WO2014119827A1 - Composition de résine thermoplastique à base de polycarbonate et article moulé - Google Patents

Composition de résine thermoplastique à base de polycarbonate et article moulé Download PDF

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WO2014119827A1
WO2014119827A1 PCT/KR2013/005727 KR2013005727W WO2014119827A1 WO 2014119827 A1 WO2014119827 A1 WO 2014119827A1 KR 2013005727 W KR2013005727 W KR 2013005727W WO 2014119827 A1 WO2014119827 A1 WO 2014119827A1
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group
polycarbonate
weight
resin composition
based thermoplastic
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PCT/KR2013/005727
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English (en)
Korean (ko)
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WO2014119827A9 (fr
Inventor
나타라잔센틸쿠마르
장주현
김동희
김일진
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제일모직주식회사
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Priority claimed from KR1020130072825A external-priority patent/KR101664844B1/ko
Application filed by 제일모직주식회사 filed Critical 제일모직주식회사
Priority to US14/763,877 priority Critical patent/US9505929B2/en
Priority to CN201380071804.4A priority patent/CN104955897B/zh
Publication of WO2014119827A1 publication Critical patent/WO2014119827A1/fr
Publication of WO2014119827A9 publication Critical patent/WO2014119827A9/fr

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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.
  • Inhibitors, pigments, dyes, flame retardants or mixtures thereof may be further included as 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 branched vinyl copolymer resin of 90,000 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition thermoplastique à base de polycarbonate comprenant (A) une résine de polycarbonate, (B) une résine de copolymère greffé à base d'acryle modifié par un caoutchouc et (C) un copolymère contenant un composé à base de silicium. La composition thermoplastique à base de polycarbonate présente une excellente coulabilité sans dégradation de la résistance au choc et une excellente résistance à la chaleur en introduisant le copolymère contenant un composé à base de silicium dans la résine de polycarbonate.
PCT/KR2013/005727 2013-01-29 2013-06-27 Composition de résine thermoplastique à base de polycarbonate et article moulé WO2014119827A1 (fr)

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US14/763,877 US9505929B2 (en) 2013-01-29 2013-06-27 Polycarbonate-based thermoplastic resin composition and molded article
CN201380071804.4A CN104955897B (zh) 2013-01-29 2013-06-27 聚碳酸酯类热塑性树脂组合物及模制品

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KR1020130072825A KR101664844B1 (ko) 2013-01-29 2013-06-25 폴리카보네이트계 열가소성 수지 조성물 및 성형품
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WO2023229298A1 (fr) * 2022-05-23 2023-11-30 롯데케미칼 주식회사 Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci

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