WO2014123373A1 - 내충격성 또는 내열성이 우수한 고분자 수지 조성물 - Google Patents
내충격성 또는 내열성이 우수한 고분자 수지 조성물 Download PDFInfo
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- WO2014123373A1 WO2014123373A1 PCT/KR2014/001029 KR2014001029W WO2014123373A1 WO 2014123373 A1 WO2014123373 A1 WO 2014123373A1 KR 2014001029 W KR2014001029 W KR 2014001029W WO 2014123373 A1 WO2014123373 A1 WO 2014123373A1
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a polymer resin 2: property, and more particularly, to a polymer resin composition capable of providing a synthetic resin exhibiting physical properties such as improved heat resistance or impact resistance.
- Polyester resins are widely used as reinforcing plastics, paints, films, molding resins, etc. due to their relatively excellent heat resistance, mechanical strength, and elastic strength. Recently, due to its characteristic properties, polyester resins are increasingly used in fields such as building interior materials or molded signboards. However, polyester resins have lower heat resistance than other polymer materials, for example, acrylic materials or polycarbonate materials, and thus have a problem of being unsuitable for use as outdoor exterior materials having severe seasonal temperature changes.
- polycarbonate water is used in various fields such as exterior, packaging materials, cases, boxes, interior and exterior materials of various building materials and electronic products.
- These polycarbonate resins are in high demand due to their excellent mechanical properties, but the appearance color of the polycarbonate changes or cracks are generated by various detergents, women's cosmetics, and baby hand sanitizers commonly used in the market. There is a problem that causes deterioration of.
- ABS acrylonitrile-butadiene-styrene graft copolymer
- polyester resin and the polycarbonate resin have different melt viscosities and molecular structures, there is a certain limit in improving heat resistance by simply blending them.
- various methods have been used to increase the chemical resistance while maintaining the mechanical properties of the polycarbonate, especially heat resistance, but the degree of improvement in chemical resistance was not sufficient to be practically applicable to industrial applications, and the appearance of the resin product manufactured There was a problem of deterioration of characteristics.
- a method of further blending one or more materials has also been attempted, but it is difficult to express an appropriate level of chemical resistance.
- the present invention is to provide a polymer resin composition capable of providing a synthetic resin exhibiting physical properties such as improved heat resistance or impact resistance.
- the present invention is a polyester copolymer comprising a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a dial component containing dianhydronuclear;
- the polyester copolymer, the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, and alkyl methacrylate- With silicone / alkylacrylate graft copolymer It may comprise 1 to 80% by weight of one or more copolymers selected from the group consisting of.
- the polymer resin composition may further include 5 to 90% by weight of polycarbonate.
- the polymer resin composition may include an aromatic vinyl-aromatic maleimide-maleic anhydride copolymer, an aromatic vinyl-unsaturated nitrile-aromatic maleimide copolymer, an aromatic vinyl- ⁇ -methyl aromatic vinyl copolymer, and an aromatic vinyl-unsaturated nitrile- It may further comprise one or more selected from the group consisting of ⁇ -methyl aromatic vinyl copolymer.
- the polyester copolymer has a weight average molecular weight of 10,000 to 100,000, the glass transition temperature may be 0 to 200 ° C.
- the dicarboxylic acid component in the polyester copolymer may further include one or more selected from the group consisting of aromatic dicarboxylic acid having 8 to 20 carbon atoms, and aliphatic dicarboxylic acid having 4 to 20 carbon atoms. have.
- the dianhydronuclear may be isosorbide in the polyester copolymer.
- the content of dianhydronucleic acid in the polyester copolymer may be 5 to 60 mol% based on the content of the total diol component.
- the diol component in the polyester copolymer may further include one or more selected from the group consisting of compounds represented by Formulas 1 2 and 3 below.
- 3 ⁇ 4 and R 4 are each independently hydrogen or carbon number 1 And a substituted or unsubstituted alkyl group of 5 to 5, and n 2 are each independently an integer of 0 to 3.
- Ri, R 2 , 3 ⁇ 4 and 4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.
- n is an integer of 1 to 7.
- the diol component in the polyester copolymer may further include 1,4-cyclonucleodiol diol and ethylene glycol.
- the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is in the form of a core-shell rubber (Core-Shell Rubber), the average particle diameter of 0.01 to 5 / / m, the graft rate is 5 to 90%, the core ( The glass transition temperature of the core) is -20 ° C or less, and the glass transition temperature of the shell may be 20 ° C or more.
- the unsaturated nitrile in the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is composed of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile. It may be one or more selected from.
- the diene rubber in the graft copolymer may be butadiene rubber or isoprene rubber.
- the aromatic vinyl in the graft copolymer is selected from the group consisting of styrene, ⁇ -methylstyrenevinylluene, t-butylstyrene, halogen-substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, and ethylstyrene. It may be one or more selected.
- the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.
- the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer may be a methyl methacrylate-butadiene-styrene graft copolymer.
- the alkyl methacrylate-silicone / alkyl acrylate graft copolymer may be a methyl methacrylate-silicone / butyl acrylate graft copolymer.
- the polycarbonate may have a glass transition temperature of 50 to 20CTC, and a weight average molecular weight of 10,000 to 200,000.
- the polymer resin composition is a unsaturated nitrile-aromatic vinyl copolymer, an unsaturated nitrile-aromatic vinyl ⁇ glycidyl methacrylate-based compatibilizer, an unsaturated nitrile-aromatic vinyl-maleic anhydride-based compatibilizer, saturated ethylene-alkyl acrylate It may further comprise at least one member selected from the group consisting of -glycidyl methacrylate-based compatibilizer, and carbodiimide-based hydrolysis agent.
- the polymer resin composition may contain at least 10% by weight of the total composition of at least one additive selected from the group consisting of antioxidants, lubricants, light stabilizers, light absorbers, transesterification inhibitors, and hydrolysis agents. have.
- a polymer resin composition which is not only environmentally friendly, but also can provide a synthetic resin having improved physical properties such as improved heat resistance or layer resistance, and a synthetic resin or a resin molded product obtained using the same can be provided.
- the present invention is a polyester copolymer comprising a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a dial component containing dianhydronuclear;
- Unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, and alkyl methacrylate ⁇ silicone / alkylacrylate graft copolymer It provides a polymer resin composition comprising at least one co-polymer.
- a polyester copolymer comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component including dianhydronuclear;
- a polymer resin composition comprising at least one copolymer may be provided.
- ABS acrylonitrile-butadiene-styrene graft copolymer
- the present inventors proceed with the research on the resin composition, which is environmentally friendly and excellent in heat resistance or layer resistance, specific polyester co-polymer; And unsaturated nitrile-diene rubber-aromatic vinyl graft copolymers, Excellent in polymer resin compositions comprising alkyl methacrylate—diene rubber-aromatic vinyl graft copolymers and at least one copolymer selected from the group consisting of alkyl methacrylate-silicone / alkyl acrylate graft copolymers It was confirmed through experiments that the physical properties such as heat resistance or impact resistance was completed, and completed the invention.
- polyester copolymers In the process of preparing the polymer resin composition, conventional methods and apparatuses used to prepare blends or mixtures of polymer resins may be used without particular limitation.
- polyester copolymers For example, polyester copolymers; And unsaturated nitrile-diene rubber-aromatic vinyl graft copolymers, alkyl methacrylate-diene rubber-aromatic vinyl graft copolymers, and alkylmethacrylate-silicone / alkylacrylate graft copolymers.
- the polymer resin composition may be provided by adding one or more selected copolymers to a conventional mixer, mixer, or tumbler and mixing the same through a twin screw extruder.
- each of the resins are preferably used in a sufficiently dried state.
- the polymer resin composition may comprise 1 to 80% by weight of one or more copolymers selected from the group consisting of acrylate-silicone / alkylacrylate graft copolymers.
- the polymer resin composition may further include 5 to 90% by weight of polycarbonate.
- the polymer resin composition is an aromatic vinyl-aromatic maleimide-maleic anhydride copolymer, aromatic vinyl-unsaturated nitrile-aromatic maleimide copolymer, aromatic vinyl- ⁇ -methyl aromatic vinyl copolymer, and aromatic vinyl-unsaturated nitrile- It may further comprise one or more selected from the group consisting of ⁇ -methyl aromatic vinyl copolymer.
- the content of 1 to 80% by weight of the components may be improved heat resistance of the polymer resin composition.
- the polymer resin composition according to the present invention has excellent impact strength in the case of general high impact applications and heat resistance of 85 to 90 ° C., and heat resistance of 90 to 100 ° C. for high impact applications.
- the heat resistance can be designed above 100 ° C.
- polycarbonate is used for high heat resistance over 100 ° C, but polycarbonate is not used for general high impact and heat resistant high impact applications, and aromatic vinyl-aromatic maleimide-maleic anhydride copolymer, aromatic And at least one selected from the group consisting of vinyl-unsaturated nitrile-aromatic maleimide copolymers, aromatic vinyl- ⁇ -methyl aromatic vinyl copolymers, and aromatic vinyl-unsaturated nitrile- ⁇ ⁇ methyl aromatic vinyl copolymers.
- 'residue' means a certain part or unit included in the result of the chemical reaction and derived from the specific compound when the specific compound participates in the chemical reaction.
- each of the 'residues' of the dicarboxylic acid component or the 'residues' of the diol component is derived from a diol component or part derived from the dicarboxylic acid component in a polyester formed of an esterification reaction or a condensation polymerization reaction. Means the derived part.
- the 'dicarboxylic acid component' is a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and a lower alkyl ester having 1 to 4 carbon atoms and / or their It is used to mean acid anhydride, and can react with a diol component to form a dicarboxylic acid nioiety such as a terephthaloyl moiety.
- the heat resistance, chemical resistance or weather resistance of the polyester resin produced for example, prevention of molecular weight reduction phenomenon or sulfur change phenomenon by UV), etc.
- the physical properties of can be improved.
- the dicarboxylic acid component may further include an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component, or a mixture thereof as other dicarboxylic acid components.
- 'other dicarboxylic acid component' means all components other than terephthalic acid among the dicarboxylic acid components.
- the dicarboxylic acid component in the polyester copolymer is carbon number
- It may further include one or more selected from the group consisting of 8 to 20 aromatic dicarboxylic acid, and aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
- the aromatic dicarboxylic acid component may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, preferably 8 to 14 carbon atoms, or a mixture thereof.
- the aromatic dicarboxylic acid include naphthalenedicarboxylic acid such as isophthalic acid and 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'- stilbendicarboxylic acid, 2, 5-furanedicarboxylic acid, 2, 5 ⁇ thiophene dicarboxylic acid, etc., but the specific examples of the aromatic dicarboxylic acid is not limited thereto.
- the aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a mixture thereof.
- the aliphatic dicarboxylic acid include cyclocarboxylic acid dicarboxylic acid such as 1,4-cyclonucleic acid dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, Linear, branched, or cyclic aliphatic dicarboxylic acid components such as maleic acid, fumaric acid, adipic acid, glutaric acid, azelaic acid, and the like, but are not limited thereto.
- the dicarboxylic acid component is 50 to 100 mol 3 ⁇ 4>, preferably 70 to 100 mol% terephthalic acid; And 0 to 50 mol%, preferably 0 to 30 mol% of at least one dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acid and aliphatic dicarboxylic acid. If the content of terephthalic acid in the dicarboxylic acid component is too small or too large, physical properties such as heat resistance, chemical resistance or weather resistance of the polyester resin may be lowered.
- the diol component (diol component) used in the synthesis of the polyester may include 5 to 60 mol% of dianhydronuclear, 5 to so of cyclohexane dimethane, and the remaining amount of other diol compounds.
- the diol component preferably comprises isosorbide (l, 4: 3,6-dianhydroglucitol) as dianhydronuclear. Therefore, not only the heat resistance of the polyester resin to be produced can be improved, but also physical properties such as chemical resistance and chemical resistance can be improved.
- the content of cyclonucleodimethanol eg, 1,2-cyclonucleodimethanol, 1,3-cyclonucleodimethane or 1,4-cyclonucleodimethanol
- the interlayer strength of the polyester resin to be produced may increase significantly.
- the diol component may further include other diol components in addition to the isosorbide and cyclonucleic acid dimethanol.
- the 'other diol component' means a diol component except for the isosorbide and cyclohexane dimethane, and may be, for example, an aliphatic diol, an aromatic diol or a combination thereof.
- the diol component in the polyester copolymer may include one or more selected from the group consisting of compounds represented by the following formula (1), (2) and (3).
- Ri, R 3 and R 4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and n 2 are each independently an integer of 0 to 3.
- 3 ⁇ 4 and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.
- n is an integer of 1 to 7.
- the diol component of the polyester resin may include 5 to 60 mol% of dianhydronuclear.
- the content of the diol component increase dianhydronuclear is less than 5 mol%, the heat resistance or chemical resistance of the polyester resin to be prepared may be unsatisfactory, and the melt viscosity characteristics of the polyester resin may not appear.
- the content of the dianhydronucleic acid exceeds 60 mol%, the polyester resin or the product may have a deterioration in appearance characteristics or yellowing.
- the polyester copolymer has a weight average molecular weight of 10,000 to 100,000, the glass transition temperature may be 0 to 200 ° C.
- the polyester resin is dicarboxylic acid containing terephthalic acid and diol component containing 5 to 60 mol% of dianhydronucleoisoisosorbide, 5 to 80 mol% of cyclohexane dimethyl methane and the remaining amount of other diol compounds Esterifying the acid component; Adding a phosphorus stabilizer when the esterification reaction proceeds at least 80%; And it may be provided by a method for producing a polyester resin comprising the step of polycondensation reaction of the esterification reaction product.
- an esterification reaction catalyst containing a zinc compound is used, and at the end of the esterification reaction, for example, a phosphorus stabilizer is added to the reaction solution at a time when the reaction proceeds at least 80%.
- a polyester resin exhibiting physical properties such as high heat resistance, flame retardant properties and layer toughness and excellent appearance properties, high transparency and excellent molding properties.
- the esterification step may be achieved by reacting the dicarboxylic acid component and diol component at a pressure of 0 to 10.0 kg / cin 2 and a temperature of 150 to 300 ° C.
- the esterification reaction conditions may be appropriately adjusted according to the specific properties of the polyester to be produced, the molar ratio of the dicarboxylic acid component and glycol, or process conditions. Specifically, preferred examples of the esterification conditions, 0 to 5.0 kg / ciif, more preferably 0.1 to 3.0 kg / cui 2 pressure; A temperature of 200 to 270 ° C, more preferably 240 to 260 ° C can be mentioned.
- the esterification reaction may be performed in a batch or continuous manner, and each raw material may be added separately, but it is preferable to add the dicarboxylic acid component to the diol component in the form of a mixed slurry.
- the diol component such as dianhydronuclear, which is a solid content at room temperature, can be dissolved in water or ethylene glycol, and then mixed with dicarboxylic acid components such as terephthalic acid to form a slurry.
- a slurry may also be prepared by mixing a dicarboxylic acid component such as tetephthalic acid and other dial components.
- water may be added to a slurry in which a dicarboxylic acid component, a dianhydronuclear and a copolymerized di-component, such as ethylene glycol, are added, to help increase the fluidity of the slurry.
- the molar ratio of the dicarboxylic acid component and diol component participating in the esterification reaction may be 1: 1.05 to 1: 3.0.
- the unbanung dicarboxylic acid component may remain in the polymerization reaction to reduce transparency of the resin, and when the molar ratio exceeds 3.0, the polymerization reaction rate may be It may be lowered or the productivity of the resin may be lowered.
- the poly-condensation reaction of the esterification reaction product comprises the esterification of the dicarboxylic acid component and di-component.
- the reaction product may include the step of reacting for 1 to 24 hours at 150 to 300 ° C temperature and reduced pressure conditions of 600 to 0.01 mmHg.
- Such polycondensation reaction is, the reaction temperature of 150 to 300 ° C, preferably 200 to 290 ° C, more preferably 260 to 280 ° C; And 600 to 0.1 ° Hg, preferably 200 to 0.05 mmHg, more preferably 100 to 0.1 mmHg.
- the polycondensation reaction occurs outside the temperature range of 150 to 300 ° C, when the polycondensation reaction proceeds to 150 ° C or less, the intrinsic viscosity of the final reaction product may not be effectively removed from the system as a glycol by-product of the polycondensation reaction. Low physical properties of the polyester resin can be lowered, and when the reaction proceeds to 300 ° C or more, the appearance of the polyester resin to be produced becomes more likely to become yellow (yellow). The polycondensation reaction can then proceed for the required time until the intrinsic viscosity of the final reaction product reaches an appropriate level, for example for an average residence time of 1 to 24 hours.
- the production method of the polyester resin composition may further comprise the step of further adding a polycondensation catalyst.
- a polycondensation catalyst may be added to the product of the esterification reaction or transesterification reaction before the initiation of the polycondensation reaction, and prior to the esterification reaction, di is added to a mixed slurry comprising a component and a dicarboxylic acid component. It may be added during the esterification reaction step.
- a titanium compound, a germanium compound, an antimony compound aluminum compound, a tin compound, or a mixture thereof can be used as the polycondensation catalyst.
- examples of the titanium compound and the germanium compound are as described above.
- the polymer resin composition according to the present invention is unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer, alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, and alkyl methacrylate- At least one copolymer selected from the group consisting of silicone / alkylacrylate graft copolymers.
- the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is in the form of a core-shell rubber (Core-She 11 Rubber), having an average particle diameter of 0.01 to 5 and a graft ratio of 5 to 90%,
- the glass transition temperature is below -20 ° C, the shell glass transition temperature may be above 20 ° C.
- the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer is a core-shell rubber manufactured through a fusion polymerization or a bulk polymerization process, and has an average particle diameter of 0.01 to 5 ⁇ m and a graft ratio of 5 to. 90%, the glass transition temperature of the core is -20 ° C or less, the shell glass transition temperature is 20 ° C or more, and optionally the glycidyl methacrylate or maleic anhydride in the shell It may or may not include functional groups such as these.
- the unsaturated nitrile is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile. It may be one or more selected.
- the diene rubber in the graft copolymers may be butadiene rubber or isoprene rubber.
- the aromatic vinyl in the graft co-polymers is a group consisting of styrene Q-methyl styrene vinylluene, t-butyl styrene, halogen-substituted styrene, 1,3- dimethyl styrene, 2, 4- dimethyl styrene, and ethyl styrene It may be one or more selected from.
- the core-shell rubber (Core-Shell Rubber) is optionally in the form of a monomorphic distribution (Morphology) having a mean particle size of 0.01 to 5) (Morphology) or a multi-particle distribution of a mean particle size of 0.01 to 5 distribution of morphology (Morphology).
- alkyl methacrylate may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, and butyl methacrylate. have.
- the unsaturated nitrile-diene rubber-aromatic vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer
- the alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer is Methylmethacrylate-butadiene-styrene graft copolymer
- the alkyl methacrylate-silicone / alkyl acrylate graft copolymer may be a methyl methacrylate-silicone / butyl acrylate graft copolymer.
- the polycarbonate may have a glass transition temperature of 50 to 200 ° C, a weight average molecular weight of 10,000 to 200, 000.
- the polymer resin composition may be unsaturated nitrile-aromatic vinyl copolymer, unsaturated nitrile-aromatic vinyl ⁇ glycidyl methacrylate compatibilizer, unsaturated nitrile-aromatic vinyl ⁇ maleic anhydride compatibilizer, saturated ethylene-alkylacrylate- It may further include one or more selected from the group consisting of glycidyl methacrylate-based compatibilizer, and carbodiimide-based hydrolysis agent.
- the unsaturated nitrile-aromatic vinyl copolymer is 80 wt% or less
- the unsaturated nitrile-aromatic vinyl-glycidyl methacrylate compatibilizer is 50% by weight or less
- the unsaturated nitrile-aromatic vinyl-maleic anhydride compatibilizer is 50 wt% or less
- saturated ethylene-alkylacrylate-glycidyl methacrylate-based compatibilizer may be 50 wt% or less
- carbodiimide-based hydrolysis agent may be included in 30 wt% or less.
- the alkyl acrylate may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, nucleosil acrylate, octyl acrylate and 2-ethyl nucleo acrylate. have.
- the unsaturated nitrile-aromatic vinyl copolymer has a glass transition temperature of 50 to 200 ° C, the weight average molecular weight may be 10,000 to 5,000,000.
- the unsaturated nitrile-aromatic vinyl-glycidyl methacrylate compatibilizer has a glass transition temperature of 20 to 200 ° C., a weight average molecular weight of 200 to 300,000, and optionally an aromatic vinyl-glycidyl methacrylate. Can replace have.
- the unsaturated nitrile-aromatic vinyl-maleic anhydride-based compatibilizer may have a glass transition temperature of 20 to 200 ° C, a weight average molecular weight of 200 to 300,000, and the saturated ethylene-alkyl acrylate-glycidyl methacrylate.
- the system compatibilizer may have a glass transition temperature of -150 to 20 CTC and a weight average molecular weight of 200 to 300,000.
- the carbodiimide-based hydrolysis agent may have a weight average molecular weight of 50 to 300,000, and may be represented by the following formula (4) or (5).
- 3 ⁇ 4 and 3 ⁇ 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms.
- R is an alkyl group having 1 to 20 carbon atoms or 6 to
- the polymer resin composition comprises at least one additive selected from the group consisting of antioxidants, lubricants, light stabilizers, light absorbers, transesterification inhibitors, and hydrolysis agents, dicarboxylic acid components containing terephthalic acid Polyester copolymer comprising a residue and a residue of a diol component including dianhydronuclear; And
- Unsaturated nitrile-diene rubber—aromatic vinyl graft copolymer, alkyl methacrylate—diene rubber-aromatic vinyl graft copolymer, and alkylmethacrylate-silicone / alkylacrylate graft copolymer It may comprise less than 10% by weight relative to the total base resin consisting of one or more copolymers.
- the hindered phenolic antioxidant may have a weight average molecular weight of 50 to 00,000.
- the phosphite-based antioxidant may be selected from the group consisting of the following formula (6), (7) and (8).
- Ri and R 2 are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and n represents a repeating unit substituted as an integer of 1 or more. .
- R 2 , R 3 and R 4 are each independently, from 1 to
- the thioester-based antioxidant may be a compound represented by the following formula (9) or formula (10).
- R 4 are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.
- the lubricant may be at least one selected from the group consisting of metal stearate lubricants, amide lubricants, paraffin lubricants, and ester lubricants.
- the light stabilizer and the light absorbent may be a Hals light stabilizer, a benzotriazole light absorber or a benzophenone light absorber.
- the transesterification reaction inhibitor may be a phosphorus compound containing a minimum hydroxyl functional group and an alkylester functional group or a hydrazine compound containing a unit represented by the following formula (11).
- the polymer resin composition according to the present invention may further include a chain extender or a coupling agent including an glycidyl methacrylate unit, an inorganic additive, It may further comprise an additive selected from the group consisting of a layer agent, a dye, a pigment, and a colorant.
- a chain extender or a coupling agent including an glycidyl methacrylate unit an inorganic additive
- It may further comprise an additive selected from the group consisting of a layer agent, a dye, a pigment, and a colorant.
- terephthalic acid-iso carbide -1, 4-cyclonucleodiol diol-ethylene glycol copolymer polyester is eco-enzyme (EC0ZEN), acrylonitrile-butadiene-styrene graft copolymer of SK Chemicals HR-181, a methyl-methacrylate-butadiene-styrene graft copolymer, is a core-shell rubber (Core— Shell) product of Kumho Petrochemical's core-shell rubber (Core-She 11 Rubber).
- Rubber-type graft MBS product, M-511, polycarbonate is made by Samyang 3020PJ, acrylonitrile styrene-glycidyl methacrylate is manufactured by SUNNY FC of China, SAG-001 and phenolic primary oxidation stabilizer of ADEKA of Japan A0-60, a phosphite secondary oxidative stabilizer, was used S-9228 manufactured by DOVER, USA.
- Tg 1301, weight average molecular weight: 40,000
- Example 3 3% by weight of nitrile-styrene-glycidyl methacrylate, 0.2% by weight of a phenolic primary oxidative stabilizer and a phosphite secondary oxidative stabilizer were respectively added to uniformly extrude the mixture to prepare pellets.
- a phenolic primary oxidative stabilizer and a phosphite secondary oxidative stabilizer were respectively added to uniformly extrude the mixture to prepare pellets.
- Terephthalic acid-isosorbide -1, 4-cyclodiamino diol-ethylene glycol copolymer polyester (Tg: 130 " C, weight average molecular weight: 4) using a biaxial kneading extruder ( ⁇ : 40 kPa, L / D 40) Acrylonitrile-styrene-glycidyl methacrylate 2 relative to 100% by weight of resin consisting of 70% by weight, 15% by weight of methyl methacrylate-butadiene-styrene graft copolymer, and 15% by weight of polycarbonate 0.2% by weight of the weight%, phenol-based primary oxidative stabilizer, phosphite secondary oxidative stabilizer, respectively, was added uniformly to the extrusion extrusion to prepare a pellet.
- Tg 130 V, weight average molecular weight: 40,000
- a biaxial kneading extruder ⁇ : 40 k
- the acrylonitrile-styrene copolymer was SAN-326 which is a Kumho Petrochemical Bulk SAN product, and the phosphite secondary oxidative stabilizer was used by Igarfos 168 and P-EPQ of Clariant, Switzerland.
- SAN-326 is a Kumho Petrochemical Bulk SAN product
- phosphite secondary oxidative stabilizer was used by Igarfos 168 and P-EPQ of Clariant, Switzerland.
- Terephthalic acid-isosorbide -1, 4-cyclonucleic acid diol- ethylene glycol copolymer polyester (Tg: 120 V, weight average molecular weight: 50,000) using a biaxial kneading extruder ( ⁇ : 40 mm, L / D 40) Acrylonitrile-styrene-glycidyl methacryl with respect to 100% by weight of a resin consisting of 70% by weight, 15% by weight of methyl methacrylate-silicone / butyl acrylate graft copolymer, and 15% by weight of polycarbonate. 0.2 wt% of a 3 wt% rate, a phenolic primary oxidative stabilizer and a phosphite secondary oxidative stabilizer were respectively added, and uniform extrusion was carried out to prepare pellets. .
- methyl methacrylate-silicone / butyl acrylate graft The copolymer used S-2001 manufactured by Mitsubishi Rayon of Japan, which is a graft MBS product in the form of a core-shell rubber (Core-She 11 Rubber).
- S-2001 manufactured by Mitsubishi Rayon of Japan
- graft MBS product in the form of a core-shell rubber (Core-She 11 Rubber).
- the general polycarbonate used Samyang 30 Samy
- Terephthalic acid-isosorbide-1,4-cyclodiacid di-ethylene glycol copolymer polyester Tg: 120 V, weight average molecular weight: 50,000
- Tg 120 V, weight average molecular weight: 50,000
- Acrylonitrile based on 100% by weight of resin, consisting of 60% by weight, acrylonitrile-butadiene-styrene graft copolymer 10% polycarbonate 23% by weight, and 7% by weight styrene-N-phenylmaleimide-maleic anhydride -2 wt% of styrene-maleic anhydride, 0.2 wt% of a phenolic primary oxidative stabilizer, and a phosphite secondary oxidative stabilizer were respectively added, and uniform extrusion was carried out to prepare pellets.
- polycarbonate is 3030PJ of Samyang
- styrene-N-phenylmaleimide-maleic anhydride is MS-NI of Japan Electrochemistry.
- Acrylonitrile-styrene-maleic anhydride was used as SAM-002 product of SUNNY FC in China.
- polycarbonate is 3030PJ of Samyang
- styrene-N-phenylmaleimide-maleic anhydride MS-NI
- acrylonitrile-styrene-maleic anhydride of DENKI KAGAKU is a compatibilizer of China SUNNY FC SAM-002 product was used.
- polycarbonate is 3030PJ of Samyang Corporation
- styrene-acrylonitrile-N-phenylmaleimide is P-1460
- acrylonitrile-styrene-maleic anhydride of NIPPON SH0KUBAI Japan Nippon Catalyst (SUNNY FC) SAM-002 product was used.
- Terephthalic acid-isosorbide -1, 4-cyclodiacid di-ethylene glycol copolymer polyester (Tg: 95 ° C, weight average molecular weight: 5) using a biaxial kneading extruder ( ⁇ : 40 kPa, L / D 40) Only) 50% by weight of acrylonitrile-butadiene-styrene graft copolymer, and 100% by weight of acrylonitrile- ⁇ -methylstyrene with respect to 100% by weight of acrylonitrile-styrene-glycidyl 0.5% by weight of methacrylate, 0.2% by weight of phenol-based primary oxidative stabilizer and phosphite secondary oxidative stabilizer were respectively added, and uniform extrusion was performed to prepare pellets.
- acrylonitrile- ⁇ -methylstyrene was used as a compatibilizer for VAG acrylonitrile-styrene-glycidyl methacrylate of STYR0LUTI0N in Germany, and SAG-005 of SUNNY FC in China.
- Example 15 acrylonitrile- ⁇ -methylstyrene was used as a compatibilizer for VAG acrylonitrile-styrene-glycidyl methacrylate of STYR0LUTI0N in Germany, and SAG-005 of SUNNY FC in China.
- Terephthalic acid-isosorbide -1, 4-cyclodiacid di-ethylene glycol copolymer polyester Tg: 110 ° C, weight average molecular weight: 50,000
- acrylonitrile- ⁇ -methylstyrene was used as a compatibilizer for VAG acrylonitrile-styrene-glycidyl methacrylate of STYR0LUTI0N in Germany, and SAG-005 of SUNNY FC in China.
- Melt index tester Melt index was measured using Flow Indexer, Davenport).
- MA-based compatibilizer maleic anhydride graft ethylene-octene copolymer
- PLA-g-MA Maleic anhydride graft polylactic acid resin
- Triaryl Isocyanate Triaryl Isocyanate from Tokyo Chemical Industries, Japan -Talc : Koch KC-3000
- MMA-Talc Talc coated with methyl methacrylate
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EP14749357.1A EP2955204B1 (en) | 2013-02-06 | 2014-02-06 | Polymer resin composition having excellent impact resistance or heat resistance |
CN201480007654.5A CN104968726B (zh) | 2013-02-06 | 2014-02-06 | 具有优良的抗冲击性或耐热性的聚合物树脂组合物 |
ES14749357T ES2698355T3 (es) | 2013-02-06 | 2014-02-06 | Composición de resina de polímero que presenta una resistencia al impacto o una resistencia al calor excelentes |
JP2015555926A JP6378211B2 (ja) | 2013-02-06 | 2014-02-06 | 耐衝撃性または耐熱性に優れた高分子樹脂組成物 |
US14/765,942 US9777151B2 (en) | 2013-02-06 | 2014-02-06 | Polymer resin composition having excellent impact resistance or heat resistance |
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KR (1) | KR101922246B1 (ko) |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3015507A1 (en) * | 2014-10-31 | 2016-05-04 | Hyundai Motor Company | Chemical resistant polymer composition for a center fascia |
CN105566877A (zh) * | 2014-10-31 | 2016-05-11 | 现代自动车株式会社 | 用于车辆顶置控制台的耐化学性聚合树脂组合物 |
CN105566879A (zh) * | 2014-10-31 | 2016-05-11 | 现代自动车株式会社 | 用于中心仪表的化学耐腐蚀聚合物组合物 |
JP2016089162A (ja) * | 2014-10-31 | 2016-05-23 | エスケー ケミカルズ カンパニー リミテッド | オーバーヘッドコンソール用耐薬品性高分子樹脂組成物 |
US9580596B2 (en) | 2014-10-31 | 2017-02-28 | Sk Chemicals Co., Ltd. | Chemical resistant polymer composition for a center fascia |
CN111225955A (zh) * | 2017-10-16 | 2020-06-02 | 科思创德国股份有限公司 | 具有低双酚a含量的耐火的聚碳酸酯-丙烯酸酯-橡胶-组合物 |
CN111393587A (zh) * | 2019-12-20 | 2020-07-10 | 赣州能之光新材料有限公司 | 一种多元单体接枝abs高胶粉共聚物及其制备方法 |
Also Published As
Publication number | Publication date |
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EP2955204A1 (en) | 2015-12-16 |
US20150368460A1 (en) | 2015-12-24 |
JP6378211B2 (ja) | 2018-08-22 |
EP2955204B1 (en) | 2018-08-22 |
ES2698355T3 (es) | 2019-02-04 |
CN104968726B (zh) | 2018-06-26 |
US9777151B2 (en) | 2017-10-03 |
KR101922246B1 (ko) | 2018-11-26 |
EP2955204A4 (en) | 2016-09-07 |
JP2016505088A (ja) | 2016-02-18 |
KR20140100301A (ko) | 2014-08-14 |
CN104968726A (zh) | 2015-10-07 |
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