KR20150015279A - Thermoplastic resin composition having improved dimensional stability - Google Patents
Thermoplastic resin composition having improved dimensional stability Download PDFInfo
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- KR20150015279A KR20150015279A KR1020130091141A KR20130091141A KR20150015279A KR 20150015279 A KR20150015279 A KR 20150015279A KR 1020130091141 A KR1020130091141 A KR 1020130091141A KR 20130091141 A KR20130091141 A KR 20130091141A KR 20150015279 A KR20150015279 A KR 20150015279A
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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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
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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Abstract
The present invention relates to a rubber composition which comprises (A) a rubber-modified vinyl-based graft copolymer, (B) an aromatic vinyl-cyanide vinyl copolymer and (C) a maleic anhydride copolymer and is excellent in impact resistance, heat resistance, mechanical strength, To a thermoplastic resin composition having excellent processability and excellent dimensional stability.
Description
The present invention relates to a thermoplastic resin composition having heat resistance, impact resistance and mechanical strength as well as excellent dimensional stability.
Generally, ABS (acrylonitrile-butadiene-styrene) resins are widely used in automobiles, electric and electronic devices, and automotive parts due to their physical properties such as impact resistance, styrene processability, moldability, colorability, stiffness and chemical resistance of acrylonitrile, Office equipment, household appliances, toys, and stationary. When applied to automobile parts, such ABS resins often have a large size of molded parts, are often bonded or assembled with metal parts, and are exposed to an external environment with severe climate change. Therefore, impact resistance, heat resistance and mechanical strength as well as dimensional stability are required .
Korean Patent No. 0694474 (Patent Document 1) discloses a thermoplastic resin composition having improved dimensional stability including an inorganic dispersion such as calcium carbonate, silica, and talc. Korean Patent Publication No. 2012-0042802 (Patent Document 2) discloses a copolymer comprising an N-substituted maleimide monomer for improving the heat resistance of a thermoplastic resin. These publications disclose copolymers containing N-substituted maleimide for improving the dimensional stability or containing an inorganic dispersant, but the dimensional stability of the molded article due to the inorganic dispersant is improved, while the impact strength , Gloss and the like may be deteriorated, and the heat resistance due to the copolymer including N-substituted maleimide is improved, but the processability due to the lowered fluidity may be deteriorated.
Accordingly, the present inventors have come to develop thermoplastic resin compositions having excellent impact resistance, heat resistance and mechanical strength, as well as excellent dimensional stability and moldability.
Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a thermoplastic resin composition having excellent impact resistance, heat resistance, mechanical strength, appearance and molding processability, and excellent dimensional stability.
The present invention also provides a molded article excellent in heat resistance, impact resistance, mechanical strength and dimensional stability from the thermoplastic resin composition.
In order to achieve the above object, the present invention provides a rubber composition comprising (A) a rubber-modified vinyl-based graft copolymer, (B) an aromatic vinyl-cyanide vinyl copolymer and (C) a maleic anhydride copolymer, Thereby providing an excellent thermoplastic resin composition.
In the thermoplastic resin composition according to one embodiment of the present invention, the composition comprises 10 to 40 wt% of the rubber-modified vinyl-based graft copolymer (A), 20 to 50 wt% of the aromatic vinyl-cyanide vinyl copolymer (B) And 10 to 50% by weight of the maleic anhydride copolymer (C).
In the thermoplastic resin composition according to one embodiment of the present invention, the maleic anhydride copolymer may be prepared by copolymerizing a mixture containing an aromatic vinyl compound, a vinyl cyanide compound and a maleic anhydride compound.
In the thermoplastic resin composition according to one embodiment of the present invention, the maleic anhydride copolymer may have a maleic anhydride-based compound content of 5 to 40% by weight.
In the thermoplastic resin composition according to one embodiment of the present invention, the rubber-modified vinyl-based graft copolymer (A) is prepared by graft-polymerizing a mixture containing a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound .
In the thermoplastic resin composition according to one embodiment of the present invention, the rubber-modified vinyl-based graft copolymer (A) is obtained by mixing 70 to 30 weight parts of a mixture of a vinyl cyanide compound and an aromatic vinyl compound in the presence of 30 to 70% Butadiene-styrene graft copolymer (g-ABS) which is graft-polymerized by emulsion polymerization.
In the thermoplastic resin composition according to one embodiment of the present invention, the aromatic vinyl-cyanide vinyl copolymer (B) is a copolymer of styrene and acrylonitrile, a copolymer of? -Methylstyrene and acrylonitrile, methyl styrene and acrylonitrile.
In the thermoplastic resin composition according to one embodiment of the present invention, the maleic anhydride copolymer (C) may have a glass transition temperature of 111 to 130 ° C.
In the thermoplastic resin composition according to an embodiment of the present invention, the composition may contain at least one selected from the group consisting of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a compatibilizer, An additive selected from the group consisting of pigments, dyes, flame retardants, flame retardant auxiliaries, anti-drip agents, endurance agents, ultraviolet absorbers, ultraviolet screening agents and mixtures thereof.
The present invention can provide a molded article produced from the thermoplastic resin composition.
The thermoplastic resin composition according to the present invention is not only excellent in impact resistance, heat resistance, mechanical strength and appearance, but also has the advantage of greatly improving dimensional stability without including inorganic materials.
Further, the present invention is advantageous in fluidity and molding processability, excellent in surface gloss and thermal stability.
Therefore, it has an advantage that it can be applied to various kinds of interior / exterior materials and parts, in particular, electric and electronic products, automobile articles, etc., which simultaneously require heat stability, impact resistance, workability and dimensional stability.
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.
The inventors of the present invention have made studies to develop a thermoplastic resin composition having excellent dimensional stability. As a result, the rubber-modified vinyl-based graft copolymer, the aromatic vinyl-cyanide vinyl copolymer and the maleic anhydride copolymer surprisingly have excellent impact resistance , Heat resistance, mechanical strength, and surface properties while maximizing dimensional stability without using inorganic components, thereby completing the present invention.
The thermoplastic resin composition having excellent dimensional stability of the present invention may comprise (A) a rubber-modified vinyl-based graft copolymer, (B) an aromatic vinyl-cyanide vinyl copolymer and (C) a maleic anhydride copolymer.
Hereinafter, each component will be described in more detail.
(A) a rubber-modified vinyl-based graft copolymer
The rubber-modified vinyl-based graft copolymer contained in the thermoplastic resin composition of the present invention is capable of improving impact strength, mechanical rigidity and appearance characteristics by combination with other components in the composition, and it is preferable that 10 to 40% by weight . If it is less than the above range, the impact strength may be lowered, and if it is more than the above range, the fluidity may be lowered.
The rubber-modified vinyl-based graft copolymer can be produced by graft-polymerizing a mixture containing a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound.
For example, 30 to 70% by weight of a mixture of an aromatic vinyl compound and a vinyl cyanide compound is graft-polymerized by the emulsion polymerization method in the presence of 30 to 70% by weight of a rubbery polymer to prepare the rubber-modified vinyl-based graft copolymer have.
At this time, the rubbery polymer may have an average particle diameter of 0.1 to 10 탆, preferably 0.2 to 1.0 탆, which is excellent in impact strength, mechanical rigidity and miscibility.
The rubbery polymer may have a glass transition temperature of preferably -10 ° C, more preferably less than 0 ° C.
The rubbery polymer may be at least one selected from the group consisting of polybutadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) and polyorganosiloxane / (Meth) acrylate rubber composite, and a polybutadiene rubber can be preferably used.
The aromatic vinyl compound in the mixture to be graft-polymerized to the rubbery polymer may be at least one selected from the group consisting of styrene, C 1 -C 10 alkyl-substituted styrene, halogen-substituted styrene, vinyltoluene, vinylnaphthalene and combinations thereof . Specific examples of the alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene and 2,4-dimethylstyrene. Styrene may be preferably used as the aromatic vinyl compound.
The vinyl cyanide compound in the mixture to be graft polymerized to the rubbery polymer may be at least one selected from acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof. Preferably, acrylonitrile may be used as the vinyl cyanide compound.
The grafted rubbery polymer may be further graft-polymerized by adding C 1 -C 8 methacrylic acid alkyl esters, C 1 -C 8 alkyl acrylates, monomers such as maleic anhydride. The C 1 -C 8 methacrylic acid alkyl esters or C 1 -C 8 acrylic acid alkyl esters are alkyl esters of methacrylic acid or acrylic acid, respectively, and esters obtained from monohydric alcohols containing 1 to 8 carbon atoms to be. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, acrylic acid ethyl ester and acrylic acid methyl ester.
As a preferred example, the rubber-modified vinyl-based graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer (g-ABS).
(B) an aromatic vinyl-cyanide vinyl copolymer
The aromatic vinyl-cyanide vinyl copolymer contained in the thermoplastic resin composition of the present invention can improve mechanical strength and chemical resistance in combination with other components in the composition, and may be contained in an amount of 20 to 50 wt% of the total composition. If the amount is less than the above range, the effect may be insignificant, and if it is more than the above range, the fluidity and dimensional stability may be poor.
The aromatic vinyl-cyanide vinyl copolymer is a copolymer of an aromatic vinyl compound and a vinyl cyanide compound.
The aromatic vinyl compound may be at least one selected from the group consisting of styrene, C 1 to C 10 alkyl-substituted styrene, halogen-substituted styrene, vinyl toluene, vinyl naphthalene, and combinations thereof. Specific examples of the alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene and 2,4-dimethylstyrene.
As the vinyl cyanide compound, at least one selected from acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof may be used.
Specific examples of the aromatic vinyl-cyanide vinyl-based copolymer include copolymers of styrene and acrylonitrile; copolymers of? -methylstyrene and acrylonitrile; Or copolymers of styrene,? -Methylstyrene and acrylonitrile, and preferably styrene-acrylonitrile copolymers can be used.
(C) a maleic anhydride copolymer
The maleic anhydride copolymer contained in the thermoplastic resin composition of the present invention can improve dimensional stability without deteriorating impact resistance, heat resistance, mechanical strength and fluidity in combination with other components in the composition. % ≪ / RTI > by weight. When the amount is less than the above range, the desired effect is difficult to exhibit, and if it is more than the above range, the impact resistance and the mechanical strength may be lowered.
The maleic anhydride copolymer can be produced by polymerizing a mixture containing an aromatic vinyl compound, a vinyl cyanide compound and a maleic anhydride compound. At this time, the maleic anhydride copolymer may have a maleic anhydride-based compound content of preferably 5 to 40% by weight. If it is less than the above range, it may be difficult to realize dimensional stability, and if it is more than the above range, polymerization may be difficult.
The maleic anhydride-based compound may be at least one selected from maleic anhydride, 2-methylmaleic anhydride, 2-ethylmaleic anhydride, and combinations thereof.
The aromatic vinyl compounds may be used any one or more selected from styrene, C 1 -C 10 alkyl-substituted styrene, halogen substituted styrene, vinyl toluene, vinyl naphthalene, and a combination thereof. Specific examples of the alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene and 2,4-dimethylstyrene.
The vinyl cyanide compound may be selected from acrylonitrile, methacrylonitrile, and fumaronitrile, and combinations thereof.
The maleic anhydride copolymer may be prepared by, for example, adding a catalyst and a chain transfer agent to a mixture of maleic anhydride, acrylonitrile, and styrene in a solvent, followed by stirring at 110 to 120 ° C for copolymerization. The reaction product may be transferred to another reactor and stirred at 120-130 ° C, which is higher than the reaction temperature of the previous step, to carry out an additional reaction. At this time, the content of the solid content in the reaction product may be preferably 5 to 20% by weight.
The maleic anhydride copolymer, which has been reacted, can remove the solvent and unreacted compound using a devolatilizer. At this time, the temperature and the pressure are not limited, but preferably 200 to 300 ° C and 10 to 20 torr.
The maleic anhydride copolymer may have a flow index of 8 to 40 g / 10 min measured at 220 ° C / 10 kg according to ASTM D1238.
The glass transition temperature of the maleic anhydride copolymer may preferably be 105 to 150 ° C.
The thermoplastic resin composition according to the present invention can be produced in the form of pellets or various molded articles by mixing the respective constituents with a known mixing method using an extruder, a kneader, a mixer or the like and extruding them.
The molded article according to the present invention may have an Izod impact strength (1/4 ") measured according to ASTM D256 of 11 kgf · cm / cm or more.
The molded article according to the present invention may have a coefficient of linear expansion of 55 to 70 占 퐉 / m 占 폚.
The thermoplastic resin composition of the present invention can be suitably used as a thermoplastic resin composition in the form of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a compatibilizer, a lubricant, an antistatic agent, An additive selected from the group consisting of anti-drip agents, antiwear agents, ultraviolet absorbers, ultraviolet screening agents, and mixtures thereof.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.
The specifications of each component used in the following examples and comparative examples are as follows.
(A) a rubber-modified vinyl-based graft copolymer
G-ABS resin having a core-shell type in which styrene and acrylonitrile were graft-polymerized with styrene-butadiene rubber having an average particle diameter of 0.27 mu m was used.
(B) an aromatic vinyl-cyanide vinyl copolymer
A styrene-acrylonitrile copolymer (SAN) resin having a weight average molecular weight of 120,000 g / mol copolymerized with 32% by weight of acrylonitrile and 68% by weight of styrene, 20% by weight of acrylonitrile and 80% Styrene-acrylonitrile copolymer resin having an average molecular weight of 140,000 g / mol was mixed at a ratio of 50:50.
(C1) a first maleic anhydride copolymer
To 100 parts by weight of a mixture containing 5% by weight of maleic anhydride, 15% by weight of acrylonitrile, 60% by weight of styrene and 20% by weight of toluene was added to a reactor equipped with a stirrer having a capacity of 100 liters, ditertiary butyl- 0.016 part by weight of t-butyl peroxide and 0.017 part by weight of t-dodecyl mercaptan were added thereto. The mixture was reacted at 115 ° C. for 2 hours while stirring, After the reaction, the reaction was further carried out at 125 DEG C for 2 hours to complete the reaction so that the solid content in the reaction mixture became 60% by weight. After the reaction was completed, the reaction mixture was transferred to a devolatilizer, and toluene and unreacted compounds were removed from the reaction mixture under the conditions of 230 ° C and 15 torr.
A maleic anhydride copolymer was prepared using a pelletizer connected to a devolatilizer, and the flow index (MI), the glass transition temperature (Tg) and the maleic anhydride content in the pellets were measured.
According to ASTM D1238 of the prepared first maleic anhydride copolymer, the flow index was 34 g / 10 min, the glass transition temperature was 114 캜, and the maleic anhydride content was 7.6% by weight, measured at 220 캜 / 10 kg.
(C2) a second maleic anhydride copolymer
100 parts by weight of a mixture containing 7% by weight of maleic anhydride, 16% by weight of acrylonitrile, 57% by weight of styrene and 20% by weight of toluene was added to a reactor equipped with a stirrer having a capacity of 100 liters, 0.013 part by weight of ditertiary butyl peroxide Maleic anhydride copolymer and 0.024 part by weight of tertiary dodecyl mercaptan were charged in the same manner as in the production of the (C1) first maleic anhydride copolymer, to thereby prepare a second maleic anhydride copolymer.
The flow index was 32 g / 10 min, the glass transition temperature was 118 占 폚, and the maleic anhydride content was 11.7% by weight as measured according to ASTM D1238 of the second maleic anhydride copolymer produced at 220 占 폚 / 10 kg.
(C3) Third maleic anhydride copolymer
100 parts by weight of a mixture containing 9% by weight of maleic anhydride, 16% by weight of acrylonitrile, 55% by weight of styrene and 20% by weight of toluene was added to a reactor equipped with a stirrer having a capacity of 100 liters, 0.012 part by weight of ditertiary butyl peroxide Maleic anhydride copolymer was prepared in the same manner as in the production of (C1) the first maleic anhydride copolymer, except that 0.029 part by weight of tertiary dodecylmercaptan was added.
The flow index was 31 g / 10 min, the glass transition temperature was 123 占 폚, and the maleic anhydride content was 14.5 wt% as measured according to ASTM D1238 of the third maleic anhydride copolymer prepared at 220 占 폚 / 10kg.
(C4) a fourth maleic anhydride copolymer
100 parts by weight of a mixture comprising 3% by weight of maleic anhydride, 14% by weight of acrylonitrile, 63% by weight of styrene and 20% by weight of toluene was added to a reactor equipped with a stirrer having a capacity of 100 liters, 0.020 parts by weight of ditertiary butyl peroxide Maleic anhydride copolymer was prepared in the same manner as in the production of the (C1) first maleic anhydride copolymer, except that 0.015 part by weight of tertiary dodecylmercaptan was added, to thereby prepare a fourth maleic anhydride copolymer.
According to ASTM D1238 of the produced fourth maleic anhydride copolymer, the flow index was 32 g / 10 min, the glass transition temperature was 110 占 폚, and the maleic anhydride content was 4.5% by weight under the condition of 220 占 폚 / 10 kg.
(C5) Fifth maleic anhydride copolymer
100 parts by weight of a mixture containing 25% by weight of maleic anhydride, 13% by weight of acrylonitrile, 42% by weight of styrene and 20% by weight of toluene was added to a reactor equipped with a stirrer having a capacity of 100 liters, 0.012 part by weight of ditertiary butyl peroxide Maleic anhydride copolymer and 0.045 part by weight of tertiary dodecylmercaptan were charged in the same manner as in the production of the (C1) first maleic anhydride copolymer. However, the fifth maleic anhydride copolymer could not be normally produced due to the fluidity deterioration which could not be measured by the flow index, and the partially sampled samples had a glass transition temperature of 153 占 폚, a maleic anhydride content of 41.7% .
(D) a copolymer comprising an N-substituted maleimide
DENKA-IP manufactured by Nippon Denka Co., Ltd., having a glass transition temperature of 196 ° C, was used.
(E) Talc
A UPN-HS-T 0.5 of Hayakushi Kasei, Japan, having a flake type having an average diameter of 2.7 탆 was used.
(F) Calcium carbonate
Oxalized TSP from Dongho Calcium, having an average particle size of 0.08 mu m, was used.
(Example 1)
100 parts by weight of a base resin mixed with 25% by weight of a rubber-modified vinyl-based graft copolymer (A), 45% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 30% by weight of a first maleic anhydride copolymer 0.1 part by weight of di-stearyl-pentaerythritol-diphosphite and 0.1 part by weight of octadecyl 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate Propionate) in a conventional mixer was extruded using a twin-screw extruder having L / D = 35 and Φ = 45 mm to prepare pellets . The prepared pellets were dried for more than 5 hours in an air flow dryer at 80 ° C before injection molding, and then specimens for measuring properties were prepared using a 10 oz injection machine at an injection temperature of 230 ° C.
(Example 2)
A base resin obtained by mixing 25% by weight of a rubber-modified vinyl-based graft copolymer (A), 50% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 25% by weight of a second maleic anhydride copolymer (C2) The procedure of Example 1 was repeated, except that < RTI ID = 0.0 >
(Example 3)
A base resin obtained by mixing 30% by weight of a rubber-modified vinyl-based graft copolymer (A), 50% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 20% by weight of a third maleic anhydride copolymer (C3) The procedure of Example 1 was repeated, except that < RTI ID = 0.0 >
(Comparative Example 1)
A base resin obtained by mixing 25% by weight of a rubber-modified vinyl-based graft copolymer (A), 30% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 45% by weight of a fourth maleic anhydride copolymer (C4) The procedure of Example 1 was repeated, except that < RTI ID = 0.0 >
(Comparative Example 2)
A base obtained by mixing 25% by weight of a rubber-modified vinyl-based graft copolymer (A), 65% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 10% by weight of a copolymer (D) containing N-substituted maleimide The procedure of Example 1 was repeated except that the resin was used.
(Comparative Example 3)
Except that a base resin containing 25% by weight of a rubber-modified vinyl-based graft copolymer (A), 69% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 6% by weight of talc (E) The procedure of Example 1 was repeated.
(Comparative Example 4)
The procedure of Comparative Example 3 was repeated except that calcium carbonate (F) was used instead of talc (E).
(Comparative Example 5)
A base resin obtained by mixing 30% by weight of a rubber-modified vinyl-based graft copolymer (A), 65% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 5% by weight of a first maleic anhydride copolymer (C1) The procedure of Example 1 was repeated, except that < RTI ID = 0.0 >
(Comparative Example 6)
A base resin obtained by mixing 15% by weight of a rubber-modified vinyl-based graft copolymer (A), 30% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 55% by weight of a first maleic anhydride copolymer (C1) The procedure of Example 1 was repeated, except that < RTI ID = 0.0 >
(Measurement of physical properties)
1) Melt-flow index (MI) (unit: g / 10min)
Measured at 220 캜 / 10 kg in accordance with ASTM D1238.
2) Izod impact strength (unit: kgf · cm / cm)
Measured according to ASTM D256 under notched conditions of 1/4 "thickness.
3) Coefficient of linear expansion (unit: 占 퐉 / m 占 폚)
TMA instrument (TA Instrument Q400) at 30 DEG C to 80 DEG C at a heating rate of 5 DEG C / min. The lower the coefficient of linear expansion, the better the dimensional stability.
4) Vicat softening temperature (VST) (unit: ℃)
Was measured under the condition of 5 kgf and 50 占 폚 / hour according to ISO 306 B-50.
5) Surface gloss (unit: G.U.)
Using a surface gloss measuring instrument (SUGA UGV-6P), a 2.5 mm thick specimen was measured at an angle of 60 degrees.
6) Glass transition temperature of maleic anhydride copolymer
Using a DSC instrument (Perkin-Elemer DSC7), the temperature was elevated from room temperature to 150 ° C at a rate of 10 ° C / minute, and the inflection point of the endothermic transition curve was measured as the glass transition temperature.
7) Analysis of maleic anhydride content in maleic anhydride copolymer
Using the relative size of the absorption peak of maleic anhydride and the carbonyl group (C═O) of PMMA in a maleic anhydride copolymer using PMMA as a standard sample using an FT-IR instrument (Bruker VERTEX80), maleic anhydride Was calculated.
As can be seen from Table 2, Examples 1 to 3 according to the present invention exhibited excellent flowability, impact resistance, heat resistance, surface gloss and low coefficient of linear expansion as compared with Comparative Examples. That is, it can be confirmed that the thermoplastic resin composition according to the embodiment of the present invention can provide a thermoplastic resin composition excellent in dimensional stability and excellent in heat resistance, impact resistance, appearance characteristics, and molding processing characteristics.
Specifically, in Comparative Example 1 in which the content of maleic anhydride in the maleic anhydride copolymer is 5% by weight or less, the impact resistance is relatively low. In order to increase the heat resistance, an excessively large amount of maleic anhydride copolymer is used will be.
In Comparative Example 2, a copolymer containing N-substituted maleimide was used. Although the heat resistance and the surface gloss were excellent, it was confirmed that both of them were deteriorated in terms of impact resistance, dimensional stability (linear expansion coefficient) and molding processability (fluidity) have. Further, in Comparative Examples 3 and 4, it was confirmed that all the properties except for dimensional stability were degraded by using an inorganic component.
In Comparative Example 5, the content of the maleic anhydride copolymer in the composition was excessively low, so that the dimensional stability, which is an effect of the present invention, was not sufficiently realized and the heat resistance was lowered. In Comparative Example 6, the use of an excess amount of maleic anhydride copolymer , The effect of improving the dimensional stability is realized, but it can be confirmed that the effect of the present invention is not fully realized as the impact strength is lowered.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (11)
(B) an aromatic vinyl-cyanide vinyl copolymer and
(C) a maleic anhydride copolymer.
The composition comprises 10 to 40% by weight of a rubber-modified vinyl-based graft copolymer (A), 20 to 50% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) and 10 to 50% by weight of a maleic anhydride copolymer (C) Wherein the thermoplastic resin composition has excellent dimensional stability.
Wherein the maleic anhydride copolymer is prepared by copolymerizing a mixture containing an aromatic vinyl compound, a vinyl cyanide compound and a maleic anhydride compound.
The maleic anhydride copolymer has a maleic anhydride-based compound content of 5 to 40% by weight, and is excellent in dimensional stability.
The rubber-modified vinyl-based graft copolymer (A) is prepared by graft-polymerizing a mixture containing a rubbery polymer, an aromatic vinyl compound, and a vinyl cyanide compound, and the thermoplastic resin composition is excellent in dimensional stability.
The rubber-modified vinyl-based graft copolymer (A) is obtained by graft-polymerizing 30 to 70% by weight of a mixture of an aromatic vinyl compound and a vinyl cyanide compound with 30 to 70% by weight of a rubbery polymer by emulsion polymerization, Butadiene-styrene graft copolymer (g-ABS) having excellent dimensional stability.
The aromatic vinyl-cyanide vinyl copolymer (B) may be selected from a copolymer of styrene and acrylonitrile, a copolymer of? -Methylstyrene and acrylonitrile, and a copolymer of styrene,? -Methylstyrene and acrylonitrile The thermoplastic resin composition is excellent in dimensional stability.
The maleic anhydride copolymer (C) has a glass transition temperature of 111 to 130 DEG C and is excellent in dimensional stability.
Antioxidants, heat stabilizers, antioxidants, mold release agents, light stabilizers, inorganic additives, surfactants, coupling agents, plasticizers, compatibilizers, lubricants, antistatic agents, colorants, pigments, dyes, flame retardants, flame retardants, An additive selected from the group consisting of an ultraviolet absorber, an ultraviolet absorber, and a mixture thereof.
Wherein the molded article has a linear expansion coefficient of 55 to 70 占 퐉 / m 占 폚.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190071457A (en) * | 2017-12-14 | 2019-06-24 | 주식회사 엘지화학 | Thermoplastic resin composition |
| WO2020091343A1 (en) * | 2018-10-31 | 2020-05-07 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article using same |
| WO2021085840A1 (en) * | 2019-10-30 | 2021-05-06 | 롯데케미칼 주식회사 | Thermoplastic resin composition, and molded article therefrom |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190071457A (en) * | 2017-12-14 | 2019-06-24 | 주식회사 엘지화학 | Thermoplastic resin composition |
| WO2020091343A1 (en) * | 2018-10-31 | 2020-05-07 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article using same |
| WO2021085840A1 (en) * | 2019-10-30 | 2021-05-06 | 롯데케미칼 주식회사 | Thermoplastic resin composition, and molded article therefrom |
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