KR20150068313A - COMPOSITION OF STYRENE RESIN HAVING Chemical Resistance and SUPERIOR HEAT RESISTANCE AND MOLDED ARTICLE MADE FROM the SAME - Google Patents
COMPOSITION OF STYRENE RESIN HAVING Chemical Resistance and SUPERIOR HEAT RESISTANCE AND MOLDED ARTICLE MADE FROM the SAME Download PDFInfo
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- KR20150068313A KR20150068313A KR1020140176027A KR20140176027A KR20150068313A KR 20150068313 A KR20150068313 A KR 20150068313A KR 1020140176027 A KR1020140176027 A KR 1020140176027A KR 20140176027 A KR20140176027 A KR 20140176027A KR 20150068313 A KR20150068313 A KR 20150068313A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- 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
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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
- 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
- C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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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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- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
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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
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
Abstract
The present invention relates to a styrene resistant chemical resistant heat resistant resin composition and a molded article produced therefrom, and more particularly to a thermoplastic resin composition excellent in chemical resistance and heat resistance and a molded article produced therefrom.
In order to achieve the above object, the present invention relates to a thermoplastic elastomer composition comprising 30 to 50% by weight of an acrylate polymer, 20 to 60% by weight of a styrene polymer, 5 to 30% by weight of a maleimide copolymer, and 3 to 25% And a molded article produced from the thermoplastic resin composition.
Description
The present invention relates to a styrene resistant chemical resistant heat resistant resin composition and a molded article produced therefrom, and more particularly to a thermoplastic resin composition excellent in chemical resistance and heat resistance and a molded article produced therefrom.
Heat-resistant acrylonitrile-butadiene-styrene (ABS) resins are used in a variety of applications such as automobile parts, electrical and electronic products, building materials, etc. because of their impact resistance, processability, attractive appearance, excellent mechanical strength and high heat distortion temperature. However, in the case of products used as interior parts, high chemical resistance is required due to a high possibility of contact with various chemical substances such as fragrance or deodorant. Existing heat resistant ABS resin has weak chemical resistance. In particular, when chemical substances such as a fragrance, a deodorant, and a fungicide are applied to an automobile air conditioner, there is a phenomenon that a crack is generated in a part of a car air vent.
To improve this, a technique of adding a crystalline polymer such as PBT to a heat resistant ABS resin is used, but sufficient chemical resistance can not be realized, and other properties are deteriorated.
In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition excellent in chemical resistance and heat resistance and a molded article produced therefrom.
The present invention also aims to provide an automobile interior material as the above molded article.
These and other objects of the present disclosure can be achieved by all of the present invention described below.
In order to achieve the above object, the present invention relates to a thermoplastic elastomer composition comprising 30 to 50% by weight of an acrylate polymer, 20 to 60% by weight of a styrene polymer, 5 to 30% by weight of a maleimide copolymer, and 3 to 25% And a thermoplastic resin composition.
The present invention also provides a molded article produced from the thermoplastic resin composition.
Further, the present invention provides an automobile interior material as the molded article.
As described above, according to the present invention, it is possible to provide a thermoplastic resin composition excellent in chemical resistance and heat resistance and a molded article produced from the thermoplastic resin composition.
Further, there is an effect of providing an automobile interior material as the molded article.
The thermoplastic resin composition according to the present invention is a thermoplastic resin composition comprising a) 30 to 50% by weight of an acrylate polymer, b) 20 to 60% by weight of a styrene polymer, c) 5 to 30% by weight of a maleimide copolymer, and d) By weight to 25% by weight, and has an excellent chemical resistance and heat resistance within this range.
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail.
a) an acrylate-based polymer
The acrylate-based polymer of the present invention may be, for example, a1) an acrylate-based rubber, a2) an acrylate-based graft copolymer, or a mixture thereof.
The acrylate-based polymer of the present invention may be, for example, 30 to 50% by weight, 30 to 45% by weight, or 30 to 40% by weight based on the thermoplastic resin composition.
Unlike a butadiene polymer having a low hydrogen dissociation energy, the acrylate polymer is stable against contact with oxygen and ozone, and has an excellent chemical resistance compared to butadiene rubber.
a1) acrylate rubber
The acrylate-based rubber may be, for example, a polymer polymerized with an acrylate monomer alone, or a copolymer obtained by polymerizing an acrylate monomer and a vinyl aromatic monomer and / or a vinyl cyan monomer. In this case, An excellent balance of physical properties is obtained.
The acrylate rubber may be at least one selected from the group consisting of butyl acrylate rubber, 2-ethylhexyl acrylate rubber, butyl acrylate-styrene copolymer and 2-ethylhexyl acrylate-acrylonitrile copolymer In this case, there is an effect of excellent heat resistance and chemical resistance.
The acrylate-based rubber may have an average particle size of 500 Å or more, 500 Å to 1 urn, 500 to 5000 Å, or 1000 to 5000 Å, for example. Within this range, color properties and impact strength are excellent.
a2) acrylate graft copolymer
The acrylate graft copolymer may be, for example, a graft copolymer of a vinyl aromatic monomer and a vinyl cyan monomer on the acrylate rubber.
The acrylate graft copolymer is preferably a mixture of i) a small-diameter acrylate graft copolymer and ii) a large-diameter acrylate graft copolymer.
The weight ratio of the i) small-diameter acrylic graft copolymer to the large-diameter acrylic graft copolymer may be, for example, 7 to 2: 3 by weight, preferably 6: 3: 3 , More preferably 5 to 4: 3, and within this range, it is possible to have excellent processability, heat resistance, weather resistance, impact resistance and appearance.
a2i) Small diameter acrylic graft copolymer
Examples of the small-diameter acryl-based graft copolymer include a vinyl aromatic monomer and a vinyl cyan monomer in an acrylate-based rubber (hereinafter referred to as "small-diameter acrylate-based rubbery polymer") having an average particle size of 500 to 2,000 Å, Can be used.
Examples of the small-diameter acrylate-based rubbery polymer include those prepared by emulsion polymerization by mixing an acrylate monomer, an emulsifier, an initiator, a crosslinking agent, an electrolyte material, and water.
As the acrylate monomer, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate or a combination thereof may be used, and butyl acrylate may be preferably used. The acrylate-based monomer may be included in an amount of 5 to 50% by weight based on the total weight of the small-diameter acryl-based graft copolymer.
As the emulsifier, for example, alkylsulfosuccinic acid metal salt derivatives having a pH of 3 to 9 and having 12 to 18 carbon atoms, or alkylsulfuric ester or sulfonic acid metal salt derivatives having 12 to 20 carbon atoms can be used. More specifically, the alkylsulfosuccinic acid metal salt derivatives having a pH of 3 to 9 and having 12 to 18 carbon atoms include sodium dicyclohexylsulfosuccinate, dihexylsulfosuccinic acid sodium salt, di-2-ethylhexylsulfosuccinic acid sodium salt, di- Ethylhexylsulfosuccinic acid potassium salt or di-2-ethylhexylsulfosuccinic acid lithium salt. The alkyl sulfates or sulfonic acid metal salt derivatives having 12 to 20 carbon atoms are preferably selected from the group consisting of sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium octadecyl sulfate, sodium oleyl sulfate, Sulfate or potassium octadecyl sulfate. The emulsifier may be used in an amount of 1 to 4% by weight, preferably 1.5 to 3% by weight based on the total weight of the small-diameter acrylate-based rubbery polymer.
The initiator may be an inorganic or organic peroxide, for example, and may be a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate, or a liquid-soluble initiator such as cumene hydroperoxide or benzoyl peroxide. . The initiator may be used in an amount of 0.05 to 0.2% by weight based on the total weight of the small-diameter acrylate-based rubbery polymer.
Examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, Neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate or trimethylolmethane triacrylate can be used. The cross-linking agent may be used in an amount of 0.02 to 0.3% by weight based on the total weight of the small-diameter acrylate-based rubbery polymer. When the grafting agent and the crosslinking agent are included, the acrylate-based rubbery polymer has more excellent physical properties such as elasticity and impact strength.
As the electrolyte material, for example, NaHCO 3 , Na 2 S 2 O 7 or K 2 CO 3 can be used. The electrolyte material may be used in an amount of 0.05 to 0.4% by weight based on the total weight of the small-diameter acrylate-based rubbery polymer.
The water may serve as a medium through which the emulsion polymerization proceeds. In one embodiment, the water may be ion-exchanged water. And the amount thereof may be used as the balance excluding the total amount of the components contained in the small-diameter acrylate-based rubbery polymer.
Each of the above components may be introduced continuously into the reactor, or may be introduced into the reactor in such a manner that the continuous introduction and the batch introduction are used in combination. By emulsion polymerization using polymerization conditions generally known in the technical field of the present invention, Based rubbery polymer can be produced.
The pH of the prepared small-diameter acrylate-based rubbery polymer may be, for example, 5 to 9, and preferably 6 to 8.
In one embodiment, the average particle size of the small-diameter acrylate-based rubbery polymer may be 500 to 2,000 angstroms, preferably 700 to 1,500 angstroms. Within this range, mechanical properties such as impact strength, tensile strength, Stability and coloring property.
The small diameter acrylate rubbery polymer may be, for example, a butyl acrylate rubbery polymer, an ethylhexyl rubbery polymer or a mixture thereof, preferably a butyl acrylate rubbery polymer.
The small diameter acrylate rubbery polymer may be, for example, a polymerized copolymer further comprising a comonomer generally known as a comonomer in the technical field of the present invention.
In one embodiment, the small-diameter acrylate-based rubber-like polymer is mixed with a vinyl aromatic monomer and a vinyl cyan monomer, followed by emulsion-polymerizing, thereby obtaining the acrylate-based rubbery polymer core with the small- Acrylic graft copolymer can be produced.
In one embodiment, 5 to 50% by weight of the small-diameter acrylate-based rubbery polymer having an average particle diameter of 500 to 2,000 Å, 10 to 50% by weight of the vinyl aromatic monomer, and 5 to 50% by weight of the vinyl cyan monomer 1 By weight to 45% by weight, and within this range, impact resistance and other physical properties are excellent.
In one embodiment, the vinyl aromatic monomer may be styrene,? -Ethylstyrene,? -Methylstyrene, p-methylstyrene, o-t-butylstyrene, bromostyrene, chlorostyrene or trichlorostyrene. These may be used singly or in combination of two or more, but are not limited thereto.
In one embodiment, the vinyl cyan monomer may be acrylonitrile, methacrylonitrile or ethacrylonitrile. These may be used singly or in combination of two or more, but are not limited thereto.
In addition, in the production of the above-mentioned small-diameter acryl-based graft copolymer, the acrylate-based rubbery polymer, the vinyl aromatic monomer and the vinyl cyanate monomer may be used in addition to the emulsifier, graft , A polymerization initiator, a molecular weight regulator and water can be suitably used.
As the emulsifier, for example, carboxylic acid metal salt derivatives such as fatty acid metal salts and rosin acid metal salts having a pH of 9 to 13 and having a carbon number of 12 to 20 can be used. More specifically, examples of the fatty acid metal salt having 12 to 20 carbon atoms include sodium fatty acid, sodium laurate, sodium oleate or potassium oleate, and sodium rosinate or potassium rosinate is preferably used as the rosin metal salt having 12 to 20 carbon atoms . The emulsifier may be used in an amount of 1 to 2 parts by weight based on 100 parts by weight of the small-diameter acrylate rubbery copolymer, the styrene-based monomer and the acrylonitrile-based monomer.
As the grafting agent, for example, allyl methacrylate, triallyl isocyanurate, triallyl amine or diallylamine can be used. The grafting agent may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the small-diameter acrylate rubbery copolymer, the styrene-based monomer and the acrylonitrile-based monomer.
As the polymerization initiator, for example, the same initiator as the initiator that can be used in the polymerization of the small-diameter acrylate-based rubbery polymer may be used, and the amount of the initiator may be selected from the above-mentioned small-caliber acrylate rubbery copolymer, styrenic monomer and acrylonitrile- 0.05 to 0.3 parts by weight based on 100 parts by weight of the monomer may be used.
As the molecular weight modifier, for example, t-dodecyl mercaptan or n-octyl mercaptan may be used. The amount of the small-molecular-weight acrylate rubber copolymer, the styrene-based monomer, and the acrylonitrile- 0.02 to 0.2 part by weight based on
The water may be, for example, ion-exchanged water, and the amount thereof may be used within the range of contents generally used in the technical field to which the present invention belongs.
In the preparation of the above-mentioned small-diameter acryl-based graft copolymer, when the reaction mixture and the additives are added in a batch, the pH of the polymerization system is temporarily increased to make grafting difficult and the stability of the copolymer particles is lowered, It is preferable to continuously inject the above-mentioned components and additives in the production of the small-diameter acrylic graft copolymer by graft polymerization.
The prepared small-diameter acrylic graft copolymer may have a pH of 8 to 11, and preferably a pH of 9 to 10.5. At the pH in the above range, the internal structure of the particles is uniform and the stability is excellent.
In one embodiment, the small-diameter acryl-based graft copolymer may be contained in an amount of 10 to 35% by weight, preferably 15 to 30% by weight, based on the total weight of the thermoplastic resin composition of the present invention, And 20 to 25% by weight. Within this range, there is an effect of excellent weather resistance, impact resistance, fluidity, hardness and scratch resistance.
The small-diameter acrylic graft copolymer may have an average particle diameter of 700 to 2,200 ANGSTROM, or 900 to 2,000 ANGSTROM, for example.
a2 ii) large-diameter acrylic graft copolymer
Examples of the above-mentioned large-diameter acrylic graft copolymer include graft-polymerized vinyl aromatic monomers and vinyl cyan monomers on acrylate rubber (hereinafter referred to as "large diameter acrylate rubber polymer") having an average particle diameter of 3,000 to 5,000 Å Can be used.
Examples of the above-mentioned large-diameter acrylate-based rubbery polymer include those prepared by mixing an acrylate monomer, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte material and water and emulsion polymerization.
As the acrylate monomer, for example, those which can be used in the production of the small-diameter acrylate-based rubber-like polymer may be used, and they may be included in an amount of 10 to 60% by weight based on the total weight of the large-diameter acrylic graft copolymer.
The emulsifier may be one which can be used in the production of the small-diameter acrylate-based rubbery polymer, and the amount of the emulsifier may be 0.1 to 1% by weight based on the total weight of the large-diameter acrylate- Can be used.
The initiator, the grafting agent, the crosslinking agent, the electrolyte material and the water used in the production of the above-mentioned large diameter acrylate rubbery polymer can be used in the same range of the materials which can be used in the production of the small diameter acrylate rubbery polymer .
In one embodiment, the above-mentioned large-diameter acrylate-based rubbery polymer is introduced into the reactor in such a manner that the above-mentioned components are continuously introduced or the continuous introduction and the batch introduction are used in combination, and polymerization is carried out using polymerization conditions generally known in the technical field of the present invention Followed by polymerization.
The pH of the prepared large-diameter acrylate-based rubbery polymer may be, for example, 5 to 9, and preferably 6 to 8.
In one embodiment, the average particle size of the large diameter acrylate-based rubbery polymer may be from 3,000 to 5,000 Å, preferably from 3,000 to 4,500 Å. Within this range, mechanical properties such as impact strength, tensile strength, And has excellent processability and gloss.
In one embodiment, the large diameter acrylate rubbery polymer may be a butyl acrylate rubbery polymer, an ethylhexyl rubbery polymer, or a mixture thereof, preferably a butyl acrylate rubbery polymer.
The above-mentioned large-diameter acrylate rubbery polymer may be a polymerized copolymer including a comonomer generally known as a comonomer in the technical field of the present invention.
In one embodiment, the large-diameter acrylate-based rubbery polymer is mixed with an aromatic vinyl-based monomer and an unsaturated nitrile-based monomer and emulsion-polymerized to obtain an acrylate-based rubbery polymer core having an aromatic vinyl-based monomer and an unsaturated nitrile- The above-mentioned large-diameter acrylic graft copolymer can be produced.
In one embodiment, 10 to 60% by weight of the large-diameter acrylate-based rubbery polymer having an average particle size of 3,000 to 5,000 Å, 10 to 50% by weight of the vinyl aromatic monomer, and 1 to 45 By weight, and excellent impact resistance and other physical properties within this range.
The vinyl aromatic monomer and the vinyl cyan monomer may be used within the range used in the preparation of the small-diameter acryl-based graft copolymer. In the production of the large-diameter acrylic graft copolymer, the large-diameter acrylate- An emulsifier, a polymerization initiator, a molecular weight regulator and water, which are conventionally used in the art to which the present invention belongs, may be appropriately used depending on the application, in addition to the vinyl aromatic monomer and the vinyl cyan monomer.
The emulsifier, the polymerization initiator, the molecular weight modifier and water can be used within a range that can be used in the preparation of the above-mentioned small-diameter acrylic graft copolymer, for example, to produce a large-diameter acrylic graft copolymer under the polymerization conditions within the same range have.
In one embodiment, the large-diameter acryl-based graft copolymer may be contained in an amount of 5 to 25% by weight, preferably 10 to 20% by weight based on the total weight of the thermoplastic resin composition of the present invention, more preferably 13 By weight to 18% by weight. Within the above range, there is an effect of excellent weather resistance, impact resistance, fluidity, hardness and scratch resistance.
The large-diameter acrylic graft copolymer may be, for example, 3,500 to 5,000 ANGSTROM.
b) a styrene polymer
The styrene type polymer of the present invention means a polymer containing 50% by weight or more of a styrene type monomer.
The styrene polymer of the present invention may be, for example, an? -Methyl styrene polymer, and in this case, the heat resistance is improved.
The content of the styrene polymer in the present invention is 20 to 60% by weight, 25 to 50% by weight, or 30 to 40% by weight based on the thermoplastic resin composition.
The? -Methylstyrene polymer may be, for example, an? -Methylstyrene homopolymer or a copolymer obtained by polymerizing? -Methylstyrene and a comonomer thereof.
The comonomer may be at least one selected from the group consisting of a vinyl aromatic compound (except? -Methyl styrene) and a vinyl cyan compound.
The vinyl aromatic compound may be at least one selected from the group consisting of styrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.
The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
As another example, the? -Methylstyrene polymer may contain 50 to 90% by weight, 50 to 80% by weight or 60 to 80% by weight of? -Methylstyrene; 10 to 50% by weight, 20 to 50% by weight or 20 to 40% by weight of a vinyl cyan monomer may be copolymerized, and within this range, an excellent balance of heat resistance and physical properties is obtained.
In one embodiment, the alpha-methylstyrene-based copolymer may comprise 35-80 wt% alpha -methylstyrene (AMS) monomer.
The styrene-based polymer may be prepared by a conventional method. For example, bulk polymerization is preferred. Toluene may be used as the solvent. Di-t-dodecylmercaptan may be used as the molecular weight modifier , But is not limited thereto.
In one embodiment, the reaction conditions of the bulk polymerization may be prepared by maintaining the charged amount of the reactant mixture at an average reaction time of 2 to 4 hours and maintaining the reaction temperature at 140 to 170 ° C. In one embodiment, the manufacturing process can be manufactured by a continuous process comprising a feed pump, a continuous stirred tank, a preheater and a volatilization tank, a polymer feed pump, and an extruder.
c) maleimide-based copolymer
The maleimide-based copolymer of the present invention means a copolymer containing at least 40% by weight of maleimide-based monomer.
The maleimide-based copolymer includes, for example, 40 to 60% by weight of a maleimide-based monomer; 35 to 55% by weight of a vinyl aromatic monomer; And 0.1 to 5% by weight of maleic acid or maleic anhydride, and has an excellent heat resistance within this range.
The content of the maleimide-based copolymer of the present invention is, for example, 5 to 30% by weight, 8 to 25% by weight, or 13 to 18% by weight based on the thermoplastic resin composition. Within the above range, there is an effect of excellent heat resistance, fluidity, hardness and scratch resistance.
The maleimide-based copolymer of the present invention may be an N-phenylmaleimide-based copolymer, and in this case, sufficient heat resistance is ensured.
The N-phenylmaleimide-based copolymer may be, for example, an N-phenylmaleimide-aromatic vinyl compound copolymer, an N-phenylmaleimide-aromatic vinyl compound-maleic anhydride copolymer, or a mixture thereof.
Examples of the N-phenylmaleimide-based copolymer include vinyl aromatic monomers, vinyl cyan monomers and N-phenyl maleimide monomers. In one embodiment, the N-phenylmaleimide-based copolymer includes, for example, 1 to 70% by weight of a vinyl aromatic monomer, 1 to 35% by weight of a vinyl cyan monomer, and 10 to 65% by weight of an N-phenylmaleimide monomer, Or may be one prepared by polymerization. Within this range, polymerization stability is excellent.
Examples of the vinyl aromatic monomers include styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, and the like, and styrene may be preferably used. As the vinyl cyan monomer, acrylonitrile or methacrylate Acrylonitrile and the like can be used.
In one embodiment, the N-phenylmaleimide-based copolymer has a weight average molecular weight of 60,000 to 300,000 g / mol, 100,000 to 200,000 g / mol, 120,000 to 180,000 g / mol, or 130,000 to 16,000 g / G / mol, and the flowability is excellent within this range, so that the processability is improved and the impact strength is improved.
In one embodiment, the glass transition temperature (T g ) of the N-phenylmaleimide-based copolymer may be 150 to 220 ° C, 180 to 210 ° C, or 190 to 205 ° C. Within this range, It is effective.
d) Polyester elastomer
In the polyester elastomer of the present invention, the crystalline portion and the amorphous portion coexist, and the crystalline portion is advantageous in terms of the chemical resistance, which is a characteristic of the polymer, and the amorphous portion improves the elongation, thereby reducing residual stress.
The polyester elastomer of the present invention may be, for example, a polymer in which a crystalline polyester group and an amorphous polyisocyanate group are bonded.
The polyester elastomer of the present invention has, for example, a shore hardness of 30 to 50 D, preferably 40 D, and has an excellent chemical resistance, impact strength and balance of physical properties within this range.
The content of the polyester elastomer in the present invention is 3 to 25% by weight or 5 to 20% by weight based on the thermoplastic resin composition. Within this range, the thermoplastic resin composition has excellent chemical resistance and impact strength.
The polyester elastomer may be, for example, a butylene terephthalate-tetramethylene glycol elastomer.
As another example, the polyester elastomer may be a copolymer of 30 to 50 wt% or 35 to 45 wt% of butylene terephthalate and 50 to 70 wt% or 55 to 65 wt% of tetramethylene glycol, The chemical resistance, the impact strength and the balance of physical properties are excellent.
Thermoplastic resin composition
The thermoplastic resin composition of the present invention contains the polymer of a) to d), and may have a melt index of 3 to 6 g / 10 min, or 3 to 5.5 g / 10 min, for example. It is effective.
For example, the thermoplastic resin composition may have a thermal deformation temperature of 95 to 105 ° C or 95 to 103 ° C, and has an excellent balance of physical properties and heat resistance within this range.
The molded article of the present invention is characterized by being produced from the thermoplastic resin composition of the present invention.
The molded article may be, for example, an automobile interior material.
The automobile interior material may be, for example, an automobile cup holder or an automotive air conditioner air vent.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention within the scope and spirit of the following claims, Such variations and modifications are intended to be within the scope of the appended claims.
[Example]
Production Example 1 (Production of large-diameter acrylic graft copolymer)
A reactor of 10 L was charged with 5 wt% of butyl acrylate, 0.015 wt% of di-2-ethylhexylsulfosuccinic acid sodium salt, 0.02 wt% of ethylene glycol dimethacrylate, 0.1 wt% of sodium hydrogencarbonate (NaHCO 3 ) % By weight and the remaining amount of ion-exchanged water were all added thereto, and the reaction temperature was raised to 70 DEG C, followed by reaction for 1 hour to prepare a polymer seed. Again, a mixture of 45 wt% of butyl acrylate, 0.285 wt% of di-2-ethylhexylsulfosuccinate sodium salt, 0.1 wt% of sodium hydrogencarbonate and a balance of ion-exchanged water and 0.06 wt% of potassium persulfate, At 70 ° C for 3 hours to prepare a large diameter acrylate rubber polymer having an average particle diameter of 3,000 Å to 4,000 Å.
To 100 parts by weight of a reaction mixture of 50% by weight of a large diameter acrylate rubber polymer having an average particle diameter of 3,000 to 4,000 Å, 35% by weight of a styrene monomer and 15% by weight of an acrylonitrile monomer, 63 parts by weight of distilled water, A mixture of 0.2 part by weight of maleurate, 1.2 parts by weight of potassium rosinate, 0.042 part by weight of potassium hydroxide, and 0.05 part by weight of t-dodecylmercaptan as a molecular weight regulator and 0.1 part by weight of potassium persulfate as a polymerization initiator The polymerization reaction was continued for 5 hours continuously, and further reacted at 80 DEG C for 1 hour in order to increase polymerization conversion, and then cooled to 60 DEG C to prepare a large-diameter acrylic graft resin containing a large-diameter acrylate-based rubbery polymer. The average diameter of the prepared large-diameter acrylic graft resin was 5,000 Å, the pH was 9.5, and the graft rate was 45%.
Production Example 2 (Production of small-diameter acryl-based graft copolymer)
10 L of a reactor was charged with 10 wt% of butyl acrylate, 1.5 wt% of di-2-ethylhexylsulfosuccinic acid sodium salt, 0.02 wt% of ethylene glycol dimethacrylate, 0.1 wt% of sodium hydrogencarbonate (NaHCO 3 ) By weight, and the remaining amount of ion-exchanged water were collectively administered, and the reaction temperature was raised to 70 캜, followed by reaction for 1 hour to prepare a polymer seed. To this was added again 30% by weight of butyl acrylate, 0.5% by weight of di-2-ethylhexylsulfosuccinic acid sodium salt, 0.1% by weight of sodium hydrogencarbonate and a mixture of residual ion-exchanged water and 0.06% by weight of initiator potassium persulfate And then polymerized at 70 DEG C for 3 hours continuously to prepare a small-diameter acrylate-based rubbery polymer having an average particle size of 800 ANGSTROM to 1,000 ANGSTROM.
To 100 parts by weight of the reaction mixture obtained by mixing 40% by weight of the small diameter acrylate rubber polymer, 40% by weight of the styrene monomer and 20% by weight of the acrylonitrile monomer, having a diameter of 800 Å to 1,000 Å, 63 parts by weight of distilled water, 0.2 parts by weight of aryl isocyanurate, 1.2 parts by weight of potassium rosinate, 0.042 part by weight of potassium hydroxide and 0.05 part by weight of t-dodecyl mercaptan as a molecular weight regulator and 0.1 part by weight of calcium persulfate as a polymerization initiator were added at 70 DEG C For 5 hours. The reaction was further continued at 80 ° C for 1 hour to increase polymerization conversion, and then cooled to 60 ° C to prepare an acrylic graft resin containing a small-diameter acrylate-based rubbery polymer. At this time, the prepared small-diameter acryl-based graft resin had an average particle diameter of 1,200 Å and a graft rate of 40%.
* Diene rubber: Butadiene rubber having an average particle diameter of 3000 Å was used.
* A: Acrylonitrile-? -Methylstyrene copolymer (? -Methyl SAN) having a weight average molecular weight of 150,000 g / mol, 75% by weight of alpha-methylstyrene and 25% by weight of acrylonitrile was used.
* B: N-Phenylmaleimide Compound-An aromatic vinyl compound-maleic anhydride copolymer was used as Denso's MSNB product.
* C: A LG Chemical product having a shore hardness of 40 D was used as the polyester elastomer resin.
* D: 5020 product of MCC Co. was used as polybutylene terephthalate.
Examples 1 to 3 and Comparative Examples 1 to 7
The components were mixed in the weight ratios shown in Table 1 below, and melt-kneaded and extruded in a twin-screw extruder at 240 ° C. to prepare pellets, which were then molded into thermoplastic resin composition specimens using an injection molding machine.
[Test Example]
The properties of the thermoplastic resin composition samples prepared in Examples 1 to 3 and Comparative Examples 1 to 7 were measured by the following methods, and the results are shown in Table 2 below.
* Izod Impact Strength: A notch was measured at a specimen thickness of 3.2 mm by the ASTM D 256 method.
* Heat distortion temperature (HDT): The specimen thickness was 6.35 mm and the load condition was 18.6 kgf / cm 2 by the ASTM D 648 method.
Flexural Strength: A specimen thickness of 6.35 mm was measured at a temperature of 23 ° C by the ASTM D790 method. The test speed was 10 mm / min.
Tensile Strength: ASTM D638 was used to measure the specimen thickness at 3.2 mm and temperature of 23 ° C.
* Chemical resistance: A specimen of 200 X 12.7 X 3.2 mm was fixed to a curvature jig having a 2.0% strain, and a face patch was placed on the specimen, followed by applying 1 ml of the following fragrance to the specimen, ) Was evaluated and evaluated in three stages (⊚: excellent, △: normal, X: weak).
Fragrance 1: Life Tech - Aromatherapy Fragrance (Aroma Naturals)
Fragrance 2: Sentec - avatar (jasmine fragrance)
* Particle size (average particle size): The average particle size of the latex was measured using an intensity Gaussian distribution (Nicomp 380) by a dynamic laser light scattering method.
* Melt index: measured according to ASTM D 1238 at 220 캜 under a load of 2.16 kg.
Graft copolymer
Graft copolymer
Copolymer (A)
Copolymer (B)
The elastomer (C)
Terephthalate (D)
(g / 10 min)
(kgf / cm 2 )
(kgf / cm 2 )
(° C)
(Fragrance 1)
(Fragrance 2)
As shown in the above Table 2, the thermoplastic resin compositions (Examples 1 to 3) of the present invention are superior to the thermoplastic resin compositions (Comparative Examples 1, 2, 4 and 5) containing no polyester elastomer or containing an excess amount of polyester elastomer It was confirmed that the mechanical properties such as strength, workability and heat resistance were equal but the chemical resistance was excellent. In particular, in the case of Comparative Examples 6 and 7 including the diene rubber, it was confirmed that the chemical resistance of the thermoplastic resin composition was remarkably lower than that of the thermoplastic resin composition of the present invention.
In addition, it was confirmed that the thermoplastic resin composition (Comparative Example 3) containing a small amount of the acrylic graft copolymer significantly lost its mechanical properties and chemical resistance.
Claims (15)
Thermoplastic resin composition.
The acrylate-based polymer is a mixture of an acrylic graft copolymer containing an acrylate-based rubber having an average particle size of 500 to 2,000 Å and an acrylate-based graft copolymer containing an acrylate-based rubber having an average particle size of 3,000 to 5,000 Å Featured
Thermoplastic resin composition.
The weight ratio of the acrylic graft copolymer containing an acrylate rubber having an average particle diameter of 500 to 2,000 angstrom and the acrylic graft copolymer containing an acrylate rubber having an average particle diameter of 3,000 to 5,000 angstroms is from 7: 3 to 2: 3 < / RTI >
Thermoplastic resin composition.
The styrene-based polymer is characterized by being an? -Methylstyrene-based polymer
Thermoplastic resin composition.
The? -Methylstyrene polymer is preferably an? -Methylstyrene homopolymer or a polymer obtained by copolymerizing? -Methylstyrene and a comonomer thereof
Thermoplastic resin composition.
Wherein the comonomer is at least one selected from the group consisting of a vinyl aromatic compound (except for? -Methyl styrene) and a vinyl cyan compound
Thermoplastic resin composition.
Wherein the maleimide-based copolymer is an N-phenylmaleimide-based copolymer
Thermoplastic resin composition.
Wherein the N-phenylmaleimide-based copolymer is an N-phenylmaleimide-aromatic vinyl compound copolymer, an N-phenylmaleimide-aromatic vinyl compound-maleic anhydride copolymer, or a mixture thereof
Thermoplastic resin composition.
Wherein the maleimide-based copolymer has a weight average molecular weight of 60,000 to 300,000 g / mol
Thermoplastic resin composition.
Wherein the polyester elastomer is a polymer comprising a crystalline polyester group and an amorphous polyisocyanate group
Thermoplastic resin composition.
Wherein the polyester elastomer is a butylene terephthalate-tetramethylene glycol elastomer
Thermoplastic resin composition.
Wherein the thermoplastic resin composition has a melt index of 3 to 6 g / 10 min
Thermoplastic resin composition.
Wherein the thermoplastic resin composition has a thermal deformation temperature of 95 to 105 ° C
Thermoplastic resin composition.
Shaped article.
Characterized in that the molded article is an automobile interior material
Shaped article.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170067318A (en) * | 2015-12-08 | 2017-06-16 | 주식회사 엘지화학 | Thermoplstic resin composition having good chemical resistance and molded product prepared thereform |
| WO2021054679A1 (en) * | 2019-09-18 | 2021-03-25 | (주) 엘지화학 | Thermoplastic resin composition, preparation method therefor, and molded product manufactured therefrom |
| CN113166510A (en) * | 2019-09-18 | 2021-07-23 | 株式会社Lg化学 | Thermoplastic resin composition, method for preparing the same and molded article manufactured using the same |
| WO2022019410A1 (en) * | 2020-07-23 | 2022-01-27 | (주) 엘지화학 | Thermoplastic resin composition and molded article thereof |
| WO2022065990A1 (en) * | 2020-09-28 | 2022-03-31 | 주식회사 엘지화학 | Resin composition and molded article |
-
2014
- 2014-12-09 KR KR1020140176027A patent/KR20150068313A/en active Search and Examination
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170067318A (en) * | 2015-12-08 | 2017-06-16 | 주식회사 엘지화학 | Thermoplstic resin composition having good chemical resistance and molded product prepared thereform |
| WO2021054679A1 (en) * | 2019-09-18 | 2021-03-25 | (주) 엘지화학 | Thermoplastic resin composition, preparation method therefor, and molded product manufactured therefrom |
| CN113166510A (en) * | 2019-09-18 | 2021-07-23 | 株式会社Lg化学 | Thermoplastic resin composition, method for preparing the same and molded article manufactured using the same |
| CN113166510B (en) * | 2019-09-18 | 2023-09-15 | 株式会社Lg化学 | Thermoplastic resin composition, method for preparing the same, and molded article manufactured using the same |
| WO2022019410A1 (en) * | 2020-07-23 | 2022-01-27 | (주) 엘지화학 | Thermoplastic resin composition and molded article thereof |
| WO2022065990A1 (en) * | 2020-09-28 | 2022-03-31 | 주식회사 엘지화학 | Resin composition and molded article |
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