WO2014119827A9 - Polycarbonate-based thermoplastic resin composition and molded article - Google Patents

Polycarbonate-based thermoplastic resin composition and molded article Download PDF

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Publication number
WO2014119827A9
WO2014119827A9 PCT/KR2013/005727 KR2013005727W WO2014119827A9 WO 2014119827 A9 WO2014119827 A9 WO 2014119827A9 KR 2013005727 W KR2013005727 W KR 2013005727W WO 2014119827 A9 WO2014119827 A9 WO 2014119827A9
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group
polycarbonate
weight
resin composition
based thermoplastic
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PCT/KR2013/005727
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French (fr)
Korean (ko)
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WO2014119827A1 (en
Inventor
나타라잔센틸쿠마르
장주현
김동희
김일진
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제일모직주식회사
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Priority claimed from KR1020130072825A external-priority patent/KR101664844B1/en
Application filed by 제일모직주식회사 filed Critical 제일모직주식회사
Priority to CN201380071804.4A priority Critical patent/CN104955897B/en
Priority to US14/763,877 priority patent/US9505929B2/en
Publication of WO2014119827A1 publication Critical patent/WO2014119827A1/en
Publication of WO2014119827A9 publication Critical patent/WO2014119827A9/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a polycarbonate-based thermoplastic resin composition. More specifically, the present invention relates to a polycarbonate-based thermoplastic resin composition excellent in fluidity without impairing impact strength and heat resistance.
  • Thermoplastic resins have a lower specific gravity than glass or metal, and have excellent physical properties such as moldability and impact resistance. Recently, due to the trend of low cost, large size, and light weight of electric and electronic products, plastic products are rapidly replacing the existing glass or metal areas, thereby expanding the use area from electric and electronic products to automobile parts. Accordingly, the function and appearance performance of the exterior material is important, and the demand for external impact and workability is also increasing.
  • thermoplastic resins polycarbonate-based thermoplastic resins have high impact strength, high heat resistance, and high transparency, and thus are used in various engineering devices.
  • polycarbonate-based thermoplastic resins have a relatively poor fluidity. Therefore, in order to improve the fluidity of the polycarbonate-based thermoplastic resin, one or more polymers and additives are mixed and used.
  • g-ABS is used as an impact modifier in the existing PC / SAN alloy technology. Because g-ABS has a high affinity with SAN, it exists inside the SAN during PC / SAN alloy, and when the external shock is applied, the impact reinforcement effect is lowered mainly because the destruction occurs first at the interface between the PC and the SAN. Therefore, when g-ABS is used as the impact reinforcing material, when an external impact is applied, there is a problem that destruction occurs mainly at the interface between the PC and the SAN.
  • the present inventors intend to improve the impact reinforcement effect by using a rubber-modified acrylic graft copolymer resin similar in affinity with both PC and SAN.
  • it is intended to develop a polycarbonate-based thermoplastic resin composition having excellent fluidity and improved moldability and processability without deteriorating mechanical properties such as impact strength and heat resistance.
  • An object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent fluidity.
  • Another object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent impact strength and heat resistance.
  • Another object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent moldability.
  • Still another object of the present invention is to provide a molded article manufactured using the polycarbonate-based thermoplastic resin composition.
  • the polycarbonate-based thermoplastic resin composition according to the present invention includes a copolymer resin containing (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a silicone-based compound.
  • Polycarbonate-based thermoplastic resin composition of the present invention is a copolymer resin containing 40 to 80% by weight of polycarbonate resin (A), 1 to 30% by weight of the rubber-modified acrylic graft copolymer resin (B) and the silicone-based compound ( C) 10 to 30% by weight.
  • the polycarbonate-based thermoplastic resin composition of the present invention is an impact reinforcing material located at the interface between the first resin in the continuous phase, the second resin in the dispersed phase and the first resin in the continuous phase and the second resin in the dispersed phase. It may include.
  • the polycarbonate-based thermoplastic resin composition of the present invention may include 40 to 80% by weight of the first resin in the continuous phase, 10 to 30% by weight of the second resin in the dispersed phase, and 1 to 30% by weight of the impact modifier.
  • the first resin in the continuous phase is a polycarbonate resin (A)
  • the second resin in the dispersed phase is a copolymer resin (C) containing a silicone compound
  • the impact modifier may be a rubber-modified acrylic graft copolymer resin (B).
  • the rubber-modified acrylic graft copolymer resin (B) may include 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and 1 to 40% by weight of vinyl aromatic monomer (b3). Can be.
  • Alkyl methacrylate (b2) may have 1 to 20 carbon atoms.
  • the copolymer resin (C) including the silicone compound may be a branched vinyl copolymer resin.
  • Copolymer (C) comprising a silicone-based compound is 10 to 80% by weight aromatic vinyl monomer (c1), 10 to 80% by weight unsaturated nitrile monomer (c2), 1 to 30% by weight (meth) acrylic monomer (c3) And it may be a copolymer prepared by copolymerizing 0.1 to 25% by weight of the silicon-based compound (c4) having two or more unsaturated reactors.
  • the weight average molecular weight of the copolymer resin (C) including the silicone compound may be 30,000 to 800,000 g / mol.
  • the aromatic vinyl monomer (c1) may be selected from the group consisting of styrene, p-methylstyrene, ⁇ -methylstyrene, halogen substituted styrene, alkyl substituted styrene, and mixtures thereof.
  • the unsaturated nitrile monomer (c2) may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile and mixtures thereof.
  • the (meth) acrylic monomer (c3) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylates and mixtures thereof.
  • the silicone compound (c4) having two or more unsaturated reactors may include a silicone compound having a structure represented by the following Chemical Formula 4 alone or in a mixture of two or more thereof:
  • R 1 to R 8 are each independently a hydrogen atom, linear or branched C An alkyl group of 1 -C 5 , a cycloalkyl group of C 4 -C 6 , an unsaturated alkyl group of C 2 -C 12 , a C 6 -C 10 aryl group, a hydroxyl group, an alkoxy group of C 1 -C 5 , an acetoxy group, an amino group, An amide group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, and a mercapto group, wherein at least two of R 1 to R 8 have a polymerizable unsaturated reactor.
  • the silicone-based compound (c4) having two or more unsaturated reactors may have a viscosity of 5000 cPs or less and a vinyl content of 0.05 to 10 mmol / g.
  • Silicone-based compounds (c4) having two or more unsaturated reactors are 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyl Trisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, ⁇ , ⁇ -divinylpolydimethylsiloxane, polyvinylmethylsilazane, 1,3-divinyl-1,1, 3,3-tetramethyldisiloxane and mixtures thereof.
  • the polycarbonate-based thermoplastic resin composition according to the present invention is excellent in fluidity, impact strength and heat resistance, and improves moldability.
  • the polycarbonate-based thermoplastic resin composition according to the present invention is excellent in fluidity, impact strength and heat resistance, and improves moldability.
  • the polycarbonate-based thermoplastic resin composition of the present invention includes a copolymer resin containing (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a silicone compound. Each component is demonstrated concretely below.
  • polycarbonate-based thermoplastic resin composition of the present invention is located at the interface between (A) the first resin in the continuous phase, (C) the second resin in the dispersed phase and (B) the first resin in the continuous phase and the second resin in the dispersed phase.
  • Impact modifiers Each component is demonstrated concretely below.
  • Polycarbonate-based thermoplastic resin composition according to the present invention is a copolymer comprising (A) 40 to 80% by weight of polycarbonate resin, (B) 1 to 30% by weight of rubber-modified acrylic graft copolymer resin and (C) silicone compound It may include 10 to 30% by weight of the resin.
  • the polycarbonate-based thermoplastic resin composition of the present invention (A) 40 to 80% by weight of the first resin in the continuous phase, (C) 10 to 30% by weight of the second resin in the dispersed phase and the first resin and the dispersed phase of the continuous phase 1 to 30% by weight of the impact modifier (B) located at the interface of the two resins.
  • A 40 to 80% by weight of the first resin in the continuous phase
  • C 10 to 30% by weight of the second resin in the dispersed phase and the first resin and the dispersed phase of the continuous phase 1 to 30% by weight of the impact modifier (B) located at the interface of the two resins.
  • the polycarbonate resin (A) is not particularly limited.
  • an aliphatic polycarbonate resin, an aromatic polycarbonate resin, a copolycarbonate thereof, a copolycarbonate carbonate resin, a polycarbonate-polysiloxane copolymer or a mixture thereof may be used as the polycarbonate resin.
  • the polycarbonate resin may have a linear or branched structure.
  • the polycarbonate resin is a continuous phase in the polycarbonate-based thermoplastic resin composition.
  • the polycarbonate resin (A) can be prepared by reacting a compound selected from the group consisting of diphenols represented by the following formula (1) with phosgene, halogen formate, carbonate, and combinations thereof.
  • A is a single bond, a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 5 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 6 carbon atoms , A substituted or unsubstituted cycloalkylidene group having 5 to 10 carbon atoms, CO, S, and SO 2 It is a linking group selected from the group, each R 1 and R 2 are each independently substituted or unsubstituted carbon 1 It is a substituent selected from the group consisting of an alkyl group of 30 to 30, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, n 1 and n 2 are each independently an integer of 0 to 4, the "substituted” is a hydrogen atom And a substituent selected from the group consisting of a halogen group, an alkyl
  • the diphenols represented by the formula (1) may combine two or more kinds to form a repeating unit of the polycarbonate resin.
  • Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane (also called 'bisphenol-A'), 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydrate Hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, etc. are mentioned.
  • 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, or 1,1-bis- in the said diphenols (4-hydroxyphenyl) -cyclohexane can be preferably used.
  • 2,2-bis- (4-hydroxyphenyl) -propane can be used more preferably.
  • the polycarbonate resin (A) is preferably a weight average molecular weight of 10,000 to 200,000 g / mol, more preferably 15,000 to 80,000 g / mol, it is possible to ensure excellent impact strength in the molecular weight range, moderate fluidity It is possible to obtain excellent workability.
  • the polycarbonate resin (A) may be a mixture of copolymers prepared from two or more kinds of diphenols.
  • a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like can be used as the polycarbonate resin (A).
  • group polycarbonate resin etc. are mentioned as linear polycarbonate resin.
  • the branched polycarbonate resin include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. It is preferable that a polyfunctional aromatic compound is contained in 0.05-2 mol% with respect to the branched polycarbonate resin total amount.
  • polyester carbonate copolymer resin what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned.
  • a diaryl carbonate such as diphenyl carbonate, cyclic ethylene carbonate, or the like may be used.
  • the polycarbonate resin (A) is based on 100% by weight of the total resin composition containing the polycarbonate resin (A), the rubber-modified acrylic graft copolymer resin (B) and the copolymer resin (C) containing the silicone compound. To 80% by weight. Preferably it may be included in 60 to 80% by weight.
  • the polycarbonate resin (A) When the polycarbonate resin (A) is less than 40% by weight, impact resistance, tensile properties and heat resistance are lowered, and when it is more than 80% by weight, fluidity is lowered.
  • the rubber-modified acrylic graft copolymer resin (B) is a copolymer obtained by grafting rubber (b1), alkyl methacrylate (b2) and vinyl-based aromatic monomer (b3) as impact modifiers.
  • the rubber-modified acrylic graft copolymer resin (B) may include 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and 1 to 40% by weight of vinyl aromatic monomer (b3). Can be.
  • Non-limiting examples of the rubber (b1) include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers in which hydrogen is added to the diene-based rubber, isoprene rubber, and chlorochloroprene rubber. And acrylic rubber such as butyl polyacrylate, ethylene-propylene rubber, and ethylene-propylene-diene terpolymer (EPDM).
  • the rubber (b1) may be used alone or in combination of two or more thereof. Among these, the diene diene rubber is preferable, and butadiene rubber is more preferable.
  • the content of the rubber (b1) is appropriately 40 to 98% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B).
  • the content of the rubber (b1) is less than 40% by weight, the impact resistance is lowered, and when it is more than 98% by weight, the heat resistance is lowered.
  • the average particle size of the rubber (b1) is preferably 0.1 to 0.7 ⁇ m in consideration of the impact strength and appearance.
  • the rubber-modified acrylic graft copolymer resin (B) is used as an impact reinforcing material, and is used at the interface between a polycarbonate resin (first resin) in a continuous phase and a copolymer resin (second resin) containing a silicone compound in a dispersed phase. Located.
  • g-ABS resin was used as an impact reinforcing material. Since g-ABS resin has a high affinity with SAN, it exists inside SAN, and when the external shock is applied, the impact reinforcing effect is inferior because the destruction occurs first at the interface between PC and SAN.
  • the rubber-modified acrylic graft copolymer resin (B) used as the impact reinforcing material in the present invention has similar affinity with the copolymer resin (C) containing a polycarbonate (A) and a silicone-based compound. That is, the affinity of the polycarbonate (A) and the rubber modified acrylic graft copolymer resin (B) and the affinity of the rubber modified acrylic graft copolymer resin (B) and the copolymer resin (C) containing a silicone compound are similar. .
  • the rubber-modified acrylic graft copolymer resin (B) is located at the interface between the continuous polycarbonate resin (first resin) and the copolymer resin (second resin) containing the disperse phase silicone-based compound, so that external impact is applied. At this time, no destruction occurs at the interface. Therefore, the polycarbonate-based resin composition according to the present invention is excellent in impact reinforcing effect.
  • alkyl methacrylate (b2) alkyl methacrylate having 1 to 20 carbon atoms may be used.
  • alkyl methacrylate examples include, but are not limited to, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These may be used alone or in mixture of two or more thereof. Most preferred is methyl methacrylate.
  • the content of the alkyl methacrylate may be applied in 1 to 30% by weight, preferably 5 to 15% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). If the content of the alkyl methacrylate is less than 1% by weight, the dispersibility may be lowered, and if it is more than 30% by weight, impact resistance may be lowered.
  • the vinyl aromatic monomer (b3) may use styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene, or a mixture thereof, preferably styrene. This is not restrictive.
  • Vinyl-based aromatic monomer (b3) may be included in 1 to 40% by weight, preferably 10 to 30% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). When the content of the vinyl aromatic monomer (b3) is less than 1% by weight, the polymerizability may be lowered, and when it is more than 40% by weight, the glossiness may be lowered.
  • the rubber-modified acrylic graft copolymer resin (B) is a total weight of 100 resin compositions comprising a polycarbonate resin (A), a rubber-modified acrylic graft copolymer resin (B) and a copolymer resin (C) containing a silicone compound. With respect to%, it may be included in 1 to 30% by weight. Preferably it may be included in 5 to 15% by weight.
  • the rubber-modified acrylic graft copolymer resin (B) is less than 1% by weight, impact resistance and flexural strength are lowered, and when it is more than 30% by weight, fluidity and heat resistance are lowered.
  • copolymer resin (C) including the silicone compound of the present invention a flexible branched vinyl copolymer resin may be used.
  • the copolymer resin containing the silicone compound is a dispersed phase in the polycarbonate thermoplastic resin composition.
  • the copolymer resin (C) including the silicone-based compound includes (c1) an aromatic vinyl monomer, (c2) an unsaturated nitrile monomer, (c3) a (meth) acrylic monomer, and (c4) two or more unsaturated reactors.
  • the copolymer prepared by copolymerizing the silicone-based compound or a mixture of these copolymers can be used.
  • the copolymer resin (C) including the silicone compound is 10 to 80 wt% of the aromatic vinyl monomer (c1), 10 to 80 wt% of the unsaturated nitrile monomer (c2), and (meth) acrylic monomer (c3) Copolymers prepared by copolymerizing 1 to 30% by weight and 0.1 to 25% by weight of the silicone-based compound (c4) having two or more unsaturated reactors or a mixture of these copolymers may be used.
  • Copolymer resin (C) containing such a silicone-based compound can be prepared using conventional polymerization methods known in the art, for example, bulk polymerization, emulsion polymerization, suspension polymerization and the like.
  • Copolymer resin (C) containing a silicone-based compound has an advantage of having low stability because of its low impurity content and low manufacturing cost because it is manufactured by a simple suspension polymerization process.
  • Copolymer resin (C) comprising the silicone compound of the present invention is characterized in that it is made of a branched structure that can improve the fluidity at the same time as the silicone-based compound having a high molecular weight during copolymerization can improve the impact of the resin.
  • Copolymer resins (C) comprising silicone-based compounds are readily dissolved and mixed with other engineering plastics due to materials having a low glass transition temperature (Tg) (eg, butyl acrylate and silicone crosslinkers). This contributes to improving physical properties such as the flowability of the result.
  • Tg glass transition temperature
  • the aromatic vinyl monomer (c1) may use styrene, p-methylstyrene, ⁇ -methylstyrene, halogen or alkyl substituted styrene, or a mixture thereof, preferably styrene, but is not limited thereto.
  • the aromatic vinyl monomer (c1) is preferably contained in 10 to 80% by weight, more preferably 50 to 70% by weight based on 100% by weight of the copolymer resin (C) containing a silicone-based compound.
  • the unsaturated nitrile monomer (c2) may be acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, ⁇ -chloroacrylonitrile, or a mixture thereof, and preferably acrylonitrile. This is not restrictive.
  • the unsaturated nitrile monomer (c2) is preferably contained in 10 to 80% by weight, more preferably 20 to 50% by weight based on 100% by weight of the copolymer resin (C) containing a silicone-based compound.
  • the (meth) acrylic monomer (c3) may preferably include an aromatic or aliphatic methacrylate having a structure represented by the following formulas (2) and (3).
  • m is an integer of 0 to 20
  • X is hydrogen or methyl
  • Y is methyl, cyclohexyl, phenyl, benzyl, methylphenyl, methylethylphenyl, methoxyphenyl, cyclohexylphenyl, chlorophenyl group , Bromophenyl group, phenylphenyl group and benzylphenyl group.
  • m is an integer of 0 to 20
  • X is hydrogen or a methyl group
  • Z is oxygen (O) or sulfur (S)
  • Ar is a phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexyl It may be selected from the group consisting of phenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group.
  • Examples of the aromatic or aliphatic methacrylate including the structures of Formulas 2 and 3 include cyclohexyl methacrylate, phenoxy methacrylate, phenoxy ethyl methacrylate, 2-ethylphenoxy methacrylate, 2- Ethylthiophenyl methacrylate, 2-ethylaminophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1 -Methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl
  • methacrylic acid esters acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxy groups, etc. may be used, and these may be used alone or in combination. It may be used by mixing more than one species.
  • methacrylic acid esters including methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate;
  • Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate;
  • Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride;
  • Esters containing hydroxy groups including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and monoglycerol acrylate; Or mixtures thereof.
  • the (meth) acrylic monomer (c3) is preferably contained in an amount of 1 to 30% by weight, more preferably 5 to 20% by weight, based on 100% by weight of the copolymer resin (C) containing the silicone compound.
  • the content range of the (meth) acrylic monomer (c3) is less than 1% by weight, the effect of improving fluidity is slight, and if it exceeds 30% by weight, there is a problem of lowering the heat resistance of the resin.
  • the silicon compound (c4) having two or more unsaturated reactors may include a silicon compound having a structure represented by the following Chemical Formula 4 in the form of one kind or a mixture of two or more kinds.
  • the silicone compound serves as a crosslinking agent in the copolymer resin.
  • R 1 to R 8 are each independently a hydrogen atom, linear or branched C 1 -C 5 alkyl group, C 4 -C 6 cycloalkyl group, C 2 -C 12 unsaturated alkyl group, C 6 -C 10 aryl group, hydroxyl group, C 1 -C 5 alkoxy group, acetoxy group, amino group, amide Group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group and a mercapto group, wherein at least two or more of R 1 to R 8 have a polymerizable unsaturated reactor.
  • silicone-based compound (c4) having two or more unsaturated reactors include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, diacetoxy methylvinylsilane, 1,1,1,3,5,5,5,- Heptamethyl-3-vinyltrisiloxane, 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, ⁇ , ⁇ -divinyl polydimethylsiloxane and vinyl modified dimethylsiloxane, 1,3,5-trivinyl-1 , 1,3,5,5-pentamethyltrisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, polyvinylmethylsilazane, 1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane and the like are possible, but are not limited thereto, and these may be used alone or in combination.
  • the silicone compound (c4) having two or more unsaturated reactors serves as a cross-linker agent, and has a vinyl content of 0.05 to 10 mmol / g.
  • the silicone compound (c4) having two or more unsaturated reactors is preferably included in an amount of 0.1 to 25% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the copolymer resin (C) containing the silicon-based compound. to be.
  • the content range of the silicone compound (c4) having two or more unsaturated reactors is 1 to 25% by weight, it has the advantage of simultaneously expressing impact resistance and fluidity improving effect.
  • the silicone compound (c4) having two or more unsaturated reactors has a viscosity of 5,000 cPs or less, specifically 0.001 to 5,000 cPs, and preferably a vinyl content of 0.05 to 10 mmol / g, more preferably 0.5 To 3,000 cPs and vinyl content of 0.1 to 5 mmol / g.
  • Copolymer resin (C) comprising the silicone compound of the present invention is 10 to 80% by weight aromatic vinyl monomer (c1), 10 to 80% by weight unsaturated nitrile monomer (c2), (meth) acrylic monomer (c3) 1
  • a composition of 0.1 to 25% by weight of the silicone-based compound (c4) having from 30 to 30% by weight and two or more unsaturated reactors it is possible to simultaneously improve impact resistance and fluidity without compromising the heat resistance of the polycarbonate resin. There is this.
  • the weight average molecular weight of copolymer resin (C) containing a silicone type compound is 30,000-800,000 g / mol.
  • the copolymer resin (C) containing the silicone-based compound has such a molecular weight range, it is possible to simultaneously increase the fluidity and impact resistance of the thermoplastic resin while maintaining the existing excellent physical properties.
  • Copolymer resin (C) comprising a silicone compound is 100% by weight of the total resin composition comprising (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a copolymer resin containing a silicone compound. With respect to%, it may be included in 10 to 30% by weight.
  • the content of the copolymer resin (C) containing a silicon-based compound is less than 10% by weight, it is impossible to obtain a sufficient impact and fluidity improvement effect, and if more than 30% by weight, impact and fluidity may be lowered.
  • the polycarbonate-based thermoplastic resin composition of the present invention is added to the blend of the polycarbonate resin (A) and the rubber-modified acrylic graft copolymer resin (g-ASA) by adding a copolymer resin containing a silicone compound to the impact strength and fluidity. At the same time, the characteristics are improved.
  • the polycarbonate-based thermoplastic resin composition of the present invention may further include an additive (D) according to each use.
  • the polycarbonate-based thermoplastic resin composition includes surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricants, and static electricity.
  • An inhibitor, a pigment, a dye, a flame retardant, or a mixture thereof may further be included as an additive (D), but is not necessarily limited thereto.
  • the polycarbonate-based thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition.
  • the components of the present invention and other additives may be mixed at the same time and then melt-extruded in an extruder to produce pellets or chips.
  • the polycarbonate-based thermoplastic resin composition of the present invention may be prepared in the form of a resin molded article according to a known resin production method.
  • the components of the present invention and other additives may be mixed at the same time and then melt extruded in an extruder to produce pellet form. And such pellets can be used to manufacture plastic injection or compression molded articles.
  • the molding method There is no particular limitation on the molding method, and for example, extrusion molding, injection molding, calender molding, vacuum molding, or the like may be applied.
  • thermoplastic resin composition of the present invention can be usefully used in various products.
  • it is widely applicable including exterior materials, components or parts of automobiles, lenses, windows, etc. that require heat resistance and impact resistance at the same time, for example, televisions, washing machines, cassettes including automotive parts or exterior materials
  • housings of electrical and electronic products such as players, MP3, DMB, navigation, mobile phones, telephones, game machines, audio players, computers, printers, copiers and the like.
  • the present invention also provides a molded article prepared from the polycarbonate-based thermoplastic resin composition.
  • a molded article prepared from the polycarbonate-based thermoplastic resin composition.
  • an extrusion, injection or casting molding method may be applied. Such molding can be easily carried out by those skilled in the art.
  • the molded article of the present invention has an Izod impact strength of 23.00 to 90.00 kgf ⁇ cm / cm for 1/8 ′′ thick specimens measured according to ASTM D256.
  • molded articles may have an Izod notch impact strength of 23.02 kgf ⁇ cm / cm, 34.10 kgf ⁇ cm / cm, 57.68 kgf ⁇ cm / cm, or 58.0 kgf ⁇ cm of a 1/8 ′′ thick specimen measured according to ASTM D256. / cm, 64.53 kgf cm / cm, 65.17 kgf cm / cm.
  • the molded article of the present invention has a melt flow index (MI) of 34.00 to 80.00 g / 10min, measured under a temperature of 220 ° C. and a load of 10 kg according to ASTM D1238.
  • MI melt flow index
  • molded articles have a melt flow index (MI) of 55.8 g / 10min, 45.6 g / 10min, 40.2 g / 10min, 38.4 g / 10min, 35.4, measured under a temperature of 220 ° C. and a load of 10 kg, in accordance with ASTM D1238.
  • MI melt flow index
  • the molded article of the present invention has a bending strength of 810 to 840 kgf / cm 2 of 1/4 ′′ thick specimen measured according to ASTM D790.
  • molded articles may have a flexural strength of 816 kgf / cm2, 828 kgf / cm2, 814 kgf / cm2, 836 kgf / cm2, 823 kgf / cm2, 835 kgf / Cm 2.
  • Cheil Industries used a 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A) having a weight average molecular weight of 30,000 g / mol based on linear carbonate.
  • a copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 110,000 g / mol.
  • a copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 150,000 g / mol.
  • a copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 190,000 g / mol.
  • a copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 250,000 g / mol.
  • a copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 335,000 g / mol.
  • SAN resin styrene-acrylonitrile copolymer resin having a weight average molecular weight of 90,000 g / mol prepared by conventional suspension polymerization at 75 ° C. using 75% by weight of styrene and 25% by weight of acrylonitrile. It was.
  • SAN resin styrene-acrylonitrile copolymer resin having a weight average molecular weight of 115,000 g / mol prepared by conventional suspension polymerization at 75 ° C. using 71% by weight of styrene and 29% by weight of acrylonitrile. It was.
  • a weight average molecular weight of 90,000 prepared by conventional suspension polymerization using 68.87% styrene and 28.13% acrylonitrile using 3% by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g A branched vinyl copolymer resin of g / mol was used.
  • Example 1-6 and Comparative Example 1-4
  • the impact strength was improved by the increased molecular weight and the silicone-based compound, and the flexible butyl acrylate monomer having a branched structure and a low glass transition temperature (Tg) was used. As a result, the fluidity was improved, and the moldability was improved.
  • Tg glass transition temperature
  • Examples 1-2 the molecular weight of the copolymer (C) is reduced, and the use of monomers (butyl acrylate and silicone-based compounds) with a flexible, low glass transition temperature (Tg) shows excellent fluidity. However, the impact strength was slightly reduced.
  • Example 3-4 impact strength and fluidity were improved by using an appropriate molecular weight of the flexible branched vinyl copolymer.
  • Comparative Example 2 the impact strength was improved by using a high molecular weight SAN resin having a high acrylonitrile content, but it was confirmed that the fluidity and the flexural properties were sharply decreased.
  • Comparative Example 3 shows that the butyl acrylate monomer having a low glass transition temperature (Tg) is used instead of the silicon-based compound (c4) having two or more unsaturated reactors, thereby improving fluidity but decreasing impact strength.
  • Tg glass transition temperature
  • Comparative Example 4 shows that the impact strength is improved by using a silicone-based compound having two or more unsaturated reactors as a crosslinking agent, but the fluidity is lowered because no (meth) acrylic monomer (c3) is used.

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Abstract

A polycarbonate-based thermoplastic composition according to the present invention comprises (A) a polycarbonate resin, (B) a rubber-modified acryl-based graft copolymer resin, and (C) a silicon-based compound containing copolymer. The polycarbonate-based thermoplastic composition has excellent flowability without deteriorations in impact strength and heat resistance by introducing the silicon-based containing copolymer into the polycarbonate resin.

Description

폴리카보네이트계 열가소성 수지 조성물 및 성형품 Polycarbonate Thermoplastic Compositions and Molded Articles
본 발명은 폴리카보네이트계 열가소성 수지 조성물에 관한 것이다. 보다 구체적으로, 충격강도 및 내열성이 저하되지 않고, 유동성이 우수한 폴리카보네이트계 열가소성 수지 조성물에 관한 것이다.The present invention relates to a polycarbonate-based thermoplastic resin composition. More specifically, the present invention relates to a polycarbonate-based thermoplastic resin composition excellent in fluidity without impairing impact strength and heat resistance.
열가소성 수지는 유리나 금속에 비해 비중이 낮으며, 성형성 및 내충격성 등과 같은 우수한 물성을 갖는다. 최근 전기 전자 제품의 저원가, 대형화, 경량화 추세에 따라 플라스틱 제품은 기존의 유리나 금속의 영역을 빠르게 대체하여 전기 전자 제품에서 자동차 부품까지 사용 영역을 넓히고 있다. 이에 따라 외장재로서의 기능 및 외관의 성능이 중요해지며, 외부 충격과 가공성에 대한 요구도 높아지고 있다.Thermoplastic resins have a lower specific gravity than glass or metal, and have excellent physical properties such as moldability and impact resistance. Recently, due to the trend of low cost, large size, and light weight of electric and electronic products, plastic products are rapidly replacing the existing glass or metal areas, thereby expanding the use area from electric and electronic products to automobile parts. Accordingly, the function and appearance performance of the exterior material is important, and the demand for external impact and workability is also increasing.
열가소성 수지 중 폴리카보네이트계 열가소성 수지는 높은 충격강도, 고내열성 및 높은 투명성을 가지고 있기 때문에 다양한 엔지니어링 기기에서 사용되고 있다.Among the thermoplastic resins, polycarbonate-based thermoplastic resins have high impact strength, high heat resistance, and high transparency, and thus are used in various engineering devices.
다만, 폴리카보네이트계 열가소성 수지는 상대적으로 좋지 않은 유동성을 가진다. 따라서, 폴리카보네이트계 열가소성 수지의 유동성을 개선시키기 위해서, 하나 이상의 폴리머 및 첨가제를 혼합하여 사용하고 있다.However, polycarbonate-based thermoplastic resins have a relatively poor fluidity. Therefore, in order to improve the fluidity of the polycarbonate-based thermoplastic resin, one or more polymers and additives are mixed and used.
종래에는 낮은 분자량의 스티렌-아크릴로니트릴(SAN) 수지를 사용함으로써, 폴리카보네이트계 열가소성 수지의 유동성을 개선시키는 시도를 하였으나, 이 시도는 유동성을 개선시키는 데는 성공하였지만 충격강도 및 내열성이 저하되는 문제점을 갖고 있다.Conventionally, attempts have been made to improve the fluidity of polycarbonate-based thermoplastic resins by using low molecular weight styrene-acrylonitrile (SAN) resins. However, these attempts have succeeded in improving the fluidity, but the impact strength and heat resistance are deteriorated. Have
또한, 기존의 PC/SAN 얼로이(alloy) 기술에서는 충격보강재로 g-ABS가 사용되었다. g-ABS는 SAN과 친화력이 높기 때문에 PC/SAN 얼로이(alloy)시 SAN 내부에 존재하고, 외부 충격이 가해졌을 때 주로 PC와 SAN의 계면에서 파괴가 먼저 일어나기에 충격보강 효과가 떨어졌다. 따라서, 충격보강재로 g-ABS 사용하는 경우, 외부 충격이 가해졌을 때 주로 PC와 SAN의 계면에서 파괴가 먼저 일어나는 문제점을 갖고 있다.In addition, g-ABS is used as an impact modifier in the existing PC / SAN alloy technology. Because g-ABS has a high affinity with SAN, it exists inside the SAN during PC / SAN alloy, and when the external shock is applied, the impact reinforcement effect is lowered mainly because the destruction occurs first at the interface between the PC and the SAN. Therefore, when g-ABS is used as the impact reinforcing material, when an external impact is applied, there is a problem that destruction occurs mainly at the interface between the PC and the SAN.
이에 본 발명자들은 PC 및 SAN 모두와 친화력이 유사한 고무변성 아크릴계 그라프트 공중합체 수지를 사용하여 충격보강 효과를 개선시키고자 한다. 또한 충격강도와 내열성과 같은 기계적 물성을 저하시키지 않고, 유동성이 우수하여 성형성 및 가공성이 개선된 폴리카보네이트계 열가소성 수지 조성물을 개발하고자 한다.The present inventors intend to improve the impact reinforcement effect by using a rubber-modified acrylic graft copolymer resin similar in affinity with both PC and SAN. In addition, it is intended to develop a polycarbonate-based thermoplastic resin composition having excellent fluidity and improved moldability and processability without deteriorating mechanical properties such as impact strength and heat resistance.
본 발명의 목적은 우수한 유동성을 가지는 폴리카보네이트계 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent fluidity.
본 발명의 다른 목적은 우수한 충격강도 및 내열성을 가지는 폴리카보네이트계 열가소성 수지 조성물을 제공하기 위한 것이다. Another object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent impact strength and heat resistance.
본 발명의 또 다른 목적은 우수한 성형성을 가지는 폴리카보네이트계 열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent moldability.
본 발명의 또 다른 목적은 상기 폴리카보네이트계 열가소성 수지 조성물을 사용하여 제조된 성형품을 제공하기 위한 것이다.Still another object of the present invention is to provide a molded article manufactured using the polycarbonate-based thermoplastic resin composition.
본 발명의 상기 및 기타의 목적들은 모두 하기 설명되는 본 발명에 의해서 달성될 수 있다.Both the above and other objects of the present invention can be achieved by the present invention described below.
본 발명에 따른 폴리카보네이트계 열가소성 수지 조성물은 (A) 폴리카보네이트 수지, (B) 고무변성 아크릴계 그라프트 공중합체 수지 및 (C) 실리콘계 화합물을 포함하는 공중합체 수지를 포함한다.The polycarbonate-based thermoplastic resin composition according to the present invention includes a copolymer resin containing (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a silicone-based compound.
본 발명의 폴리카보네이트계 열가소성 수지 조성물은 폴리카보네이트 수지(A) 40 내지 80 중량%, 상기 고무변성 아크릴계 그라프트 공중합체 수지(B) 1 내지 30 중량% 및 상기 실리콘계 화합물을 포함하는 공중합체 수지(C) 10 내지 30 중량%를 포함할 수 있다.Polycarbonate-based thermoplastic resin composition of the present invention is a copolymer resin containing 40 to 80% by weight of polycarbonate resin (A), 1 to 30% by weight of the rubber-modified acrylic graft copolymer resin (B) and the silicone-based compound ( C) 10 to 30% by weight.
또한, 다른 구체예에 있어서, 본 발명의 폴리카보네이트계 열가소성 수지 조성물은 연속상인 제1수지, 분산상인 제2수지 및 상기 연속상인 제1수지 및 상기 분산상인 제2수지의 계면에 위치하는 충격보강재를 포함할 수 있다.In another embodiment, the polycarbonate-based thermoplastic resin composition of the present invention is an impact reinforcing material located at the interface between the first resin in the continuous phase, the second resin in the dispersed phase and the first resin in the continuous phase and the second resin in the dispersed phase. It may include.
본 발명의 폴리카보네이트계 열가소성 수지 조성물은 연속상인 제1수지 40 내지 80 중량%, 상기 분산상인 제2수지 10 내지 30 중량%, 및 상기 충격보강재 1 내지 30 중량%를 포함할 수 있다.The polycarbonate-based thermoplastic resin composition of the present invention may include 40 to 80% by weight of the first resin in the continuous phase, 10 to 30% by weight of the second resin in the dispersed phase, and 1 to 30% by weight of the impact modifier.
연속상인 제1수지는 폴리카보네이트 수지(A)이고, 분산상인 제2수지는 실리콘계 화합물을 포함하는 공중합체 수지(C)이고, 충격보강재는 고무변성 아크릴계 그라프트 공중합체 수지(B)일 수 있다. The first resin in the continuous phase is a polycarbonate resin (A), the second resin in the dispersed phase is a copolymer resin (C) containing a silicone compound, and the impact modifier may be a rubber-modified acrylic graft copolymer resin (B). .
고무변성 아크릴계 그라프트 공중합체 수지(B)는 고무(b1) 40 내지 98 중량%, 알킬메타크릴레이트(b2) 1 내지 30 중량% 및 비닐계 방향족 단량체(b3) 1 내지 40 중량%를 포함할 수 있다. The rubber-modified acrylic graft copolymer resin (B) may include 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and 1 to 40% by weight of vinyl aromatic monomer (b3). Can be.
알킬메타크릴레이트(b2)는 탄소원자수가 1 내지 20일 수 있다.Alkyl methacrylate (b2) may have 1 to 20 carbon atoms.
실리콘계 화합물을 포함하는 공중합체 수지(C)는 분지형 비닐계 공중합체 수지일 수 있다.The copolymer resin (C) including the silicone compound may be a branched vinyl copolymer resin.
실리콘계 화합물을 포함하는 공중합체(C)는 방향족 비닐계 단량체(c1) 10 내지 80 중량%, 불포화 니트릴계 단량체(c2) 10 내지 80 중량%, (메타)아크릴계 단량체(c3) 1 내지 30 중량% 및 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4) 0.1 내지 25 중량%를 공중합하여 제조된 공중합체일 수 있다. Copolymer (C) comprising a silicone-based compound is 10 to 80% by weight aromatic vinyl monomer (c1), 10 to 80% by weight unsaturated nitrile monomer (c2), 1 to 30% by weight (meth) acrylic monomer (c3) And it may be a copolymer prepared by copolymerizing 0.1 to 25% by weight of the silicon-based compound (c4) having two or more unsaturated reactors.
실리콘계 화합물을 포함하는 공중합체 수지(C)의 중량 평균 분자량은 30,000 내지 800,000 g/mol일 수 있다.The weight average molecular weight of the copolymer resin (C) including the silicone compound may be 30,000 to 800,000 g / mol.
방향족 비닐계 단량체(c1)는 스티렌, p-메틸스티렌, α-메틸스티렌, 할로겐 치환 스티렌, 알킬 치환 스티렌 및 이들의 혼합물로 이루어진 군에서 선택할 수 있다. The aromatic vinyl monomer (c1) may be selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, halogen substituted styrene, alkyl substituted styrene, and mixtures thereof.
불포화 니트릴계 단량체(c2)는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 페닐아크릴로니트릴, α-클로로아크릴로니트릴 및 이들의 혼합물로 이루어진 군에서 선택할 수 있다.The unsaturated nitrile monomer (c2) may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile and mixtures thereof.
(메타)아크릴계 단량체(c3)는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 프로필 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 헥실 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트 및 이들의 혼합물로 이루어진 군에서 선택할 수 있다.  The (meth) acrylic monomer (c3) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylates and mixtures thereof.
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 하기 화학식 4로 표시되는 구조를 갖는 실리콘계 화합물을 단독 또는 2종 이상의 혼합물 형태로 포함될 수 있다:The silicone compound (c4) having two or more unsaturated reactors may include a silicone compound having a structure represented by the following Chemical Formula 4 alone or in a mixture of two or more thereof:
[화학식 4][Formula 4]
Figure PCTKR2013005727-appb-I000001
Figure PCTKR2013005727-appb-I000001
(상기 화학식 4에서, l, m 및 n은 0 내지 100의 정수이며(단, l, m 및 n은 동시에 0은 아님), R1 내지 R8은 각각 독립적으로 수소원자, 선형 또는 분지형 C1-C5의 알킬기, C4-C6의 사이클로알킬기, C2-C12의 불포화알킬기, C6-C10 아릴기, 수산기, C1-C5의 알콕시기, 아세톡시기, 아미노기, 아미드기, 에폭시기, 카르복실기, 할로겐기, 에스테르기, 이소시아네이트기 및 메르캅토기로 구성된 군에서 선택되며, 이때 상기 R1 내지 R8 중 적어도 두 개 이상은 중합 가능한 불포화 반응기를 가짐.)(In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not 0 at the same time), R 1 to R 8 are each independently a hydrogen atom, linear or branched C An alkyl group of 1 -C 5 , a cycloalkyl group of C 4 -C 6 , an unsaturated alkyl group of C 2 -C 12 , a C 6 -C 10 aryl group, a hydroxyl group, an alkoxy group of C 1 -C 5 , an acetoxy group, an amino group, An amide group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, and a mercapto group, wherein at least two of R 1 to R 8 have a polymerizable unsaturated reactor.)
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 점도가 5000 cPs 이하이고, 비닐 함량이 0.05 내지 10 mmol/g일 수 있다.  The silicone-based compound (c4) having two or more unsaturated reactors may have a viscosity of 5000 cPs or less and a vinyl content of 0.05 to 10 mmol / g.
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 2,4,6,8-테트라메틸 테트라비닐 사이클로테트라실록산, 1,3,5- 트리비닐-1,1,3,5,5-펜타메틸트리실록산, 2,4,6-트리비닐-1,3,5-트리메틸사이클로실라잔, α,ω-디비닐폴리디메틸실록산, 폴리비닐메틸실라잔, 1,3-디비닐-1,1,3,3-테트라메틸디실록산 및 이들의 혼합물로 구성된 군에서 선택할 수 있다.Silicone-based compounds (c4) having two or more unsaturated reactors are 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyl Trisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, α, ω-divinylpolydimethylsiloxane, polyvinylmethylsilazane, 1,3-divinyl-1,1, 3,3-tetramethyldisiloxane and mixtures thereof.
또한, 본 발명의 폴리카보네이트계 열가소성 수지 조성물로부터 제조되는 성형품을 포함한다.In addition, the molded article produced from the polycarbonate-based thermoplastic resin composition of the present invention.
이하 본 발명의 구체적인 내용을 하기에 상세히 설명한다.Hereinafter, specific contents of the present invention will be described in detail below.
본 발명에 따른 폴리카보네이트계 열가소성 수지 조성물은 유동성, 충격강도 및 내열성이 우수하고, 성형성을 개선시킨다.The polycarbonate-based thermoplastic resin composition according to the present invention is excellent in fluidity, impact strength and heat resistance, and improves moldability.
본 발명에 따른 폴리카보네이트계 열가소성 수지 조성물은 유동성, 충격강도 및 내열성이 우수하고, 성형성을 개선시킨다.The polycarbonate-based thermoplastic resin composition according to the present invention is excellent in fluidity, impact strength and heat resistance, and improves moldability.
본 발명의 폴리카보네이트계 열가소성 수지 조성물은 (A) 폴리카보네이트 수지, (B) 고무변성 아크릴계 그라프트 공중합체 수지 및 (C) 실리콘계 화합물을 포함하는 공중합체 수지를 포함한다. 이하 각 성분에 대하여 구체적으로 설명한다.The polycarbonate-based thermoplastic resin composition of the present invention includes a copolymer resin containing (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a silicone compound. Each component is demonstrated concretely below.
또한, 본 발명의 폴리카보네이트계 열가소성 수지 조성물은 (A) 연속상인 제1수지, (C) 분산상인 제2수지 및 (B) 상기 연속상인 제1수지와 분산상의 제2수지의 계면에 위치하는 충격보강재를 포함한다. 이하 각 성분에 대하여 구체적으로 설명한다.In addition, the polycarbonate-based thermoplastic resin composition of the present invention is located at the interface between (A) the first resin in the continuous phase, (C) the second resin in the dispersed phase and (B) the first resin in the continuous phase and the second resin in the dispersed phase. Impact modifiers. Each component is demonstrated concretely below.
폴리카보네이트계 열가소성 수지 조성물Polycarbonate Thermoplastic Resin Composition
본 발명에 따른 폴리카보네이트계 열가소성 수지 조성물은 (A) 폴리카보네이트 수지 40 내지 80 중량%, (B) 고무변성 아크릴계 그라프트 공중합체 수지 1 내지 30 중량% 및 (C) 실리콘계 화합물을 포함하는 공중합체 수지 10 내지 30 중량%를 포함할 수 있다.Polycarbonate-based thermoplastic resin composition according to the present invention is a copolymer comprising (A) 40 to 80% by weight of polycarbonate resin, (B) 1 to 30% by weight of rubber-modified acrylic graft copolymer resin and (C) silicone compound It may include 10 to 30% by weight of the resin.
또한, 본 발명의 폴리카보네이트계 열가소성 수지 조성물은 (A) 연속상인 제1수지 40 내지 80 중량%, (C) 분산상인 제2수지 10 내지 30 중량% 및 상기 연속상인 제1수지와 분산상의 제2수지의 계면에 위치하는 (B) 충격보강재 1 내지 30 중량% 를 포함한다. 이하 각 성분에 대하여 구체적으로 설명한다.In addition, the polycarbonate-based thermoplastic resin composition of the present invention (A) 40 to 80% by weight of the first resin in the continuous phase, (C) 10 to 30% by weight of the second resin in the dispersed phase and the first resin and the dispersed phase of the continuous phase 1 to 30% by weight of the impact modifier (B) located at the interface of the two resins. Each component is demonstrated concretely below.
(A) 폴리카보네이트 수지(A) polycarbonate resin
본 발명에서, 폴리카보네이트 수지(A)는 특별히 제한되지 않는다. 예를 들어, 상기 폴리카보네이트 수지로서 지방족 폴리카보네이트 수지, 방향족 폴리카보네이트 수지, 이들의 코폴리카보네이트, 코폴리에스테르카보네이트 수지, 폴리카보네이트-폴리실록산 공중합체 또는 이들의 혼합물이 사용될 수 있다. 또한, 상기 폴리카보네이트 수지는 선형 또는 분지형 구조를 가질 수 있다.In the present invention, the polycarbonate resin (A) is not particularly limited. For example, an aliphatic polycarbonate resin, an aromatic polycarbonate resin, a copolycarbonate thereof, a copolycarbonate carbonate resin, a polycarbonate-polysiloxane copolymer or a mixture thereof may be used as the polycarbonate resin. In addition, the polycarbonate resin may have a linear or branched structure.
본 발명에서, 폴리카보네이트 수지는 폴리카보네이트계 열가소성 수지 조성물에서 연속상이다.In the present invention, the polycarbonate resin is a continuous phase in the polycarbonate-based thermoplastic resin composition.
본 발명에서, 폴리카보네이트 수지(A)는 하기 화학식 1로 표시되는 디페놀류와 포스겐, 할로겐 포르메이트, 카보네이트, 및 이들의 조합으로 이루어진 군에서 선택되는 화합물을 반응시켜 제조될 수 있다.In the present invention, the polycarbonate resin (A) can be prepared by reacting a compound selected from the group consisting of diphenols represented by the following formula (1) with phosgene, halogen formate, carbonate, and combinations thereof.
[화학식 1][Formula 1]
Figure PCTKR2013005727-appb-I000002
Figure PCTKR2013005727-appb-I000002
상기 화학식 1에서, A는 단일 결합, 치환 또는 비치환된 탄소수 1 내지 5의 알킬렌기, 치환 또는 비치환된 탄소수 2 내지 5의 알킬리덴기, 치환 또는 비치환된 탄소수 5 내지 6의 사이클로알킬렌기, 치환 또는 비치환된 탄소수 5 내지 10의 사이클로알킬리덴기, CO, S, 및 SO2로 이루어진 군에서 선택되는 연결기이고, 각각의 R1　및 R2는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 및 치환 또는 비치환된 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 치환기이고, n1　및 n2는 각각 독립적으로 0 내지 4의 정수이며, 상기 "치환된"이란 수소 원자가 할로겐기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 할로알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 1 내지 20의 알콕시기, 및 이들의 조합으로 이루어진 군에서 선택되는 치환기로 치환된 것을 의미한다.In Formula 1, A is a single bond, a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 5 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 6 carbon atoms , A substituted or unsubstituted cycloalkylidene group having 5 to 10 carbon atoms, CO, S, and SO 2 It is a linking group selected from the group, each R 1 and R 2 are each independently substituted or unsubstituted carbon 1 It is a substituent selected from the group consisting of an alkyl group of 30 to 30, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, n 1 and n 2 are each independently an integer of 0 to 4, the "substituted" is a hydrogen atom And a substituent selected from the group consisting of a halogen group, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a combination thereof. It means the.
상기 화학식 1로 표시되는 디페놀류는 2종 이상이 조합되어 폴리카보네이트수지의 반복단위를 구성할 수 있다. 상기 디페놀류의 구체예로는 히드로퀴논, 레조시놀, 4,4'-디히드록시디페닐, 2,2-비스-(4-히드록시페닐)-프로판('비스페놀-A'라고도 함), 2,4-비스-(4-히드록시페닐)-2-메틸부탄, 1,1-비스-(4-히드록시페닐)-사이클로헥산, 2,2-비스-(3-클로로-4-히드록시페닐)-프로판, 2,2-비스-(3,5-디클로로-4-히드록시페닐)-프로판 등을 들 수 있다. 상기 디페놀류 중에서, 2,2-비스-(4-히드록시페닐)-프로판, 2,2-비스-(3,5-디클로로-4-히드록시페닐)-프로판, 또는 1,1-비스-(4-히드록시페닐)-사이클로헥산을 바람직하게 사용할 수 있다. 또한 2,2-비스-(4-히드록시페닐)-프로판을 더욱 바람직하게 사용할 수 있다.The diphenols represented by the formula (1) may combine two or more kinds to form a repeating unit of the polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane (also called 'bisphenol-A'), 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydrate Hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, etc. are mentioned. 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, or 1,1-bis- in the said diphenols (4-hydroxyphenyl) -cyclohexane can be preferably used. Also, 2,2-bis- (4-hydroxyphenyl) -propane can be used more preferably.
상기 폴리카보네이트 수지(A)는 중량평균 분자량이 10,000 내지 200,000 g/mol인 것이 바람직하며, 15,000 내지 80,000 g/mol인 것이 더욱 바람직하다, 상기 분자량 범위에서 우수한 충격강도를 확보할 수 있으며, 적당한 유동성을 가지게 되어 우수한 가공성을 얻을 수 있다. The polycarbonate resin (A) is preferably a weight average molecular weight of 10,000 to 200,000 g / mol, more preferably 15,000 to 80,000 g / mol, it is possible to ensure excellent impact strength in the molecular weight range, moderate fluidity It is possible to obtain excellent workability.
폴리카보네이트 수지(A)는 두 종류 이상의 디페놀류로부터 제조된 공중합체의 혼합물일 수도 있다. 또한 폴리카보네이트 수지(A)는 선형 폴리카보네이트 수지, 분지형(branched) 폴리카보네이트 수지, 폴리에스테르카보네이트 공중합체 수지 등을 사용할 수 있다. 선형 폴리카보네이트 수지로는 비스페놀-A계 폴리카보네이트 수지 등을 들 수 있다. 분지형 폴리카보네이트 수지로는 트리멜리틱 무수물, 트리멜리틱산 등과 같은 다관능성 방향족 화합물을 디페놀류 및 카보네이트와 반응시켜 제조한 것을 들 수 있다.　다관능성 방향족 화합물은 분지형 폴리카보네이트 수지 총량에 대하여 0.05 내지 2 몰%로 포함되는 것이 바람직하다.　폴리에스테르카보네이트 공중합체 수지로는 이관능성 카르복실산을 디페놀류 및 카보네이트와 반응시켜 제조한 것을 들 수 있다. 이때 카보네이트로는 디페닐카보네이트와 같은 디아릴카보네이트, 시클릭 에틸렌 카보네이트(cyclic ethylene carbonate) 등을 사용할 수 있다.The polycarbonate resin (A) may be a mixture of copolymers prepared from two or more kinds of diphenols. In addition, as the polycarbonate resin (A), a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like can be used. Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as linear polycarbonate resin. Examples of the branched polycarbonate resin include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. It is preferable that a polyfunctional aromatic compound is contained in 0.05-2 mol% with respect to the branched polycarbonate resin total amount. As polyester carbonate copolymer resin, what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, a diaryl carbonate such as diphenyl carbonate, cyclic ethylene carbonate, or the like may be used.
폴리카보네이트 수지(A)는 폴리카보네이트 수지(A), 고무변성 아크릴계 그라프트 공중합체 수지(B) 및 실리콘계 화합물을 포함하는 공중합체 수지(C)를 포함하는 전체 수지 조성물 100 중량%에 대하여, 40 내지 80 중량%로 포함될 수 있다. 바람직하게는 60 내지 80 중량%로 포함될 수 있다.The polycarbonate resin (A) is based on 100% by weight of the total resin composition containing the polycarbonate resin (A), the rubber-modified acrylic graft copolymer resin (B) and the copolymer resin (C) containing the silicone compound. To 80% by weight. Preferably it may be included in 60 to 80% by weight.
폴리카보네이트 수지(A)가 40 중량% 미만인 경우 내충격성, 인장물성 및 내열성이 저하되고, 80 중량% 초과인 경우 유동성이 저하된다.When the polycarbonate resin (A) is less than 40% by weight, impact resistance, tensile properties and heat resistance are lowered, and when it is more than 80% by weight, fluidity is lowered.
(B) 고무변성 아크릴계 그라프트 공중합체 수지(B) Rubber Modified Acrylic Graft Copolymer Resin
본 발명에서 고무변성 아크릴계 그라프트 공중합체 수지(B)는 충격보강재로서 고무(b1), 알킬메타크릴레이트(b2) 및 비닐계 방향족 단량체(b3)를 그라프트 시킨 공중합체이다. 고무변성 아크릴계 그라프트 공중합체 수지(B)는 고무(b1) 40 내지 98 중량%, 알킬메타크릴레이트(b2) 1 내지 30 중량% 및 비닐계 방향족 단량체(b3) 1 내지 40 중량%를 포함할 수 있다. In the present invention, the rubber-modified acrylic graft copolymer resin (B) is a copolymer obtained by grafting rubber (b1), alkyl methacrylate (b2) and vinyl-based aromatic monomer (b3) as impact modifiers. The rubber-modified acrylic graft copolymer resin (B) may include 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and 1 to 40% by weight of vinyl aromatic monomer (b3). Can be.
고무(b1)의 비제한적 예로는 폴리부타디엔, 폴리(스티렌-부타디엔), 폴리(아크릴로니트릴-부타디엔)등의 디엔계 고무,　상기 디엔계　고무에 수소를 첨가한 포화고무, 이소프렌고무,　클로로프렌고무, 폴리아크릴산부틸　등의 아크릴계　고무, 에틸렌-프로필렌고무, 에틸렌-프로필렌-디엔단량체 삼원공중합체(EPDM) 등이 있다. 상기 고무(b1)는 단독 또는 2종 이상 혼합하여 사용될 수 있다. 이 중　디엔계 고무가 바람직하며, 더욱 바람직하게는 부타디엔계 고무가 적합하다. 고무(b1)의 함량은 고무변성 아크릴계 그라프트 공중합체 수지(B) 전체 중량　중 40　내지 98 중량%가 적당하다.　고무(b1)의 함량이 40 중량% 미만인 경우, 내충격성이 저하되고, 98 중량% 초과인 경우 내열성 저하된다. 바람직하게는 60 내지 80 중량%를 포함할 수 있다. 상기 고무(b1)의 평균 입자 크기는 충격강도 및 외관을 고려하여 0.1 내지 0.7 μm 가 적합하다. Non-limiting examples of the rubber (b1) include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers in which hydrogen is added to the diene-based rubber, isoprene rubber, and chlorochloroprene rubber. And acrylic rubber such as butyl polyacrylate, ethylene-propylene rubber, and ethylene-propylene-diene terpolymer (EPDM). The rubber (b1) may be used alone or in combination of two or more thereof. Among these, the diene diene rubber is preferable, and butadiene rubber is more preferable. The content of the rubber (b1) is appropriately 40 to 98% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). When the content of the rubber (b1) is less than 40% by weight, the impact resistance is lowered, and when it is more than 98% by weight, the heat resistance is lowered. Preferably 60 to 80% by weight. The average particle size of the rubber (b1) is preferably 0.1 to 0.7 μm in consideration of the impact strength and appearance.
본 발명에서 고무변성 아크릴계 그라프트 공중합체 수지(B)는 충격보강재로 사용되며, 연속상인 폴리카보네이트 수지(제1수지)와 분산상인 실리콘계 화합물을 포함하는 공중합체 수지(제2수지)의 계면에 위치한다. In the present invention, the rubber-modified acrylic graft copolymer resin (B) is used as an impact reinforcing material, and is used at the interface between a polycarbonate resin (first resin) in a continuous phase and a copolymer resin (second resin) containing a silicone compound in a dispersed phase. Located.
기존의 폴리카보네이트계 수지조성물(예를 들면, PC/SAN alloy)에서는 충격보강재로 g-ABS수지가 사용되었다. g-ABS수지는 SAN과 친화력이 높기 때문에 SAN 내부에 존재하고, 외부 충격이 가해졌을 때 주로 PC와 SAN의 계면에서 파괴가 먼저 일어나기에 충격보강 효과가 떨어졌다. In the existing polycarbonate resin composition (eg, PC / SAN alloy), g-ABS resin was used as an impact reinforcing material. Since g-ABS resin has a high affinity with SAN, it exists inside SAN, and when the external shock is applied, the impact reinforcing effect is inferior because the destruction occurs first at the interface between PC and SAN.
그러나, 본원발명에서 충격보강재로 사용되는 고무변성 아크릴계 그라프트 공중합체 수지(B)는 폴리카보네이트(A) 및 실리콘계 화합물을 포함하는 공중합체 수지(C)와의 친화력이 유사하다. 즉, 폴리카보네이트(A)와 고무변성 아크릴계 그라프트 공중합체 수지(B)의 친화력 및 고무변성 아크릴계 그라프트 공중합체 수지(B)와 실리콘계 화합물을 포함하는 공중합체 수지(C)와의 친화력이 유사하다. 따라서, 고무변성 아크릴계 그라프트 공중합체 수지(B)는 연속상인 폴리카보네이트 수지(제1수지)와 분산상인 실리콘계 화합물을 포함하는 공중합체 수지(제2수지)의 계면에 위치함으로써 외부 충격이 가해졌을 때 계면에서 파괴가 먼저 일어나지 않게 한다. 따라서, 본원발명에 따른 폴리카보네이트계 수지 조성물은 충격보강효과가 우수하다.However, the rubber-modified acrylic graft copolymer resin (B) used as the impact reinforcing material in the present invention has similar affinity with the copolymer resin (C) containing a polycarbonate (A) and a silicone-based compound. That is, the affinity of the polycarbonate (A) and the rubber modified acrylic graft copolymer resin (B) and the affinity of the rubber modified acrylic graft copolymer resin (B) and the copolymer resin (C) containing a silicone compound are similar. . Therefore, the rubber-modified acrylic graft copolymer resin (B) is located at the interface between the continuous polycarbonate resin (first resin) and the copolymer resin (second resin) containing the disperse phase silicone-based compound, so that external impact is applied. At this time, no destruction occurs at the interface. Therefore, the polycarbonate-based resin composition according to the present invention is excellent in impact reinforcing effect.
알킬메타크릴레이트(b2)로는 탄소원자수가 1 내지 20인 알킬메타크릴레이트가 사용될 수 있다. As the alkyl methacrylate (b2), alkyl methacrylate having 1 to 20 carbon atoms may be used.
상기 알킬메타크릴레이트의 예로는 메틸메타크릴레이트, 에틸메타크릴레이트, 부틸메타크릴레이트, 2-에틸헥실 메타크릴레이트 등이 있으나 이에 한정되지는 않는다. 이들은 단독 또는 2종 이상의 혼합물로도 사용될 수 있다. 이중 메틸메타크릴레이트가 가장 바람직하다. 알킬메타크릴레이트의 함량은 고무변성 아크릴계 그라프트 공중합체 수지(B) 전체 중량 중 1 내지 30 중량%, 바람직하게는 5 내지 15 중량%로 적용될 수 있다. 알킬메타크릴레이트의 함량이 1 중량% 미만인 경우 분산성이 저하되고, 30 중량% 초과인 경우 내충격성이 저하될 수 있다.Examples of the alkyl methacrylate include, but are not limited to, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These may be used alone or in mixture of two or more thereof. Most preferred is methyl methacrylate. The content of the alkyl methacrylate may be applied in 1 to 30% by weight, preferably 5 to 15% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). If the content of the alkyl methacrylate is less than 1% by weight, the dispersibility may be lowered, and if it is more than 30% by weight, impact resistance may be lowered.
비닐계 방향족 단량체(b3)는 스티렌, α-메틸스티렌, p-메틸스티렌, 비닐톨루엔, 2,4-디메틸스티렌, 할로겐 또는 알킬 치환 스티렌, 또는 이들의 혼합물을 사용할 수 있고, 바람직하게는 스티렌이지만, 이에 제한되지 않는다. 비닐계 방향족 단량체(b3)는 고무변성 아크릴계 그라프트 공중합체 수지(B) 전체 중량 중 1 내지 40 중량%, 바람직하게는 10 내지 30 중량%로 포함될 수 있다. 비닐계 방향족 단량체(b3)의 함량이 1 중량% 미만인 경우 중합성이 저하되고, 40 중량% 초과인 경우 광택성이 저하될 수 있다. The vinyl aromatic monomer (b3) may use styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene, or a mixture thereof, preferably styrene. This is not restrictive. Vinyl-based aromatic monomer (b3) may be included in 1 to 40% by weight, preferably 10 to 30% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). When the content of the vinyl aromatic monomer (b3) is less than 1% by weight, the polymerizability may be lowered, and when it is more than 40% by weight, the glossiness may be lowered.
고무변성 아크릴계 그라프트 공중합체 수지(B)는 폴리카보네이트 수지(A), 고무변성 아크릴계 그라프트 공중합체 수지(B) 및 실리콘계 화합물을 포함하는 공중합체 수지(C)를 포함하는 전체 수지 조성물 100 중량%에 대하여, 1 내지 30 중량%로 포함될 수 있다. 바람직하게는 5 내지 15 중량%로 포함될 수 있다.The rubber-modified acrylic graft copolymer resin (B) is a total weight of 100 resin compositions comprising a polycarbonate resin (A), a rubber-modified acrylic graft copolymer resin (B) and a copolymer resin (C) containing a silicone compound. With respect to%, it may be included in 1 to 30% by weight. Preferably it may be included in 5 to 15% by weight.
고무변성 아크릴계 그라프트 공중합체 수지(B)가 1 중량% 미만인 경우 내충격성 및 굴곡강도가 저하되고, 30 중량% 초과인 경우 유동성 및 내열성이 저하된다.When the rubber-modified acrylic graft copolymer resin (B) is less than 1% by weight, impact resistance and flexural strength are lowered, and when it is more than 30% by weight, fluidity and heat resistance are lowered.
(C) 실리콘계 화합물을 포함하는 공중합체 수지(C) Copolymer Resin Containing Silicone Compound
본 발명의 실리콘계 화합물을 포함하는 공중합체 수지(C)는 유연한(flexible) 분지형 (branched) 비닐계 공중합체 수지가 사용될 수 있다.As the copolymer resin (C) including the silicone compound of the present invention, a flexible branched vinyl copolymer resin may be used.
본 발명에서, 실리콘계 화합물을 포함하는 공중합체 수지는 폴리카보네이트계 열가소성 수지 조성물에서 분산상이다.In the present invention, the copolymer resin containing the silicone compound is a dispersed phase in the polycarbonate thermoplastic resin composition.
본 발명에서 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)는 (c1) 방향족 비닐계 단량체, (c2) 불포화 니트릴계 단량체, (c3) (메타)아크릴계 단량체 및 (c4) 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물을 공중합하여 제조된 공중합체 또는 이들 공중합체의 혼합물이 사용될 수 있다. In the present invention, the copolymer resin (C) including the silicone-based compound includes (c1) an aromatic vinyl monomer, (c2) an unsaturated nitrile monomer, (c3) a (meth) acrylic monomer, and (c4) two or more unsaturated reactors. The copolymer prepared by copolymerizing the silicone-based compound or a mixture of these copolymers can be used.
본 발명에서 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)는 방향족 비닐계 단량체(c1) 10 내지 80 중량%, 불포화 니트릴계 단량체(c2) 10 내지 80 중량%, (메타)아크릴계 단량체(c3) 1 내지 30 중량% 및 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4) 0.1 내지 25 중량%를 공중합하여 제조된 공중합체 또는 이들 공중합체의 혼합물이 사용될 수 있다. In the present invention, the copolymer resin (C) including the silicone compound is 10 to 80 wt% of the aromatic vinyl monomer (c1), 10 to 80 wt% of the unsaturated nitrile monomer (c2), and (meth) acrylic monomer (c3) Copolymers prepared by copolymerizing 1 to 30% by weight and 0.1 to 25% by weight of the silicone-based compound (c4) having two or more unsaturated reactors or a mixture of these copolymers may be used.
이러한 실리콘계 화합물을 포함하는 공중합체 수지(C)는 당업계에 공지된 통상의 중합 방법, 예를 들면, 괴상중합, 유화중합, 현탁중합 등을 이용하여 제조할 수 있다. Copolymer resin (C) containing such a silicone-based compound can be prepared using conventional polymerization methods known in the art, for example, bulk polymerization, emulsion polymerization, suspension polymerization and the like.
실리콘계 화합물을 포함하는 공중합체 수지(C)는 불순물 함량이 적기 때문에 우수한 안정성을 가지고, 단순한 현탁중합 공정에 의해 제조되기에 제조 단가가 낮다는 장점을 가진다.Copolymer resin (C) containing a silicone-based compound has an advantage of having low stability because of its low impurity content and low manufacturing cost because it is manufactured by a simple suspension polymerization process.
본 발명의 실리콘계 화합물을 포함하는 공중합체 수지(C)는 공중합시 높은 분자량을 가지면서 수지의 충격을 향상시킬 수 있는 실리콘계 화합물과 동시에 유동성을 향상시킬 수 있는 분지형 구조로 이루어짐을 특징으로 한다. Copolymer resin (C) comprising the silicone compound of the present invention is characterized in that it is made of a branched structure that can improve the fluidity at the same time as the silicone-based compound having a high molecular weight during copolymerization can improve the impact of the resin.
실리콘계 화합물을 포함하는 공중합체 수지(C)는 낮은 유리전이온도(Tg)를 갖는 물질(예를 들면, 부틸아크릴레이트 및 실리콘 가교제) 때문에 다른 엔지니어링 플라스틱과 쉽게 녹아서 혼합된다. 이는 결과물의 유동성과 같은 물리적 성질을 개선시키는데 기여한다.Copolymer resins (C) comprising silicone-based compounds are readily dissolved and mixed with other engineering plastics due to materials having a low glass transition temperature (Tg) (eg, butyl acrylate and silicone crosslinkers). This contributes to improving physical properties such as the flowability of the result.
방향족 비닐계 단량체(c1)는 스티렌, p-메틸스티렌, α-메틸스티렌, 할로겐 또는 알킬 치환 스티렌, 또는 이들의 혼합물을 사용할 수 있고, 바람직하게는 스티렌이지만, 이에 제한되지 않는다. 방향족 비닐계 단량체(c1)는 실리콘계 화합물을 포함하는 공중합체 수지(C) 100 중량%에 대해 10 내지 80 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 50 내지 70 중량%이다. The aromatic vinyl monomer (c1) may use styrene, p-methylstyrene, α-methylstyrene, halogen or alkyl substituted styrene, or a mixture thereof, preferably styrene, but is not limited thereto. The aromatic vinyl monomer (c1) is preferably contained in 10 to 80% by weight, more preferably 50 to 70% by weight based on 100% by weight of the copolymer resin (C) containing a silicone-based compound.
불포화 니트릴계 단량체(c2)는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 페닐아크릴로니트릴, α-클로로아크릴로니트릴, 또는 이들의 혼합물을 사용할 수 있고, 바람직하게는 아크릴로니트릴이지만, 이에 제한되지 않는다. 불포화 니트릴계 단량체(c2)는 실리콘계 화합물을 포함하는 공중합체 수지(C) 100 중량%에 대해 10 내지 80 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 20 내지 50 중량%이다. The unsaturated nitrile monomer (c2) may be acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile, or a mixture thereof, and preferably acrylonitrile. This is not restrictive. The unsaturated nitrile monomer (c2) is preferably contained in 10 to 80% by weight, more preferably 20 to 50% by weight based on 100% by weight of the copolymer resin (C) containing a silicone-based compound.
(메타)아크릴계 단량체(c3)는 바람직하게는 하기 화학식 2 및 3으로 표시되는 구조를 갖는 방향족 또는 지방족 메타크릴레이트를 포함할 수 있다.The (meth) acrylic monomer (c3) may preferably include an aromatic or aliphatic methacrylate having a structure represented by the following formulas (2) and (3).
[화학식 2][Formula 2]
상기 화학식 2에서 m은 0 내지 20의 정수이며, X는 수소 또는 메틸기이고, Y는 메틸기, 사이클로헥실기, 페닐기, 벤질기, 메틸페닐기, 메틸에틸페닐기, 메톡시페닐기, 사이클로헥실페닐기, 클로로페닐기, 브로모페닐기, 페닐페닐기 및 벤질페닐기로 이루어진 군으로부터 선택될 수 있다.In Formula 2, m is an integer of 0 to 20, X is hydrogen or methyl, Y is methyl, cyclohexyl, phenyl, benzyl, methylphenyl, methylethylphenyl, methoxyphenyl, cyclohexylphenyl, chlorophenyl group , Bromophenyl group, phenylphenyl group and benzylphenyl group.
[화학식 3][Formula 3]
Figure PCTKR2013005727-appb-I000004
Figure PCTKR2013005727-appb-I000004
상기 화학식 3에서 m은 0 내지 20의 정수이며, X는 수소 또는 메틸기이고, Z는 산소(O) 또는 황(S)이고, Ar은 페닐기, 메틸페닐기, 메틸에틸페닐기, 메톡시페닐기, 사이클로헥실페닐기, 클로로페닐기, 브로모페닐기, 페닐페닐기 및 벤질페닐기로 이루어진 군에서 선택될 수 있다.In Formula 3, m is an integer of 0 to 20, X is hydrogen or a methyl group, Z is oxygen (O) or sulfur (S), Ar is a phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexyl It may be selected from the group consisting of phenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group.
이러한 상기 화학식 2 및 3의 구조를 포함하는 방향족 또는 지방족 메타크릴레이트의 예로는 사이클로헥실 메타아크릴레이트, 페녹시 메타크릴레이트, 페녹시 에틸 메타크릴레이트, 2-에틸페녹시 메타크릴레이트, 2-에틸티오페닐 메타크릴레이트, 2-에틸아미노페닐 메타크릴레이트, 페닐 메타크릴레이트, 벤질 메타크릴레이트, 2-페닐에틸 메타크릴레이트, 3-페닐프로필 메타크릴레이트, 4-페닐부틸 메타크릴레이트, 2-2-메틸페닐에틸 메타크릴레이트, 2-3-메틸페닐에틸 메타크릴레이트, 2-4-메틸페닐에틸 메타크릴레이트, 2-(4-프로필페닐)에틸메타크릴레이트, 2-(4-(1-메틸에틸)페닐)에틸 메타크릴레이트, 2-(4-메톡시페닐)에틸메타크릴레이트, 2-(4-사이클로헥실페닐)에틸 메타크릴레이트, 2-(2-클로로페닐)에틸 메타크릴레이트, 2-(3-클로로페닐)에틸 메타크릴레이트, 2-(4-클로로페닐)에틸 메타크릴레이트, 2-(4-브로모페닐)에틸 메타크릴레이트, 2-(3-페닐페닐)에틸 메타크릴레이트, 2-(4-벤질페닐)에틸 메타크릴레이트 등이 있다.Examples of the aromatic or aliphatic methacrylate including the structures of Formulas 2 and 3 include cyclohexyl methacrylate, phenoxy methacrylate, phenoxy ethyl methacrylate, 2-ethylphenoxy methacrylate, 2- Ethylthiophenyl methacrylate, 2-ethylaminophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1 -Methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- (4-cyclohexylphenyl) ethyl methacrylate, 2- (2-chlorophenyl) ethyl methacrylate Rate, 2- (3-chlorophenyl) ethyl methacrylate , 2- (4-chlorophenyl) ethyl methacrylate, 2- (4-bromophenyl) ethyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate, 2- (4-benzylphenyl) Ethyl methacrylate and the like.
또한, (메타)아크릴계 단량체(c3)의 다른 구체예로는 메타크릴산 에스테르류, 아크릴산 에스테르류, 불포화 카르복실산, 산 무수물, 하이드록시기를 함유하는 에스테르 등이 사용될 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용될 수 있다. 구체적으로는 메틸 메타크릴레이트, 에틸 메타크릴레이트, 프로필 메타크릴레이트, 부틸 메타크릴레이트, 헥실 메타크릴레이트, 2-에틸헥실 메타크릴레이트, 및 벤질 메타크릴레이트를 포함하는 메타크릴산 에스테르류; 메틸 아크릴레이트, 에틸 아크릴레이트, 프로필 아크릴레이트, 부틸 아크릴레이트, 헥실 아크릴레이트, 2-에틸헥실 아크릴레이트, 사이클로헥실 메타아크릴레이트, 페닐 메타크릴레이트, 벤질 메타크릴레이트를 포함하는 아크릴산 에스테르류; 아크릴산 및 메타크릴산을 포함하는 불포화 카르복실산; 무수말레산을 포함하는 산 무수물; 2-하이드록시에틸 아크릴레이트, 2-하이드록시프로필 아크릴레이트 및 모노글리세롤 아크릴레이트를 포함하는 하이드록시기를 함유하는 에스테르; 또는 이들의 혼합물이 사용 가능하다.Further, as another specific example of the (meth) acrylic monomer (c3), methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxy groups, etc. may be used, and these may be used alone or in combination. It may be used by mixing more than one species. Specifically, methacrylic acid esters including methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate; Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; Esters containing hydroxy groups, including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and monoglycerol acrylate; Or mixtures thereof.
(메타)아크릴계 단량체(c3)는 실리콘계 화합물을 포함하는 공중합체 수지(C) 100 중량%에 대해 1 내지 30 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 5 내지 20 중량%이다. The (meth) acrylic monomer (c3) is preferably contained in an amount of 1 to 30% by weight, more preferably 5 to 20% by weight, based on 100% by weight of the copolymer resin (C) containing the silicone compound.
(메타)아크릴계 단량체(c3)의 함량 범위가 1 중량% 미만이면, 유동성 개선 효과가 경미하며, 30 중량%를 초과하면 수지의 내열성을 저하시키는 문제점이 있다.If the content range of the (meth) acrylic monomer (c3) is less than 1% by weight, the effect of improving fluidity is slight, and if it exceeds 30% by weight, there is a problem of lowering the heat resistance of the resin.
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 하기 화학식 4로 표시되는 구조를 갖는 실리콘계 화합물을 1종 또는 2종 이상의 혼합물 형태로 포함할 수 있다. 본 발명에서 실리콘계 화합물은 공중합체 수지 내에서 가교제로서의 역할을 수행한다.The silicon compound (c4) having two or more unsaturated reactors may include a silicon compound having a structure represented by the following Chemical Formula 4 in the form of one kind or a mixture of two or more kinds. In the present invention, the silicone compound serves as a crosslinking agent in the copolymer resin.
[화학식 4][Formula 4]
Figure PCTKR2013005727-appb-I000005
Figure PCTKR2013005727-appb-I000005
상기 화학식 4에서, l, m 및 n은 0 내지 100의 정수이며(단, l, m 및 n은 동시에 0은 아님), R1 내지 R8은 각각 독립적으로 수소원자, 선형 또는 분지형 C1-C5의 알킬기, C4-C6의 사이클로알킬기, C2-C12의 불포화알킬기, C6-C10 아릴기, 수산기, C1-C5의 알콕시기, 아세톡시기, 아미노기, 아미드기, 에폭시기, 카르복실기, 할로겐기, 에스테르기, 이소시아네이트기 및 메르캅토기로 구성된 군에서 선택되며, 이때 상기 R1 내지 R8 중 적어도 두 개 이상은 중합 가능한 불포화 반응기를 가진다.In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not simultaneously 0), R 1 to R 8 are each independently a hydrogen atom, linear or branched C 1 -C 5 alkyl group, C 4 -C 6 cycloalkyl group, C 2 -C 12 unsaturated alkyl group, C 6 -C 10 aryl group, hydroxyl group, C 1 -C 5 alkoxy group, acetoxy group, amino group, amide Group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group and a mercapto group, wherein at least two or more of R 1 to R 8 have a polymerizable unsaturated reactor.
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)의 구체적인 예로는 디메톡시메틸비닐실란, 디에톡시메틸비닐실란, 디아세톡시 메틸비닐실란, 1,1,1,3,5,5,5,-헵타메틸-3-비닐트리실록산, 2,4,6,8-테트라메틸 테트라비닐 사이클로테트라실록산, α,ω-디비닐 폴리디메틸실록산 및 비닐변성 디메틸실록산, 1,3,5-트리비닐-1,1,3,5,5-펜타메틸트리실록산, 2,4,6-트리비닐-1,3,5-트리메틸사이클로실라잔, 폴리비닐메틸실라잔, 1,3-디비닐-1,1,3,3-테트라메틸디실록산 등이 가능하지만, 이에 제한되지 않으며, 이들을 단독으로 또는 혼합하여 사용할 수 있다.Specific examples of the silicone-based compound (c4) having two or more unsaturated reactors include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, diacetoxy methylvinylsilane, 1,1,1,3,5,5,5,- Heptamethyl-3-vinyltrisiloxane, 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, α, ω-divinyl polydimethylsiloxane and vinyl modified dimethylsiloxane, 1,3,5-trivinyl-1 , 1,3,5,5-pentamethyltrisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, polyvinylmethylsilazane, 1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane and the like are possible, but are not limited thereto, and these may be used alone or in combination.
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 가교제(cross-linker agent) 역할을 하는 것으로, 비닐함량이 0.05 내지 10 mmol/g이다. The silicone compound (c4) having two or more unsaturated reactors serves as a cross-linker agent, and has a vinyl content of 0.05 to 10 mmol / g.
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 실리콘계 화합물을 포함하는 공중합체 수지(C) 100 중량%에 대해 0.1 내지 25 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 1 내지 10 중량%이다. The silicone compound (c4) having two or more unsaturated reactors is preferably included in an amount of 0.1 to 25% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the copolymer resin (C) containing the silicon-based compound. to be.
두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)의 함량 범위가 1 내지 25 중량%일 때, 내충격성과 유동성 개선 효과를 동시에 발현하는 장점을 갖는다.When the content range of the silicone compound (c4) having two or more unsaturated reactors is 1 to 25% by weight, it has the advantage of simultaneously expressing impact resistance and fluidity improving effect.
또한, 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 점도가 5,000 cPs 이하, 구체적으로 0.001 내지 5,000 cPs이고, 비닐함량이 0.05 내지 10 mmol/g인 것이 바람직하며, 더욱 바람직하게는 점도가 0.5 내지 3,000 cPs이고 비닐함량이 0.1 내지 5 mmol/g이다.In addition, the silicone compound (c4) having two or more unsaturated reactors has a viscosity of 5,000 cPs or less, specifically 0.001 to 5,000 cPs, and preferably a vinyl content of 0.05 to 10 mmol / g, more preferably 0.5 To 3,000 cPs and vinyl content of 0.1 to 5 mmol / g.
본 발명의 실리콘계 화합물을 포함하는 공중합체 수지(C)가 방향족 비닐계 단량체(c1) 10 내지 80 중량%, 불포화 니트릴계 단량체(c2) 10 내지 80 중량%, (메타)아크릴계 단량체(c3) 1 내지 30 중량% 및 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4) 0.1 내지 25 중량%의 조성으로 제조될 때, 폴리카보네이트계 수지의 내열성을 해치지 않으면서 내충격성 및 유동성을 동시에 개선시킬 수 있는 장점이 있다. Copolymer resin (C) comprising the silicone compound of the present invention is 10 to 80% by weight aromatic vinyl monomer (c1), 10 to 80% by weight unsaturated nitrile monomer (c2), (meth) acrylic monomer (c3) 1 When prepared in a composition of 0.1 to 25% by weight of the silicone-based compound (c4) having from 30 to 30% by weight and two or more unsaturated reactors, it is possible to simultaneously improve impact resistance and fluidity without compromising the heat resistance of the polycarbonate resin. There is this.
실리콘계 화합물을 포함하는 공중합체 수지(C)의 중량 평균 분자량은 30,000 내지 800,000 g/mol인 것이 바람직하다. 실리콘계 화합물을 포함하는 공중합체 수지(C)가 이러한 분자량 범위를 갖는 경우, 기존의 우수한 물성을 유지하면서 열가소성 수지의 유동성과 내충격성을 동시에 높일 수 있게 된다. It is preferable that the weight average molecular weight of copolymer resin (C) containing a silicone type compound is 30,000-800,000 g / mol. When the copolymer resin (C) containing the silicone-based compound has such a molecular weight range, it is possible to simultaneously increase the fluidity and impact resistance of the thermoplastic resin while maintaining the existing excellent physical properties.
실리콘계 화합물을 포함하는 공중합체 수지(C)는 (A) 폴리카보네이트 수지, (B) 고무변성 아크릴계 그라프트 공중합체 수지 및 (C) 실리콘계 화합물을 포함하는 공중합체 수지를 포함하는 전체 수지 조성물 100 중량%에 대하여, 10 내지 30 중량%로 포함될 수 있다. Copolymer resin (C) comprising a silicone compound is 100% by weight of the total resin composition comprising (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a copolymer resin containing a silicone compound. With respect to%, it may be included in 10 to 30% by weight.
실리콘계 화합물을 포함하는 공중합체 수지(C)의 함량이 10 중량% 미만이면 충분한 충격성 및 유동성 개선 효과를 얻을 수 없게 되며, 30 중량% 이상이면 충격성과 유동성이 저하될 수 있는 문제점이 있다.If the content of the copolymer resin (C) containing a silicon-based compound is less than 10% by weight, it is impossible to obtain a sufficient impact and fluidity improvement effect, and if more than 30% by weight, impact and fluidity may be lowered.
본 발명의 폴리카보네이트계 열가소성 수지 조성물은 특히, 폴리카보네이트 수지(A)와 고무변성 아크릴계 그라프트 공중합체 수지(g-ASA)의 블렌드에 실리콘계 화합물을 포함한 공중합체 수지를 첨가함으로써 충격강도와 유동성이 동시에 개선되는 특징을 갖는다.In particular, the polycarbonate-based thermoplastic resin composition of the present invention is added to the blend of the polycarbonate resin (A) and the rubber-modified acrylic graft copolymer resin (g-ASA) by adding a copolymer resin containing a silicone compound to the impact strength and fluidity. At the same time, the characteristics are improved.
(D) 첨가제(D) additive
본 발명의 폴리카보네이트계 열가소성 수지 조성물은 각각의 용도에 따라 첨가제(D)를 더 포함할 수 있다. 폴리카보네이트계 열가소성 수지 조성물은 계면활성제, 핵제, 커플링제, 충전재, 가소제, 충격보강재, 활제, 항균제, 이형제, 열안정제, 산화방지제, 광안정제, 상용화제, 무기물 첨가제, 착색제, 안정제, 윤활제, 정전기방지제, 안료, 염료, 방염제 또는 이들의 혼합물을 첨가제(D)로 더 포함할 수 있으며, 반드시 이에 제한되는 것은 아니다. The polycarbonate-based thermoplastic resin composition of the present invention may further include an additive (D) according to each use. The polycarbonate-based thermoplastic resin composition includes surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricants, and static electricity. An inhibitor, a pigment, a dye, a flame retardant, or a mixture thereof may further be included as an additive (D), but is not necessarily limited thereto.
본 발명에 따른 폴리카보네이트계 열가소성 수지 조성물은 수지 조성물을 제조하는 공지의 방법으로 제조할 수 있다. 예를 들면, 본 발명의 구성 성분과 기타 첨가제들을 동시에 혼합한 후, 압출기 내에서 용융 압출하여 펠렛 또는 칩 형태로 제조할 수 있다. The polycarbonate-based thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be mixed at the same time and then melt-extruded in an extruder to produce pellets or chips.
본 발명의 폴리카보네이트계 열가소성 수지 조성물은 공지의 수지 제조방법에 따라 수지 성형품 형태로 제조될 수 있다. 예를 들면, 본 발명의 구성성분과 기타 첨가제들을 동시에 혼합한 후에, 압출기 내에서 용융 압출하여 펠렛 형태로 제조할 수 있다. 그리고 이런 펠렛을 이용하여 플라스틱 사출 또는 압축 성형품을 제조할 수 있다. 성형방법에는 특별한 제한이 없으며, 예를 들어, 압출성형, 사출성형, 캘린더 성형, 진공성형 등이 모두 적용될 수 있다. The polycarbonate-based thermoplastic resin composition of the present invention may be prepared in the form of a resin molded article according to a known resin production method. For example, the components of the present invention and other additives may be mixed at the same time and then melt extruded in an extruder to produce pellet form. And such pellets can be used to manufacture plastic injection or compression molded articles. There is no particular limitation on the molding method, and for example, extrusion molding, injection molding, calender molding, vacuum molding, or the like may be applied.
본 발명의 폴리카보네이트계 열가소성 수지 조성물을 성형하여 여러 가지 제품에 유용하게 이용될 수 있다. 특히 각종 전기 전자 제품의 외장재, 부품 또는 자동차 부품, 렌즈, 유리창 등 내열성 및 내충격성을 동시에 요구하는 부위를 포함하여 광범위하게 적용 가능하며, 예를 들면, 자동차 부품 또는 외장재를 비롯한 텔레비전, 세탁기, 카세트 플레이어, MP3, DMB, 네비게이션, 휴대폰, 전화기, 게임기, 오디오 플레이어, 컴퓨터, 프린터, 복사기 등의 전기 전자 제품의 하우징 제조에 이용될 수 있다. By molding the polycarbonate-based thermoplastic resin composition of the present invention can be usefully used in various products. In particular, it is widely applicable including exterior materials, components or parts of automobiles, lenses, windows, etc. that require heat resistance and impact resistance at the same time, for example, televisions, washing machines, cassettes including automotive parts or exterior materials It can be used to manufacture housings of electrical and electronic products such as players, MP3, DMB, navigation, mobile phones, telephones, game machines, audio players, computers, printers, copiers and the like.
성형품Molded article
본 발명은 또한 상기 폴리카보네이트계 열가소성 수지 조성물로부터 제조된 성형품을 제공한다. 성형품을 성형하는 방법에는 특별한 제한이 없으며, 압출, 사출 혹은 캐스팅 성형방법이 적용될 수 있다. 이러한 성형은 본 발명이 속하는 분야에서 통상의 지식을 가진 자에 의해 용이하게 실시될 수 있다.The present invention also provides a molded article prepared from the polycarbonate-based thermoplastic resin composition. There is no particular limitation on the method of molding the molded article, and an extrusion, injection or casting molding method may be applied. Such molding can be easily carried out by those skilled in the art.
본 발명의 성형품은 ASTM D256에 준하여 측정한 1/8″ 두께 시편의 Izod 충격강도가 23.00 내지 90.00 kgf·cm/cm이다. 예를 들면, 성형품은 ASTM D256에 준하여 측정한 1/8″ 두께 시편의 Izod 노치 충격강도가 23.02 kgfㆍcm/cm, 34.10 kgfㆍcm/cm, 57.68 kgfㆍcm/cm, 또는 58.0 kgfㆍcm/cm, 64.53 kgfㆍcm/cm, 65.17 kgfㆍcm/cm이다.The molded article of the present invention has an Izod impact strength of 23.00 to 90.00 kgf · cm / cm for 1/8 ″ thick specimens measured according to ASTM D256. For example, molded articles may have an Izod notch impact strength of 23.02 kgf · cm / cm, 34.10 kgf · cm / cm, 57.68 kgf · cm / cm, or 58.0 kgf · cm of a 1/8 ″ thick specimen measured according to ASTM D256. / cm, 64.53 kgf cm / cm, 65.17 kgf cm / cm.
본 발명의 성형품은 ASTM D1238에 준하여 220 ℃의 온도 및 10 kg의 하중 하에서 측정한 용융흐름지수(MI)가 34.00 내지 80.00 g/10min이다. 예를 들면, 성형품은 ASTM D1238에 준하여 220 ℃의 온도 및 10 kg의 하중 하에서 측정한 용융흐름지수(MI)가 55.8 g/10min, 45.6 g/10min, 40.2 g/10min, 38.4 g/10min, 35.4 g/10min, 34.2 g/10min이다.The molded article of the present invention has a melt flow index (MI) of 34.00 to 80.00 g / 10min, measured under a temperature of 220 ° C. and a load of 10 kg according to ASTM D1238. For example, molded articles have a melt flow index (MI) of 55.8 g / 10min, 45.6 g / 10min, 40.2 g / 10min, 38.4 g / 10min, 35.4, measured under a temperature of 220 ° C. and a load of 10 kg, in accordance with ASTM D1238. g / 10 min, 34.2 g / 10 min.
본 발명의 성형품은 ASTM D790에 준하여 측정한 1/4″두께 시편의 굴곡강도가 810 내지 840 kgf/㎠이다. 예를 들면, 성형품은 ASTM D790에 준하여 측정한 1/4″ 두께 시편의 굴곡강도가 816 kgf/㎠, 828 kgf/㎠, 814 kgf/㎠, 836 kgf/㎠, 823 kgf/㎠, 835 kgf/㎠이다.The molded article of the present invention has a bending strength of 810 to 840 kgf / cm 2 of 1/4 ″ thick specimen measured according to ASTM D790. For example, molded articles may have a flexural strength of 816 kgf / cm2, 828 kgf / cm2, 814 kgf / cm2, 836 kgf / cm2, 823 kgf / cm2, 835 kgf / Cm 2.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예 및 비교예Examples and Comparative Examples
실시예 및 비교예에서 사용되는 각 구성성분은 다음과 같다.Each component used in the Example and the comparative example is as follows.
(A) 폴리카보네이트 수지(A) polycarbonate resin
제일모직社 선형 카보네이트 기반의 중량평균 분자량이 30,000 g/mol인 2,2- 비스-(4-하이드록시페닐)-프로판 (비스페놀-A)을 사용하였다.Cheil Industries used a 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A) having a weight average molecular weight of 30,000 g / mol based on linear carbonate.
(B) 고무변성 아크릴계 그라프트 공중합체 수지(B) Rubber Modified Acrylic Graft Copolymer Resin
Mitsubishi Rayon Corporate社, metable C-223A를 사용하였다.Mitsubishi Rayon Corporate, metable C-223A was used.
(C) 실리콘계 화합물을 포함하는 공중합체 수지(C) Copolymer Resin Containing Silicone Compound
(C1) 실리콘계 화합물을 포함하는 공중합체 수지(C1) Copolymer Resin Containing Silicone Compound
[규칙 제91조에 의한 정정 27.02.2014]　
스티렌 58.22 중량%, 아크릴로니트릴 23.78 중량%, 부틸아크릴레이트 15 중량%에 점도가 100 cPs, 비닐함량이 0.5 mmol/g인 비닐변성 디메틸실록산 화합물 3 중량%를 사용하여, 통상의 현탁중합에 의해 제조된 중량 평균 분자량이 90,000 g/mol인 실리콘계 화합물을 포함하는 공중합체 수지를 사용하였다.[Correction under Article 91 of the Rule 27.02.2014]
58.22 wt% styrene, 23.78 wt% acrylonitrile, 15 wt% butyl acrylate, using conventional suspension polymerization, using 3 wt% of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. A copolymer resin containing a silicone compound having a weight average molecular weight of 90,000 g / mol was used.
(C2) 실리콘계 화합물을 포함하는 공중합체 수지(C2) Copolymer Resin Containing Silicone Compound
중량 평균 분자량이 110,000 g/mol인 것만을 제외하고는 (C1)과 동일한 실리콘계 화합물을 포함하는 공중합체 수지를 사용하였다.A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 110,000 g / mol.
(C3) 실리콘계 화합물을 포함하는 공중합체 수지(C3) Copolymer Resin Containing Silicone Compound
중량 평균 분자량이 150,000 g/mol인 것만을 제외하고는 (C1)과 동일한 실리콘계 화합물을 포함하는 공중합체 수지를 사용하였다.A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 150,000 g / mol.
(C4) 실리콘계 화합물을 포함하는 공중합체 수지(C4) Copolymer Resin Containing Silicone Compound
중량 평균 분자량이 190,000 g/mol인 것만을 제외하고는 (C1)과 동일한 실리콘계 화합물을 포함하는 공중합체 수지를 사용하였다.A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 190,000 g / mol.
(C5) 실리콘계 화합물을 포함하는 공중합체 수지(C5) Copolymer Resin Containing Silicone Compound
중량 평균 분자량이 250,000 g/mol인 것만을 제외하고는 (C1)과 동일한 실리콘계 화합물을 포함하는 공중합체 수지를 사용하였다.A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 250,000 g / mol.
(C6) 실리콘계 화합물을 포함하는 공중합체 수지(C6) Copolymer Resin Containing Silicone Compound
중량 평균 분자량이 335,000 g/mol인 것만을 제외하고는 (C1)과 동일한 실리콘계 화합물을 포함하는 공중합체 수지를 사용하였다.A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 335,000 g / mol.
(C7) 선형 방향족 비닐계 공중합체 수지(C7) linear aromatic vinyl copolymer resin
스티렌 75 중량% 및 아크릴로니트릴 25 중량%를 사용하여, 75 ℃에서 5 시간 동안 통상의 현탁중합으로 제조된 중량 평균 분자량 90,000 g/mol인 스티렌-아크릴로니트릴 공중합체 수지(SAN 수지)를 사용하였다.Using styrene-acrylonitrile copolymer resin (SAN resin) having a weight average molecular weight of 90,000 g / mol prepared by conventional suspension polymerization at 75 ° C. using 75% by weight of styrene and 25% by weight of acrylonitrile. It was.
(C8) 선형 방향족 비닐계 공중합체 수지(C8) linear aromatic vinyl copolymer resin
스티렌 71 중량% 및 아크릴로니트릴 29 중량%를 사용하여, 75 ℃에서 5 시간 동안 통상의 현탁중합으로 제조된 중량 평균 분자량 115,000 g/mol인 스티렌-아크릴로니트릴 공중합체 수지(SAN 수지)를 사용하였다.Using styrene-acrylonitrile copolymer resin (SAN resin) having a weight average molecular weight of 115,000 g / mol prepared by conventional suspension polymerization at 75 ° C. using 71% by weight of styrene and 29% by weight of acrylonitrile. It was.
(C9) 선형 방향족 비닐계 공중합체 수지(C9) linear aromatic vinyl copolymer resin
스티렌 60.35 중량% 및 아크릴로니트릴 24.65 중량% 및 부틸아크릴레이트 15 중량%를 사용하여, 75 ℃에서 5 시간 동안 통상의 현탁중합으로 제조된 중량 평균 분자량 90,000 g/mol인 공중합체 수지를 사용하였다.Using 60.35% styrene and 24.65% acrylonitrile and 15% butyl acrylate, a copolymer resin having a weight average molecular weight of 90,000 g / mol prepared by conventional suspension polymerization at 75 ° C. for 5 hours was used.
(C10) 분지형 방향족 비닐계 공중합체 수지(C10) Branched Aromatic Vinyl Copolymer Resin
[규칙 제91조에 의한 정정 27.02.2014]　
스티렌 68.87 중량% 및 아크릴로니트릴 28.13 중량%에 점도가 100 cPs, 비닐함량이 0.5 mmol/g인 비닐변성 디메틸실록산 화합물 3 중량%를 사용하여, 통상의 현탁중합에 의해 제조된 중량 평균 분자량이 90,000 g/mol인 분지형 비닐계공중합체 수지를 사용하였다.[Correction under Article 91 of the Rule 27.02.2014]
A weight average molecular weight of 90,000 prepared by conventional suspension polymerization using 68.87% styrene and 28.13% acrylonitrile using 3% by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g A branched vinyl copolymer resin of g / mol was used.
실시예 1-6 및 비교예 1-4Example 1-6 and Comparative Example 1-4
하기 표 1의 조성으로 각 성분을 첨가한 후 용융, 혼련 압출하여 펠렛을 제조하였다. 이때, 압출은 L/D=29, 직경 45 mm인 이축 압출기를 사용하였으며, 제조된 펠렛은 70 ℃에서 6 시간 건조후 6 oz 사출기에서 사출하여 물성평가를 위한 시편을 제조하였다.Each component was added to the composition shown in Table 1, followed by melting and kneading to prepare a pellet. At this time, the extrusion was used L / D = 29, 45 mm diameter twin-screw extruder, and the prepared pellet was dried for 6 hours at 70 ℃ and injected in a 6 oz injection machine to prepare a specimen for evaluation of physical properties.
하기 [표 1]에서 (A), (B) 및 (C)의 혼합비는 (A), (B) 및 (C) 전체 100 중량%에 대하여 중량%로 나타낸 것이다. In the following [Table 1], the mixing ratios of (A), (B) and (C) are expressed in weight% based on 100% by weight of the total of (A), (B) and (C).
표 1
Figure PCTKR2013005727-appb-T000001
 Table 1
Figure PCTKR2013005727-appb-T000001
제조된 시편에 대하여 하기와 같은 방법으로 물성을 측정하였으며 그 결과를 표 2에 나타내었다.The physical properties of the prepared specimens were measured by the following method, and the results are shown in Table 2.
(1) 충격강도(kgfㆍcm/cm): ASTM D256에 규정된 평가방법에 의하여 1/8″ 아이조드 시편에 노치(Notch)를 만들어 평가하였다.(1) Impact strength (kgf · cm / cm): Notch was evaluated by making a notch on 1/8 ″ Izod specimens according to the evaluation method specified in ASTM D256.
(2) 유동지수(g/10minute): ASTM D1238에 규정된 평가방법에 의하여 220 ℃, 10 kg 조건에서 측정하였다.(2) Flow index (g / 10minute): measured at 220 ℃, 10 kg conditions by the evaluation method specified in ASTM D1238.
(3) 굴곡강도: ASTM D790에 규정된 평가방법에 의하여 1/4″두께의 시편으로 측정하였다.(3) Flexural strength: Measured by a 1/4 "thickness specimen by the evaluation method specified in ASTM D790.
(4) 내열도(HDT): ASTM D648 (1/4 인치, 18.6 kgf/㎠, 120 ℃/hr)에 따라 측정하였다.(4) Heat resistance (HDT): Measured according to ASTM D648 (1/4 inch, 18.6 kgf / cm 2, 120 ° C./hr).
표 2
Figure PCTKR2013005727-appb-T000002
 TABLE 2
Figure PCTKR2013005727-appb-T000002
[표 2]에 나타나 있듯이, 실시예 1-6에서는 증가된 분자량 및 실리콘계 화합물에 의해 충격강도가 개선되며, 분지형 구조 및 낮은 유리전이온도(Tg)를 가진 유연한(flexible) 부틸 아크릴레이트 단량체에 의해 유동성이 개선되어 성형성이 향상되는 결과를 보였다. As shown in Table 2, in Examples 1-6, the impact strength was improved by the increased molecular weight and the silicone-based compound, and the flexible butyl acrylate monomer having a branched structure and a low glass transition temperature (Tg) was used. As a result, the fluidity was improved, and the moldability was improved.
실시예 1-2에서는, 공중합체(C)의 분자량이 줄고, 유연하고(flexible), 낮은 유리전이온도(Tg)를 가진 단량체(부틸 아크릴레이트 및 실리콘계 화합물)의 사용으로 우수한 유동성을 보여준다. 그러나 충격강도는 약간 감소되었다.In Examples 1-2, the molecular weight of the copolymer (C) is reduced, and the use of monomers (butyl acrylate and silicone-based compounds) with a flexible, low glass transition temperature (Tg) shows excellent fluidity. However, the impact strength was slightly reduced.
실시예 3-4에서는 유연한(flexible) 분지형 비닐계 공중합체의 적절한 분자량의 사용으로 충격강도 및 유동성이 개선되었다. In Example 3-4, impact strength and fluidity were improved by using an appropriate molecular weight of the flexible branched vinyl copolymer.
실시예 5-6에서는, 고분자량의 분지형 공중합체의 사용으로 우수한 충격강도 및 상대적으로 높은 유동성이 나타났다. In Examples 5-6, the use of high molecular weight branched copolymers showed excellent impact strength and relatively high flowability.
비교예 2는 아크릴로니트릴 함량이 높은 고분자량의 SAN 수지를 사용하여 충격강도가 개선되나, 유동성 및 굴곡 물성이 급격히 저하되는 것을 확인하였다. In Comparative Example 2, the impact strength was improved by using a high molecular weight SAN resin having a high acrylonitrile content, but it was confirmed that the fluidity and the flexural properties were sharply decreased.
비교예 3은 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)을 사용하지 않고, 낮은 유리전이온도(Tg)를 가진 부틸 아크릴레이트 단량체를 사용하였기에 유동성은 개선되나 충격강도가 저하되는 것을 나타낸다.Comparative Example 3 shows that the butyl acrylate monomer having a low glass transition temperature (Tg) is used instead of the silicon-based compound (c4) having two or more unsaturated reactors, thereby improving fluidity but decreasing impact strength.
비교예 4는 가교제로 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물의 사용으로 충격강도는 개선되나, (메타)아크릴계 단량체(c3)를 사용하지 않았기에 유동성이 저하되는 것을 나타낸다.Comparative Example 4 shows that the impact strength is improved by using a silicone-based compound having two or more unsaturated reactors as a crosslinking agent, but the fluidity is lowered because no (meth) acrylic monomer (c3) is used.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (23)

  1. (A) 폴리카보네이트 수지;(A) polycarbonate resin;
    (B) 고무변성 아크릴계 그라프트 공중합체 수지; 및(B) rubber modified acrylic graft copolymer resin; And
    (C) 실리콘계 화합물을 포함하는 공중합체 수지;(C) a copolymer resin containing a silicone compound;
    를 포함하는 폴리카보네이트계 열가소성 수지 조성물.Polycarbonate-based thermoplastic resin composition comprising a.
  2. 제1항에 있어서, 상기 폴리카보네이트 수지(A) 40 내지 80 중량%, 상기 고무변성 아크릴계 그라프트 공중합체 수지(B) 1 내지 30 중량% 및 상기 실리콘계 화합물을 포함하는 공중합체 수지(C) 10 내지 30 중량%인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The copolymer resin (C) according to claim 1, comprising 40 to 80 wt% of the polycarbonate resin (A), 1 to 30 wt% of the rubber-modified acrylic graft copolymer resin (B) and the silicone compound. To 30% by weight of polycarbonate-based thermoplastic resin composition.
  3. 제1항에 있어서, 상기 고무변성 아크릴계 그라프트 공중합체 수지(B)는 고무(b1) 40 내지 98 중량%, 알킬메타크릴레이트(b2) 1 내지 30 중량% 및 비닐계 방향족 단량체(b3) 1 내지 40 중량%를 포함하는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.According to claim 1, wherein the rubber-modified acrylic graft copolymer resin (B) is 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and vinyl aromatic monomer (b3) 1 Polycarbonate-based thermoplastic resin composition comprising from 40% by weight.
  4. 제3항에 있어서, 상기 알킬메타크릴레이트(b2)는 탄소원자수가 1 내지 20인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition according to claim 3, wherein the alkyl methacrylate (b2) has 1 to 20 carbon atoms.
  5. 제1항에 있어서, 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)는 분지형 비닐계 공중합체 수지인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition according to claim 1, wherein the copolymer resin (C) containing the silicone compound is a branched vinyl copolymer resin.
  6. 제1항에 있어서, 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)는 방향족 비닐계 단량체(c1) 10 내지 80 중량%, 불포화 니트릴계 단량체(c2) 10 내지 80 중량%, (메타)아크릴계 단량체(c3) 1 내지 30 중량% 및 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4) 0.1 내지 25 중량%를 공중합하여 제조된 공중합체인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The copolymer resin (C) of claim 1, wherein the copolymer resin (C) including the silicone compound is 10 to 80 wt% of an aromatic vinyl monomer (c1), 10 to 80 wt% of an unsaturated nitrile monomer (c2), and a (meth) acrylic monomer. (c3) Polycarbonate-based thermoplastic resin composition, characterized in that the copolymer prepared by copolymerizing 1 to 30% by weight and 0.1 to 25% by weight of the silicone-based compound (c4) having two or more unsaturated reactors.
  7. 제1항에 있어서, 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)의 중량 평균 분자량은 30,000 내지 800,000 g/mol인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the copolymer resin (C) containing the silicone compound is 30,000 to 800,000 g / mol.
  8. 제6항에 있어서, 상기 방향족 비닐계 단량체(c1)는 스티렌, p-메틸스티렌, α-메틸스티렌, 할로겐 치환 스티렌, 알킬 치환 스티렌 및 이들의 혼합물로 이루어진 군에서 선택되고,The method of claim 6, wherein the aromatic vinyl monomer (c1) is selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, halogen substituted styrene, alkyl substituted styrene, and mixtures thereof,
    상기 불포화 니트릴계 단량체(c2)는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 페닐아크릴로니트릴, α-클로로아크릴로니트릴 및 이들의 혼합물로 이루어진 군에서 선택되고,The unsaturated nitrile monomer (c2) is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile and mixtures thereof,
    상기 (메타)아크릴계 단량체(c3)는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 프로필 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 헥실 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트 및 이들의 혼합물로 이루어진 군에서 선택되는 것을 포함하는 지방족 (메타)아크릴레이트이며,The (meth) acrylic monomer (c3) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic (meth) acrylates, including those selected from the group consisting of meth) acrylates and mixtures thereof,
    상기 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 하기 화학식 4로 표시되는 구조를 갖는 실리콘계 화합물을 단독 또는 2종 이상의 혼합물 형태로 포함하는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물: The silicone-based compound (c4) having two or more unsaturated reactors is a polycarbonate-based thermoplastic resin composition comprising a silicon-based compound having a structure represented by the following formula (4) alone or in mixture of two or more thereof:
    [화학식 4][Formula 4]
    Figure PCTKR2013005727-appb-I000006
    Figure PCTKR2013005727-appb-I000006
    (상기 화학식 4에서, l, m 및 n은 0 내지 100의 정수이며(단, l, m 및 n은 동시에 0은 아님), R1 내지 R8은 각각 독립적으로 수소원자, 선형 또는 분지형 C1-C5의 알킬기, C4-C6의 사이클로알킬기, C2-C12의 불포화알킬기, C6-C10 아릴기, 수산기, C1-C5의 알콕시기, 아세톡시기, 아미노기, 아미드기, 에폭시기, 카르복실기, 할로겐기, 에스테르기, 이소시아네이트기 및 메르캅토기로 구성된 군에서 선택되며, 이때 상기 R1 내지 R8 중 적어도 두 개 이상은 중합 가능한 불포화 반응기를 가짐.)(In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not 0 at the same time), R 1 to R 8 are each independently a hydrogen atom, linear or branched C An alkyl group of 1 -C 5 , a cycloalkyl group of C 4 -C 6 , an unsaturated alkyl group of C 2 -C 12 , a C 6 -C 10 aryl group, a hydroxyl group, an alkoxy group of C 1 -C 5 , an acetoxy group, an amino group, An amide group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, and a mercapto group, wherein at least two of R 1 to R 8 have a polymerizable unsaturated reactor.)
  9. 제6항에 있어서, 상기 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 점도가 5,000 cPs 이하이고, 비닐 함량이 0.05 내지 10 mmol/g인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition of claim 6, wherein the silicone-based compound (c4) having two or more unsaturated reactors has a viscosity of 5,000 cPs or less and a vinyl content of 0.05 to 10 mmol / g.
  10. 제6항에 있어서, 상기 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 2,4,6,8-테트라메틸 테트라비닐 사이클로테트라실록산, 1,3,5- 트리비닐-1,1,3,5,5-펜타메틸트리실록산, 2,4,6-트리비닐-1,3,5-트리메틸사이클로실라잔, α,ω-디비닐폴리디메틸실록산, 폴리비닐메틸실라잔, 1,3-디비닐-1,1,3,3-테트라메틸디실록산 및 이들의 혼합물로 구성된 군에서 선택되는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The method of claim 6, wherein the silicon-based compound (c4) having two or more unsaturated reactors is 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, 1,3,5-trivinyl-1,1,3 , 5,5-pentamethyltrisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, α, ω-divinylpolydimethylsiloxane, polyvinylmethylsilazane, 1,3- A polycarbonate-based thermoplastic resin composition selected from the group consisting of divinyl-1,1,3,3-tetramethyldisiloxane and mixtures thereof.
  11. 제1항 내지 제10항 중 어느 한 항에 의한 폴리카보네이트계 열가소성 수지 조성물로부터 제조되는 성형품.A molded article prepared from the polycarbonate-based thermoplastic resin composition according to any one of claims 1 to 10.
  12. 연속상인 제1수지;A first resin in continuous phase;
    분산상인 제2수지; 및Second resin which is a dispersed phase; And
    상기 연속상인 제1수지 및 상기 분산상인 제2수지의 계면에 위치하는 충격보강재;An impact reinforcing material located at an interface between the first resin in the continuous phase and the second resin in the dispersed phase;
    를 포함하는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.Polycarbonate-based thermoplastic resin composition comprising a.
  13. 제12항에 있어서, 상기 연속상인 제1수지 40 내지 80 중량%, 상기 분산상인 제2수지 10 내지 30 중량%, 및 상기 충격보강재 1 내지 30 중량%를 포함하는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic according to claim 12, comprising 40 to 80 wt% of the first resin in the continuous phase, 10 to 30 wt% of the second resin in the dispersed phase, and 1 to 30 wt% of the impact modifier. Resin composition.
  14. 제12항에 있어서, 상기 연속상인 제1수지는 폴리카보네이트 수지(A)이고, 상기 분산상인 제2수지는 실리콘계 화합물을 포함하는 공중합체 수지(C)이고, 상기 충격보강재는 고무변성 아크릴계 그라프트 공중합체 수지(B)인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The method of claim 12, wherein the first resin in the continuous phase is a polycarbonate resin (A), the second resin in the dispersed phase is a copolymer resin (C) containing a silicone-based compound, the impact modifier is a rubber-modified acrylic graft It is a copolymer resin (B), The polycarbonate type thermoplastic resin composition characterized by the above-mentioned.
  15. 제14항에 있어서, 상기 고무변성 아크릴계 그라프트 공중합체 수지(B)는 고무(b1) 40 내지 98 중량%, 알킬메타크릴레이트(b2) 1 내지 30 중량% 및 비닐계 방향족 단량체(b3) 1 내지 40 중량%를 포함하는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The rubber-modified acrylic graft copolymer resin (B) is 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and vinyl aromatic monomer (b3) 1 Polycarbonate-based thermoplastic resin composition comprising from 40% by weight.
  16. 제15항에 있어서, 상기 알킬메타크릴레이트(b2)는 탄소원자수가 1 내지 20인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition according to claim 15, wherein the alkyl methacrylate (b2) has 1 to 20 carbon atoms.
  17. 제14항에 있어서, 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)는 분지형 비닐계 공중합체 수지인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition according to claim 14, wherein the copolymer resin (C) containing the silicone compound is a branched vinyl copolymer resin.
  18. 제14항에 있어서, 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)는 방향족 비닐계 단량체(c1) 10 내지 80 중량%, 불포화 니트릴계 단량체(c2) 10 내지 80 중량%, (메타)아크릴계 단량체(c3) 1 내지 30 중량% 및 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4) 0.1 내지 25 중량%를 공중합하여 제조된 공중합체인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The copolymer resin (C) comprising the silicone-based compound is 10 to 80% by weight of the aromatic vinyl monomer (c1), 10 to 80% by weight of the unsaturated nitrile monomer (c2), (meth) acrylic monomer (c3) Polycarbonate-based thermoplastic resin composition, characterized in that the copolymer prepared by copolymerizing 1 to 30% by weight and 0.1 to 25% by weight of the silicone-based compound (c4) having two or more unsaturated reactors.
  19. 제14항에 있어서, 상기 실리콘계 화합물을 포함하는 공중합체 수지(C)의 중량 평균 분자량은 30,000 내지 800,000 g/mol인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition according to claim 14, wherein the weight average molecular weight of the copolymer resin (C) containing the silicone compound is 30,000 to 800,000 g / mol.
  20. 제18항에 있어서, 상기 방향족 비닐계 단량체(c1)는 스티렌, p-메틸스티렌, α-메틸스티렌, 할로겐 치환 스티렌, 알킬 치환 스티렌 및 이들의 혼합물로 이루어진 군에서 선택되고,19. The method of claim 18, wherein the aromatic vinyl monomer (c1) is selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, halogen substituted styrene, alkyl substituted styrene, and mixtures thereof,
    상기 불포화 니트릴계 단량체(c2)는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 페닐아크릴로니트릴, α-클로로아크릴로니트릴 및 이들의 혼합물로 이루어진 군에서 선택되고,The unsaturated nitrile monomer (c2) is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile and mixtures thereof,
    상기 (메타)아크릴계 단량체(c3)는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 프로필 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 헥실 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트 및 이들의 혼합물로 이루어진 군에서 선택되는 것을 포함하는 지방족 (메타)아크릴레이트이며,The (meth) acrylic monomer (c3) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic (meth) acrylates, including those selected from the group consisting of meth) acrylates and mixtures thereof,
    상기 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 하기 화학식 4로 표시되는 구조를 갖는 실리콘계 화합물을 단독 또는 2종 이상의 혼합물 형태로 포함하는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물:The silicone-based compound (c4) having two or more unsaturated reactors is a polycarbonate-based thermoplastic resin composition comprising a silicon-based compound having a structure represented by the following formula (4) alone or in mixture of two or more thereof:
    [화학식 4][Formula 4]
    Figure PCTKR2013005727-appb-I000007
    Figure PCTKR2013005727-appb-I000007
    (상기 화학식 4에서, l, m 및 n은 0 내지 100의 정수이며(단, l, m 및 n은 동시에 0은 아님), R1 내지 R8은 각각 독립적으로 수소원자, 선형 또는 분지형 C1-C5의 알킬기, C4-C6의 사이클로알킬기, C2-C12의 불포화알킬기, C6-C10 아릴기, 수산기, C1-C5의 알콕시기, 아세톡시기, 아미노기, 아미드기, 에폭시기, 카르복실기, 할로겐기, 에스테르기, 이소시아네이트기 및 메르캅토기로 구성된 군에서 선택되며, 이때 상기 R1 내지 R8 중 적어도 두 개 이상은 중합 가능한 불포화 반응기를 가짐.)(In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not 0 at the same time), R 1 to R 8 are each independently a hydrogen atom, linear or branched C An alkyl group of 1 -C 5 , a cycloalkyl group of C 4 -C 6 , an unsaturated alkyl group of C 2 -C 12 , a C 6 -C 10 aryl group, a hydroxyl group, an alkoxy group of C 1 -C 5 , an acetoxy group, an amino group, An amide group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, and a mercapto group, wherein at least two of R 1 to R 8 have a polymerizable unsaturated reactor.)
  21. 제18항에 있어서, 상기 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 점도가 5,000 cPs 이하이고, 비닐 함량이 0.05 내지 10 mmol/g인 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.The polycarbonate-based thermoplastic resin composition of claim 18, wherein the silicone-based compound (c4) having two or more unsaturated reactors has a viscosity of 5,000 cPs or less and a vinyl content of 0.05 to 10 mmol / g.
  22. 제18항에 있어서, 상기 두 개 이상의 불포화 반응기를 가지는 실리콘계 화합물(c4)은 2,4,6,8-테트라메틸 테트라비닐 사이클로테트라실록산, 1,3,5- 트리비닐-1,1,3,5,5-펜타메틸트리실록산, 2,4,6-트리비닐-1,3,5-트리메틸사이클로실라잔, α,ω-디비닐폴리디메틸실록산, 폴리비닐메틸실라잔, 1,3-디비닐-1,1,3,3-테트라메틸디실록산 및 이들의 혼합물로 구성된 군에서 선택되는 것을 특징으로 하는 폴리카보네이트계 열가소성 수지 조성물.19. The method of claim 18, wherein the silicone-based compound (c4) having two or more unsaturated reactors is 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, 1,3,5-trivinyl-1,1,3 , 5,5-pentamethyltrisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, α, ω-divinylpolydimethylsiloxane, polyvinylmethylsilazane, 1,3- A polycarbonate-based thermoplastic resin composition selected from the group consisting of divinyl-1,1,3,3-tetramethyldisiloxane and mixtures thereof.
  23. 제12항 내지 제22항 중 어느 한 항에 의한 폴리카보네이트계 열가소성 수지 조성물로부터 제조되는 성형품.A molded article produced from the polycarbonate-based thermoplastic resin composition according to any one of claims 12 to 22.
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