolymer (c2) includes a unit derived from an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer.

Examples of the non-graft copolymer (c2) include polymers or copolymers obtained by polymerizing an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, or a mixture thereof; A copolymer obtained by polymerizing an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer and an aromatic vinyl monomer; Acrylic acid alkyl ester monomers, methacrylic acid alkyl ester monomers, aromatic vinyl monomers and unsaturated nitrile monomers. They may be used alone or as a mixture.

The specific kind of the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer is not particularly limited.

In one embodiment of the present invention, the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer may be selected from the group consisting of C1 to C10 alkyl acrylates, C1 to C10 alkyl methacrylates, and mixtures thereof .

Examples of the C1 to C10 alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, t-butyl acrylate, n-butyl acrylate, n-octyl acrylate, And examples of the C1 to C10 alkyl methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, n-butyl methacrylate , n-octyl methacrylate, 2-ethylhexyl methacrylate, and the like. Preferably, methyl methacrylate can be used.

The specific kind of the aromatic vinyl-based monomer is not particularly limited.

Examples of the aromatic vinyl monomer include styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, vinyl naphthalene, etc. These may be used alone or as a mixture.

In one embodiment of the present invention, the aromatic vinyl monomer is at least one selected from the group consisting of styrene, C1 to C10 alkyl substituted styrene substituted with hydrogen of vinyl group, C1 to C10 alkyl substituted styrene substituted with hydrogen of benzene group, Substituted halogenated styrene, halogen substituted styrene substituted with hydrogen of a benzene group, vinyl naphthalene, and mixtures thereof.

In one embodiment of the present invention, the aromatic vinyl-based monomer is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, , p-ethylstyrene, propylstyrene, butylstyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, and mixtures thereof.

It is preferable to use styrene as the aromatic vinyl monomer.

The unsaturated nitrile monomer is a compound containing an unsaturated hydrocarbon capable of radical polymerization and a cyanating group, and the specific kind thereof is not particularly limited.

Examples of the unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile. These monomers may be used alone or as a mixture. Preferably, acrylonitrile can be used.

In one embodiment of the present invention, the polymer or copolymer obtained by polymerizing the acrylic acid alkyl ester monomer, the methacrylic acid alkyl ester monomer, or a mixture thereof is polymethyl methacrylate.

In one embodiment of the present invention, the copolymer obtained by polymerizing the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer and the aromatic vinyl monomer is a methyl methacrylate-styrene copolymer.

In one embodiment of the present invention, the copolymer obtained by polymerizing the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer, aromatic vinyl monomer and unsaturated nitrile monomer is a copolymer of methyl methacrylate-styrene-acrylonitrile copolymer to be.

In one embodiment of the present invention, the methyl methacrylate-styrene-acrylonitrile copolymer is a low flow methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 100,000 to 150,000 g / mol and a weight average Styrene-acrylonitrile copolymer having a molecular weight of 50,000 to 100,000 g / mol. In this case, the injection processability can be further improved.

In one embodiment of the present invention, the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer may be used in an amount of 40 to 100% by weight among 100% by weight of the non-graft copolymer (c2). In this case, glossiness, scratch resistance, coloring property and weather resistance can be kept excellent.

In one embodiment of the present invention, the non-graft copolymer (c2) may be contained in an amount of 50 to 95% by weight based on 100% by weight of the graft copolymer (c1) and the non-graft copolymer (c2).

(A), the modified acrylic copolymer (B), and the transparent rubber-modified aromatic vinyl copolymer (C). The aromatic rubber-modified aromatic vinyl copolymer (C) And 5 to 20% by weight based on 100% by weight of the composition. In this case, the colorability, impact resistance and scratch resistance of the polycarbonate resin composition can be kept excellent.

(D) Syndiotactic polystyrene

In one embodiment of the present invention, the polycarbonate resin composition may further comprise syndiotactic polystyrene.

Polystyrene is generally divided into an isotactic, isotactic and syndiotactic structures depending on the position of the side chain benzene rings. In the atactic polystyrene, the benzene ring has an irregular arrangement, and the isotactic polystyrene has a structure in which a benzene ring is arranged on one side of the polymer main chain. On the other hand, syndiotactic polystyrene has a structure in which benzene rings are alternately and regularly arranged.

Examples of the syndiotactic polystyrene include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiary butylstyrene) ), Poly (p-fluorostyrene), and poly (p-cyclohexylstyrene). They may be used alone or as a mixture.

In one embodiment of the present invention, the syndiotactic polystyrene (D) is a mixture of 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber-modified aromatic vinyl copolymer (C) , And 0 to 5 parts by weight. In this case, the impact resistance of the polycarbonate resin composition, particularly the gate portion of the injection-molded article made of the composition, can be improved without deteriorating the other physical properties of the polycarbonate resin composition.

(E) Surface Conditioning Agent

The polycarbonate resin composition according to the present invention may further comprise a surface modifier. In the present invention, the surface modifier serves to improve the resistance to mar scratches such as micro-scratches or living scratches without deteriorating other physical properties of the polycarbonate resin composition.

Examples of the surface modifier include (e1) a siloxane-based surface modifier, and (e2) a fatty acid amide-based surface modifier. They may be used alone or as a mixture.

(e1) Siloxane-based surface modifier

The siloxane-based surface modifier (e1) comprises a repeating unit represented by the following formula (4): < EMI ID =

[Chemical Formula 4]

Wherein R ¹ is a C ¹ to C 6 alkyl group and R ² is a C 6 to C 12 aryl group.

Examples of the siloxane-based surface modifier (e1) include polymethylphenylsiloxane, polyethylphenylsiloxane, polypropylphenylsiloxane, polybutylphenylsiloxane, polypentylphenylsiloxane, and polyhexylphenylsiloxane. They may be used alone or as a mixture. Of these, polymethylphenylsiloxane is preferred.

In one embodiment of the present invention, the siloxane-based surface modifier (e1) has a refractive index of 1.42 to 1.59, preferably 1.47 to 1.59, more preferably 1.49 to 1.59. In this case, it is possible to maintain excellent resistance to mar scratches such as fine scratches or living scratches while maintaining excellent coloring property.

In one embodiment of the present invention, the siloxane-based surface modifier (e1) has a weight average molecular weight of 400 to 1,000 g / mol, preferably 600 to 800 g / mol. In this case, the surface of the polycarbonate resin composition or the molded article produced therefrom does not bleed out, and the siloxane-based surface modifier (e1) can easily move to the surface.

In one embodiment of the present invention, the siloxane-based surface modifier (e1) has a viscosity of 20 to 120 mPa · s, preferably 30 to 100 mPa · s at 25 ° C. In this case, the surface of the polycarbonate resin composition or the molded article produced therefrom does not bleed out, and the siloxane-based surface modifier (e1) can easily move to the surface.

In one embodiment of the present invention, the siloxane-based surface modifier (e1) may have a fluid form.

In one embodiment of the present invention, the siloxane-based surface modifier (e1) is added to 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber modified aromatic vinyl copolymer (C) 0.1 to 10 parts by weight, relative to the total weight of the composition. In this case, it is possible to maintain excellent resistance to mar scratches such as fine scratches or living scratches without deteriorating other physical properties.

(e2) fatty acid amide-based surface conditioner

Examples of the fatty acid amide type surface modifier (e2) include C15 to C30 alkyl amide. Examples of the C 15 to C 30 alkyl amides include stearamide, erucamide, oleamide, behenamide, and the like. They may be used alone or as a mixture.

In one embodiment of the present invention, the fatty acid amide type surface modifier (e2) is prepared by mixing 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber modified aromatic vinyl copolymer (C) 0.1 to 5 parts by weight based on 100 parts by weight of the composition. In this case, it is possible to maintain excellent resistance to mar scratches such as fine scratches or living scratches without deteriorating other physical properties.

(F) Additive

In one embodiment of the present invention, the polycarbonate resin composition may contain at least one of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a compatibilizer, a lubricant, an antistatic agent, An additive selected from the group consisting of dyes, flame retardants, flame retardant adjuvants, anti-drip agents, weathering stabilizers, ultraviolet absorbers, ultraviolet screening agents and mixtures thereof.

Examples of the antioxidant include a phenol type, a phosphite type, a thioether type, and an amine type antioxidant.

Examples of the releasing agent include a fluorine-containing polymer, a silicone oil, a metal salt of stearic acid, a metal salt of montanic acid, a montanic ester wax, and a polyethylene wax.

Examples of the inorganic additive include glass fiber, carbon fiber, silica, mica, alumina, clay, calcium carbonate, calcium sulfate, glass beads and the like.

Examples of the pigment or dye include titanium dioxide, carbon black, and the like. Examples of the carbon black include graphitized carbon, furnace black, acetylene black, and Ketjen black.

Examples of the flame retardant include phosphorus-based, nitrogen-based, and halogen-based flame retardants.

Examples of the flame retardant auxiliary include antimony oxide and the like.

Examples of the drip inhibitor include polytetrafluoroethylene and the like.

Examples of the weathering stabilizer include benzophenone type or amine type weathering stabilizer.

In one embodiment of the present invention, the additive is added in an amount of 0.1 to 40 parts by weight (based on 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber modified aromatic vinyl copolymer ≪ / RTI >

In one embodiment of the present invention, the polycarbonate resin composition further comprises carbon black as a pigment, and has an L value of 26.5 to 28.0 measured under a D65 light source using CCM equipment according to ASTM D1925.

In one embodiment of the present invention, the polycarbonate resin composition has a notched Izod impact strength of from 40 to 65 kgf · cm / cm in a 3.175 mm thick specimen measured according to ASTM D256.

In one embodiment of the present invention, the polycarbonate resin composition is prepared by injection molding a 2 mm thick specimen in a pin point gate mold, placing a metal tip with a diameter of 10 mm on the gate of the specimen, Is measured at free fall from a height of 70 cm and the rate of gate breakage is less than 50%.

In one embodiment of the present invention, the polycarbonate resin composition has a scratch width of 275 to 300 m measured according to the BSP test, and a pencil hardness of not less than HB measured at a load of 500 g according to ASTM D3362.

The polycarbonate resin composition according to the present invention can be produced by a known method for producing a resin composition. For example, the polycarbonate resin composition according to the present invention may be prepared in the form of pellets by mixing the constituents of the present invention and other additives simultaneously, followed by melt extrusion in an extruder.

The polycarbonate resin composition according to the present invention can be suitably applied to a molded article for non-coating, and can be suitably applied to a molded article requiring excellent coloring property, impact resistance and scratch resistance at the same time. For example, the polycarbonate resin composition according to the present invention can be preferably applied to a housing for an electric / electronic product, a home appliance, an office automation product, or a mobile phone product or an automobile material.

There is no particular limitation on the method for producing a molded article using the polycarbonate resin composition according to the present invention. For example, extrusion, injection molding or cast molding methods can be applied. Such molding can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.

The present invention will be further illustrated by the following examples, but the following examples are used for the purpose of illustrating the present invention and are not intended to limit the scope of protection of the present invention.

Example

The components used in Examples and Comparative Examples are as follows.

(A) Polycarbonate resin

A bisphenol-A type polycarbonate (trade name: INFINO Polycarbonate) having a melt flow index of 8 g / 10 min measured at a temperature of 310 ° C. and a load of 1.2 kg according to ASTM D1238 was used.

(B) a modified acrylic copolymer

A copolymer obtained by polymerizing 35% by weight of phenyl methacrylate and 65% by weight of methyl methacrylate, having a refractive index of 1.514 to 1.516 and a weight average molecular weight of 20,000 g / mol was used.

(C) a transparent rubber-modified aromatic vinyl copolymer

(c1) graft copolymer

Wherein the average particle size of the rubber-like polymer is 0.245 탆 and the content of the rubber-like polymer is 55% by weight, wherein the average particle size of the rubber-like polymer is 0.245 탆 and the content of the rubber- 25 wt% of g-MABS was used.

(c2) Vigreft copolymer

75% by weight of a copolymer (MSAN) obtained by polymerizing methyl methacrylate, styrene and acrylonitrile was used.

The refractive index of the transparent rubber-modified aromatic vinyl-based copolymer is 1.515.

(C ') ABS resin

ABS resin (trade name: STAREX SD-0150) manufactured by Cheil Industries was used.

(D) Syndiotactic polystyrene

Syndiotactic polystyrene (trade name: Zarex 130ZC) manufactured by Idemitsu Co., Ltd. was used.

(E) Surface Conditioning Agent

(e1) Siloxane-based surface modifier

Polymethylphenylsiloxane (trade name: TSF437) of GE Toshiba Silicones with a refractive index of 1.499 was used.

(e2) fatty acid amide-based surface conditioner

Erucamide (trade name: Finawax ER) from Fine Chemical Co. was used.

(F) Additive

Carbon black (trade name: Hi-BLACK) manufactured by Korea Carbon Black Company was used.

Example  1 to 9 and Comparative Example  1 to 6

Each of the above components was dry mixed according to the contents shown in Table 1, and the mixture was extruded using a twin screw extruder having a diameter of 45 mm. The extrudate was prepared in the form of pellets. The prepared pellets were dried in a dehumidifying dryer at 100 캜 for 4 hours and then injected to prepare specimens for measuring properties. The properties of the prepared specimens were measured in the following manner. The results are shown in Table 1.

(1) Coloring property: The L value was measured under a D65 light source using a CCM equipment (model name: 3600D) manufactured by Konica Minolta, Inc. according to ASTM D1925. In the case of black color, the lower the L value, the better the coloring property.

(2-1) Impact resistance: The notched Izod impact strength of a 3.175 mm (1/8 ") thick specimen was measured according to ASTM D256.

(2-2) Impact resistance: A 2 mm thick specimen was injection molded in a pin point gate mold, and a metal tip of 10 mm in diameter was placed on the gate of the specimen. A weight of 2 kg was placed 50 cm or 70 cm And the fracture rate of the gate region was measured.

(3-1) Scratch resistance: A load of 1 kg was applied to a specimen using a tungsten carbide stylus having a diameter of 0.7 mm and a sharp-pointed tip, and a scratch was applied to the specimen at a speed of 75 mm / And the scratch width was measured using a surface profiler (Ball-type Scratch Profile Test (BSP test)). The narrower the scratch width, the better the scratch resistance.

(3-2) Scratch resistance: The pencil hardness was measured according to ASTM D3362 under a load of 500 g.

(3-3) Scratch resistance (mar scratch resistance): The microfiber cloth was applied to the specimen using an abrasion rubbing tester, and the appearance was ascertained after 500 reciprocations. The rubbing test was performed according to the following criteria (Rubbing test)).

9 (Best) - 7 (Good) - 5 (Moderate) - 3 (Bad) - 1 (Worst)

From Table 1, it can be seen that Examples 1 to 6 are all excellent in coloring property, impact resistance and scratch resistance by including all the constituents of the present invention. In addition, Example 7 further includes syndiotactic polystyrene (D), so that the gate breakage ratio at 2 kg / 70 cm is more excellent than that in Example 2, and Example 8 shows a siloxane-based surface modifier (e1) The marbling test also showed a better mar scratch resistance rating compared to Example 2, and Example 9 showed a better mar scratch resistance rating than the Example 2 in the rubbing test using the fatty acid amide based surface conditioner (e2) .

In Comparative Example 1, the colorability and scratch resistance were remarkably lowered by using the polycarbonate resin (A) and the ABS resin (C '). In Comparative Example 2, only the polycarbonate resin (A) and the modified acrylic copolymer (B) were used, and the impact resistance was remarkably lowered than in the Examples. In the rubbing test, the mar scratch resistance rating . In Comparative Examples 3 to 4, the impact resistance was remarkably lowered as compared with the case of using the transparent rubber-modified aromatic vinyl-based copolymer (C) in a smaller amount than the preferable content range. In Comparative Examples 5 to 6, It can be seen that the aromatic vinyl copolymer (C) was used in a larger amount than the preferred range, and the colorability and scratch resistance were remarkably lowered as compared with Example 6.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (20)

(A) a polycarbonate resin;
(B) a modified acrylic copolymer; And
(C) a transparent rubber-modified aromatic vinyl-based copolymer;
Wherein the transparent rubber-modified aromatic vinyl-based copolymer (C) is a polycarbonate resin composition comprising
(C1) comprising a core comprising a rubbery polymer and a shell formed by graft polymerizing an acrylic acid alkyl ester monomer or an alkyl methacrylate ester monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer on the surface of the core, 5 to 50% by weight of a graft copolymer; And
From 50 to 95% by weight of a (c2) non-graft copolymer comprising a unit derived from an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer;
Wherein the polycarbonate resin composition is a polycarbonate resin composition.
The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin (A) is contained in an amount of 25 to 94 wt%, the modified acrylic copolymer (B) is contained in an amount of 1 to 70 wt% (C) is contained in an amount of 5 to 20% by weight based on the total weight of the polycarbonate resin composition.
The polycarbonate resin composition according to claim 1, wherein the modified acrylic copolymer (B) comprises (b1) a unit derived from an acrylate or methacrylate containing an aliphatic cyclic or aromatic hydrocarbon group.
The positive resist composition according to claim 1, wherein the modified acrylic copolymer (B) comprises (b1) 5 to 95% by weight of an acrylate or methacrylate containing an aliphatic cyclic or aromatic hydrocarbon group, and (b2) % Of the total weight of the polycarbonate resin composition.
The polycarbonate resin composition according to claim 3 or 4, wherein the aliphatic cyclic or aromatic hydrocarbon group-containing acrylate or methacrylate (b1) is represented by the following general formula (2), (3) :
(2)

Wherein m is an integer from 0 to 10; X is a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group or a substituted or unsubstituted C6 to C30 aryl group; Y is hydrogen or a methyl group;
(3)

Wherein m is an integer from 0 to 10; X is a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group or a substituted or unsubstituted C6 to C30 aryl group; Y is hydrogen or a methyl group; Z is oxygen (O) or sulfur (S).
The positive photosensitive resin composition according to claim 4, wherein the monofunctional unsaturated monomer (b2) comprises an acrylate or methacrylate, an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, an unsaturated monomer including a hydroxyl group, and an epoxy group containing an aliphatic cyclic hydrocarbon group Wherein the polycarbonate resin composition is selected from the group consisting of unsaturated monomers, unsaturated amide monomers, unsaturated imide monomers, unsaturated nitrile monomers, aromatic vinyl monomers, and mixtures thereof.
The polycarbonate resin composition according to claim 1, wherein the refractive index of the modified acrylic copolymer (B) is from 1.495 to 1.590.
The polycarbonate resin composition according to claim 1, wherein the modified acrylic copolymer (B) has a weight average molecular weight of 5,000 to 50,000 g / mol.
delete delete The rubber composition according to claim 1, wherein the rubbery polymer is at least one selected from the group consisting of a butadiene rubber, an acrylic rubber, an ethylene-propylene copolymer rubber, a butadiene-styrene copolymer rubber, an acrylonitrile-butadiene copolymer rubber, an isoprene rubber, A rubber, a polyorganosiloxane-polyalkyl (meth) acrylate rubber composite, and a mixture thereof.
The polycarbonate resin composition according to claim 1, wherein the shell comprises an inner shell and an outer shell, and the outer shell comprises a unit derived from an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer .
The composition according to claim 1, wherein the graft copolymer (c1) comprises 30 to 70% by weight of the core, 15 to 55% by weight of a unit derived from the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer, 1 to 5% by weight of a unit derived from an aromatic monomer, and 5 to 35% by weight of a unit derived from the aromatic vinyl-based monomer.
The positive resist composition according to claim 1, wherein (D) 100 parts by weight of syndiotactic polystyrene is replaced by 0 part by weight of 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber modified aromatic vinyl copolymer To 5 parts by weight or less of the polycarbonate resin composition.
The composition according to claim 1, wherein (e1) a siloxane-based surface modifier is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin (A), the modified acrylic copolymer (B) and the transparent rubber- (E2) 0.1 to 5 parts by weight of a fatty acid amide-based surface modifier, or a mixture thereof. The polycarbonate resin composition of
The composition according to any one of claims 1 to 3, wherein the antioxidant, heat stabilizer, antioxidant, mold releasing agent, light stabilizer, inorganic additive, surfactant, coupling agent, plasticizer, compatibilizer, lubricant, antistatic agent, colorant, pigment, dye, Wherein the polycarbonate resin composition further comprises an additive selected from the group consisting of an ultraviolet absorber, an ultraviolet absorber, and a mixture thereof.
The polycarbonate resin composition according to claim 1, further comprising carbon black as a pigment and having an L value of 26.5 to 28.0 as measured under a D65 light source using CCM equipment according to ASTM D1925.
The polycarbonate resin composition according to claim 1, wherein the 3.175 mm thick specimen measured according to ASTM D256 has a notched Izod impact strength of 40 to 65 kgf / cm / cm.
The method of claim 1, wherein the 2 mm thick specimen is injection molded from a pin point gate mold, a metal tip of 10 mm diameter is placed on the gate of the specimen, 2 kg of the weight is free from a height of 70 cm And a gate breakage rate measured by dropping is less than 50%.
The polycarbonate resin composition according to claim 1, wherein a scratch width measured from the BSP test is 275 to 300 占 퐉, and a pencil hardness measured at 500 g load according to ASTM D3362 is not less than HB.

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