KR101466152B1 - Acrylic based resin composition and molded product using the same - Google Patents
Acrylic based resin composition and molded product using the same Download PDFInfo
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- KR101466152B1 KR101466152B1 KR1020100134928A KR20100134928A KR101466152B1 KR 101466152 B1 KR101466152 B1 KR 101466152B1 KR 1020100134928 A KR1020100134928 A KR 1020100134928A KR 20100134928 A KR20100134928 A KR 20100134928A KR 101466152 B1 KR101466152 B1 KR 101466152B1
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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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid 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
- 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
- C08L33/18—Homopolymers or copolymers of 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
- C08L35/06—Copolymers with vinyl aromatic monomers
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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
- C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
(A) a first acrylic copolymer having a core-shell structure including a double-layer rubber, (B) a second acrylic copolymer having a core-shell structure including a single-layer rubber, (C) (Meth) acrylate having a weight average molecular weight of 20,000 to 30,000 g / mol, and (D) a heat-resistant copolymer of an aromatic vinyl compound and a vinyl cyanide compound containing a substituted maleimide, A resin composition and a molded article using the same are provided.
Description
The present invention relates to an acrylic resin composition and a molded article using the acrylic resin composition.
ASA (acrylonitrile-styrene-acrylate) resins are widely used in the production of molded articles such as electric and electronic products, automobile exterior parts, and construction materials because of their excellent weather resistance, light resistance, chemical resistance and heat resistance.
However, the ASA resin is poor in coloring property, mechanical properties, and appearance, and therefore, application of a molded product is limited.
To solve this problem, an ASA (acrylonitrile-styrene-acrylate) resin, an acrylonitrile-butadiene-methyl methacrylate graft copolymer, and an alkyl acrylate copolymer may be mixed and used together, , There is a limit to improvement in scratch resistance and surface gloss characteristics.
In addition, two kinds of ASA (acrylonitrile-styrene-acrylate) resin, ABS (acrylonitrile-butadiene-styrene) graft copolymer having different particle diameters, and an impact modifier may be mixed and used together, There is a limit to improvement in gloss characteristics.
An aspect of the present invention is to provide an acrylic resin composition excellent in weatherability, scratch resistance, surface gloss, and heat resistance.
Another aspect of the present invention is to provide a molded article using the acrylic resin composition.
One aspect of the present invention relates to a thermoplastic resin composition comprising (A) a first acrylic copolymer having a core-shell structure including a double layer rubber; (B) a second acrylic copolymer of a core-shell structure comprising a single-layer rubber; (C) a heat-resistant copolymer of an aromatic vinyl compound and a vinyl cyanide compound including? -Methylstyrene, phenyl N-substituted maleimide, or a combination thereof; And (D) a polyalkyl (meth) acrylate having a weight average molecular weight of 20,000 to 30,000 g / mol.
Wherein the acrylic resin composition comprises 10 to 50% by weight of the first acrylic copolymer (A); 10 to 30% by weight of the second acrylic copolymer (B); 30 to 70% by weight of the heat-resistant copolymer (C) of the aromatic vinyl compound and the vinyl cyanide compound; And 2 to 4 parts by weight of the polyalkyl (meth) acrylate (D) relative to 100 parts by weight of the total amount of the components (A), (B) and (C) And (C) are based on the total weight of the components (A), (B) and (C).
The double layer rubber may have an average particle size of 0.1 to 0.5 占 퐉, and the double layer rubber may include an inner layer comprising a copolymer of an acrylic compound and an aromatic vinyl compound, and an outer layer comprising an acrylic compound.
The single layer rubber may include a first rubber having an average particle diameter of 0.5 to 1.0 mu m and a second rubber having an average particle diameter of 0.1 to 0.3 mu m, and the single layer rubber may include an acrylic compound.
The first acrylic copolymer (A) and the second acrylic copolymer (B) may be contained in a weight ratio of 80:20 to 20:80.
The polyalkyl (meth) acrylate (D) may be contained in an amount of 2 to 3 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C).
The acrylic resin composition may further comprise (E) a copolymer of an aromatic vinyl compound and a vinyl cyanide compound, and the aromatic vinyl compound may be a copolymer of styrene, o-ethylstyrene, , Or a combination thereof.
Another aspect of the present invention provides a molded article produced using the acrylic resin composition.
Other aspects of the present invention are included in the following detailed description.
Since the acrylic resin composition is excellent in weather resistance, scratch resistance, surface gloss and heat resistance, it can be advantageously applied to various molded articles, especially plastic exterior articles such as electric and electronic parts and automobile parts.
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible. "(Meth) acrylic acid ester" means that both "acrylic acid alkyl ester" and "methacrylic acid alkyl ester" can be used. It means that it is possible.
Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.
Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S and P is included in the ring group.
The acrylic resin composition according to one embodiment comprises (A) a first acrylic copolymer having a core-shell structure including a double-layer rubber, (B) a second acrylic copolymer having a core- ) A heat-resistant copolymer of an aromatic vinyl compound and a vinyl cyanide compound, and (D) a polyalkyl (meth) acrylate.
Hereinafter, each component included in the acrylic resin composition according to one embodiment will be specifically described.
(A) a first acrylic copolymer having a core-shell structure
The first acrylic copolymer may have a core-shell structure in which a shell is grafted to a rubber core.
The rubber core may have the structure of a double layer rubber consisting of an inner layer and an outer layer.
The double-layer rubber may have an average particle diameter of 0.1 to 0.5 mu m, and more specifically, an average particle diameter of 0.1 to 0.3 mu m. When the first acrylic copolymer containing the double-layer rubber having an average particle size within the above range is used, the difference in refractive index between the aromatic vinyl compound and the copolymer of the vinyl cyanide compound described below is small, the hiding power is low and the coloring property can be improved, In addition, it is possible to obtain an excellent balance of physical properties such as weather resistance, scratch resistance, surface gloss, and heat resistance.
The inner layer may include a copolymer of an acrylic compound and an aromatic vinyl compound, and the outer layer may include an acrylic compound.
The acrylic compound constituting the inner layer and the outer layer may be (meth) acrylic acid alkyl ester, (meth) acrylic acid ester or a combination thereof. Wherein the alkyl may be C1 to C10 alkyl. Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. Examples of the (meth) acrylic acid esters include (meth) , But are not limited thereto.
The aromatic vinyl compound may be styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene or a combination thereof. Examples of the alkyl-substituted styrene include, but are not limited to, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.
The double layer rubber may be composed of 10 to 70% by weight of the inner layer and 30 to 90% by weight of the outer layer, specifically 10 to 50% by weight of the inner layer and 50 to 90% by weight of the outer layer . When the double-layered rubber is in the above range, the coloring property is improved according to the increase of the refractive index, and the impact resistance and the coloring property can be improved simultaneously by preventing the lowering of the low temperature impact strength as the glass transition temperature is increased.
The shell grafted to the rubber core may contain an unsaturated compound.
The unsaturated compound may be an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a combination thereof. Among them, a mixture or copolymer of an aromatic vinyl compound and a vinyl cyanide compound may be preferably used. At this time, the aromatic vinyl compound and the vinyl cyanide compound may be composed of 50 to 80% by weight and 20 to 50% by weight.
As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene or a combination thereof may be used. Examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.
As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.
As the heterocyclic compound, maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof may be used.
The first acrylic copolymer may comprise 20 to 80% by weight of the rubber core and 20 to 80% by weight of the shell, specifically 30 to 70% by weight of the rubber core and 30 to 70% can do. When the ratio is within the above range, the acrylic resin composition has less variation in physical properties and a good gloss.
The first acrylic copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization.
The first acrylic copolymer is preferably used in an amount of 10 to 50 parts by weight based on the total amount of the first acrylic copolymer (A), the second acrylic copolymer (B) and the heat resistant copolymer (C) of the aromatic vinyl compound and the vinyl cyanide compound. By weight, and specifically from 20 to 40% by weight. When the first acrylic copolymer is contained in the above range, excellent physical properties such as impact resistance and coloring property can be obtained.
(B) a second acrylic copolymer having a core-shell structure
The second acrylic copolymer may have a core-shell structure in which a shell is grafted to a rubber core.
The rubber core may have the structure of a single layer rubber.
The single-layer rubber may include a first rubber having an average particle diameter of 0.5 to 1.0 mu m and a second rubber having an average particle diameter of 0.1 to 0.3 mu m. More specifically, the first rubber and the second rubber And may have a structure mixed on the same matrix. The first rubber may have a specific average particle diameter of 0.5 to 0.7 탆, and the second rubber may have a specific average particle diameter of 0.1 to 0.2 탆. When the second acrylic copolymer in which the first rubber having an average particle diameter within the above range and the second rubber having an average particle diameter within the above range are mixed is used, it is possible to obtain a resin composition having excellent balance of weatherability, scratch resistance, surface gloss, Can be obtained.
The first rubber and the second rubber may be mixed at a weight ratio of 9: 1 to 1: 9, and more specifically, may be mixed at a weight ratio of 8: 2 to 2: 8. When they are mixed in the weight ratio range, a balance of physical properties excellent in impact resistance, fluidity and colorability can be obtained.
The single layer rubber may comprise an acrylic compound.
The acrylic compound may be (meth) acrylic acid alkyl ester, (meth) acrylic acid ester or a combination thereof. Wherein the alkyl may be C1 to C10 alkyl. Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. Examples of the (meth) acrylic acid esters include (meth) , But are not limited thereto.
The shell grafted to the rubber core may contain an unsaturated compound.
The unsaturated compound may be an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a combination thereof. Among them, a mixture or copolymer of an aromatic vinyl compound and a vinyl cyanide compound may be preferably used. At this time, the aromatic vinyl compound and the vinyl cyanide compound may be composed of 50 to 80% by weight and 20 to 50% by weight.
As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene or a combination thereof may be used. Examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.
As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.
As the heterocyclic compound, maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof may be used.
The second acrylic copolymer may comprise 20 to 80% by weight of the rubber core and 20 to 80% by weight of the shell, specifically 30 to 70% by weight of the rubber core and 30 to 70% by weight of the shell can do. When the ratio is within the above range, the acrylic resin composition has less variation in physical properties and a good gloss.
The second acrylic copolymer may be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization.
The second acrylic copolymer is used in an amount of 10 to 30 parts by weight based on the total amount of the first acrylic copolymer (A), the second acrylic copolymer (B) and the heat-resistant copolymer (C) of the aromatic vinyl compound and the vinyl cyanide compound. By weight, and specifically from 15 to 25% by weight. When the second acrylic copolymer is contained within the above range, excellent balance of physical properties such as weather resistance, scratch resistance, surface gloss and heat resistance can be obtained.
The first acrylic copolymer (A) and the second acrylic copolymer (B) may be mixed at a weight ratio of 80:20 to 20:80, and may be mixed at a weight ratio of 75:25 to 40:60 Can be used. When used in the above weight ratio range, excellent balance of physical properties such as weather resistance, scratch resistance, surface gloss and heat resistance can be obtained.
(C) a heat-resistant copolymer of an aromatic vinyl compound and a vinyl cyanide compound
By using the heat-resistant copolymer of the aromatic vinyl compound and the vinyl cyanide compound, the heat resistance can be improved without affecting the weather resistance, scratch resistance and surface gloss characteristics of the acrylic resin composition.
As the aromatic vinyl compound,? -Methylstyrene, phenyl N-substituted maleimide and the like can be used, and these can be used alone or in combination of two or more.
As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.
The heat-resistant copolymer may be a copolymer formed by polymerizing 50 to 80% by weight of the aromatic vinyl compound and 20 to 50% by weight of the vinyl cyanide compound. When the heat-resistant copolymer is in the above-mentioned ratio range, the acrylic resin composition is excellent in coloring property, impact resistance and weather resistance.
The heat-resistant copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, and has a weight average molecular weight of 15,000 to 400,000 g / mol.
The heat-resistant copolymer of the aromatic vinyl compound and the vinyl cyanide compound is a copolymer of the first acrylic copolymer (A), the second acrylic copolymer (B), and the heat resistant copolymer (C) of the aromatic vinyl compound and the vinyl cyanide compound May be contained in an amount of 30 to 70% by weight based on the total amount, specifically 30 to 50% by weight. When the heat-resistant copolymer is contained in the above range, excellent balance of physical properties such as weather resistance, scratch resistance, surface gloss and heat resistance can be obtained.
(D) Polyalkyl ( Meta ) Acrylate
The polyalkyl (meth) acrylate may be a low molecular weight polyalkyl (meth) acrylate, and may specifically have a weight average molecular weight of 20,000 to 40,000 g / mol, more specifically 20,000 to 30,000 g / mol. When a polyalkyl (meth) acrylate having a weight average molecular weight within the above range is used, the weather resistance, scratch resistance, and surface gloss characteristics can be simultaneously improved.
The polyalkyl (meth) acrylate may be a homopolymer based on alkyl (meth) acrylate; Copolymers or mixtures of alkyl acrylates and alkyl methacrylates may be used. The alkyl may be substituted or unsubstituted C1 to C10 alkyl. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) Hydroxyethyl (meth) acrylate, and the like.
The polyalkyl (meth) acrylate can be obtained by polymerizing a starting monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization or emulsion polymerization.
The polyalkyl (meth) acrylate is obtained by copolymerizing 100 parts by weight of the total amount of the first acrylic copolymer (A), the second acrylic copolymer (B), and the heat resistant copolymer (C) of the aromatic vinyl compound and the vinyl cyanide compound 2 to 4 parts by weight, and specifically 2 to 3 parts by weight. When the polyalkyl (meth) acrylate is contained in the above range, excellent balance of physical properties such as weather resistance, scratch resistance, surface gloss and heat resistance can be obtained.
(E) a copolymer of an aromatic vinyl compound and a vinyl cyanide compound
The acrylic resin composition may further include a copolymer of the aromatic vinyl compound and the vinyl cyanide compound.
As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene or a combination thereof may be used. Examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene.
As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.
The copolymer of the aromatic vinyl compound and the vinyl cyanide compound may be a copolymer formed by polymerizing 50 to 80% by weight of the aromatic vinyl compound and 20 to 50% by weight of the vinyl cyanide compound, 77% by weight of the vinyl cyanide compound and 23 to 45% by weight of the vinyl cyanide compound. When the copolymer is in the above range, the acrylic resin composition is excellent in coloring property, impact resistance and weather resistance.
The copolymer may be prepared by a method of emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and has a weight average molecular weight of 15,000 to 400,000 g / mol.
The copolymer of the aromatic vinyl compound and the vinyl cyanide compound is a copolymer of the first acrylic copolymer (A), the second acrylic copolymer (B), and the total amount of the heat resistant copolymer (C) of the aromatic vinyl compound and the vinyl cyanide compound 20 to 60 parts by weight, and specifically 20 to 50 parts by weight, based on 100 parts by weight of the composition. When the copolymer is contained in the above range, excellent balance of physical properties such as weather resistance, scratch resistance, surface gloss and heat resistance can be obtained.
(F) Other additives
The acrylic resin composition may contain at least one of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, a surfactant, a coupling agent, a plasticizer, an admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a colorant, a flame retardant, A nucleating agent, an adhesion promoter, an adhesive, or a combination thereof.
As the antioxidant, phenol type, phosphite type, thioether type or amine type antioxidant may be used. Examples of the releasing agent include fluorine-containing polymer, silicone oil, metal salt of stearic acid, montanic acid, , A montanic ester wax or a polyethylene wax can be used. Further, benzophenone type or amine type endurance agent can be used as the weathering agent, and a dye or pigment can be used as the coloring agent. Titanium dioxide (TiO 2 ) or carbon black can be used as the ultraviolet ray blocking agent. As the nucleating agent, talc or clay may be used.
The additive may be appropriately contained within a range that does not impair the physical properties of the acrylic resin composition. Specifically, the additive may be contained in the first acrylic copolymer (A), the second acrylic copolymer (B), and the aromatic vinyl compound May be contained in an amount of 40 parts by weight or less based on 100 parts by weight of the total amount of the heat-resistant copolymer (C) of the vinyl cyanide compound, and more specifically 0.1 to 30 parts by weight.
The above-mentioned acrylic resin composition can be produced by a known method for producing a resin composition. For example, the components and other additives according to one embodiment may be simultaneously mixed and then melt-extruded in an extruder and produced in the form of pellets.
According to another embodiment, there is provided a molded article produced by molding the above acrylic resin composition. That is, the acrylic resin composition can be used to produce a molded article by various processes such as injection molding, blow molding, extrusion molding, and thermoforming. Specifically, it can be effectively applied to molded articles requiring weather resistance, scratch resistance, surface gloss, and heat resistance, and particularly to plastic exterior products such as electric and electronic parts and automobile parts.
Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.
(Example)
Each component used in the production of the acrylic resin composition according to one embodiment is as follows.
(A) the first acrylic copolymer
To 50 parts by weight of a double-layer rubber composed of an inner layer made of a copolymer of butyl acrylate rubber and styrene and an outer layer made of butyl acrylate rubber, 50 parts by weight of a mixture of acrylonitrile and 67% by weight of styrene was grafted To obtain an acrylonitrile-styrene-butyl acrylate graft copolymer. The average particle size of the double-layer rubber is about 0.16 탆.
(B) the second acrylic copolymer
Acrylonitrile-styrene-butyl acrylate graft copolymer was prepared by emulsion polymerization in 60 parts by weight of butyl acrylate rubber so that 40 parts by weight of a mixture of acrylonitrile and acrylonitrile was grafted. At this time, the rubber has a rubber having an average particle diameter of 0.5 mu m or more and a rubber having an average particle diameter of 0.2 mu m.
(C) a heat-resistant copolymer of an aromatic vinyl compound and a vinyl cyanide compound
30% by weight of acrylonitrile and 70% by weight of? -Methylstyrene was used. The weight average molecular weight of the copolymer is about 100,000 g / mol.
(D) Polyalkyl ( Meta ) Acrylate
(D-1) Polymethyl methacrylate having a weight average molecular weight of about 20,000 was used.
(D-2) Polymethyl methacrylate having a weight average molecular weight of about 10,000 was used.
(D-3) Polymethyl methacrylate having a weight average molecular weight of about 50,000 was used.
(E) a copolymer of an aromatic vinyl compound and a vinyl cyanide compound
A copolymer (SAN) composed of 32% by weight of acrylonitrile and 68% by weight of styrene was used. Wherein the weight average molecular weight of the copolymer is about 120,000 g / mol.
(F) Methyl methacrylate - styrene- Acrylonitrile ( MSAN ) Copolymer
15% by weight of acrylonitrile, 70% by weight of styrene, and 15% by weight of methyl methacrylate was used. Wherein the weight average molecular weight of the copolymer is about 145,000 g / mol.
Example 1 to 4 and Comparative Example 1 to 7
Using the above-mentioned components, the acrylic resin composition according to each of Examples 1 to 4 and Comparative Examples 1 to 7 was prepared with the composition shown in Table 1 below.
Each component was mixed with the composition shown in the following Table 1, and 0.4 parts by weight of a lubricant (HI-LUB B-50 from Cha Yang Kasei Co., Ltd.), an impact modifier (L-45 from NIPPON UNICAR Co., ), 0.5 part by weight of a UV stabilizer (TINUVIN 770DF from CIBA SPECIALTY CHEMICALS), 0.5 part by weight of an ultraviolet absorber (TINUVIN 327 from IBA SPECIALTY CHEMICALS) and 0.5 part by weight of carbon black (HI50L from EVONIK) Followed by melting and kneading extrusion to produce pellets. A twin-screw extruder having an L / D of 29 and a diameter of 45 mm was used for the extrusion, and the barrel temperature was set at 220 占 폚.
The weight unit of the lubricant, the impact modifier, the ultraviolet light stabilizer, the ultraviolet absorber and the carbon black is 100 parts by weight based on the total amount of the first acrylic copolymer (A), the second acrylic copolymer (B) and the heat resistant copolymer (C) It is the unit expressed by the standard.
(Test Example)
The pellets were dried at 80 DEG C for 2 hours and then set at a cylinder temperature of 240 DEG C and a mold temperature of 60 DEG C by using an injection molding machine having an injection capability of 6 oz and extruded with an ASTM dumb- The specimens were fabricated by molding. The physical properties of the prepared physical specimens were measured by the following methods, and the results are shown in Table 1 below.
1) IZOD impact strength: measured according to ASTM D256 (specimen thickness 1/8 ").
2) Weatherability: The color difference (ΔE) and Δb after the weathering test of the sample of 9cm × 5cm × 0.2cm size before weathering test and 3,000 hours according to SAE J 1960 condition using ATLAS Ci5000 WOM instrument were measured with a Minolta CM-2500C color difference Respectively.
3) Glossiness: Measured at an angle of 60 ° for 3,000 hours using a UGA UGV-6P DIGITAL VARIABLE GLOSS METER.
4) Scratch resistance: Based on JIS K5401, a specimen having a thickness of 3 mm, a length of 10 mm and a width of 10 mm was loaded at a temperature of 23 ° C. at a temperature of 23 ° C., and the scratch degree was visually determined five times on the surface of the specimen. The pencil hardness grades 4B to 4B were determined.
5) Heat resistance: A specimen with a thickness of 3 mm, a length of 10 mm and a width of 10 mm was prepared based on ISO R 306, and a temperature of 1 mm deformation was measured at a rate of 50 ° C / hr with a load of 5 kg.
Parts by weight based on 100 parts by weight of the total amount of (A) the first acrylic copolymer, (B) the second acrylic copolymer, (C) the heat-resistant copolymer and (E) SAN.
Through the above Table 1, it can be seen that, in accordance with one embodiment, (A) a first acrylic copolymer having a core-shell structure including a double layer rubber, (B) a second acrylic copolymer having a core- (Meth) acrylate were used in the case of Examples 1 to 4 including the thermoplastic copolymer (C), the heat-resistant copolymer of the aromatic vinyl compound and the vinyl cyanide compound, and the polyalkyl (meth) Compared with the case of Comparative Examples 1 to 7 using a polyalkyl (meth) acrylate which does not have a weight average molecular weight range according to one embodiment, it has excellent impact resistance, weather resistance, surface gloss, scratch resistance and heat resistance can confirm.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (10)
(B) a second acrylic copolymer of a core-shell structure comprising a single-layer rubber;
(C) a heat-resistant copolymer of an aromatic vinyl compound and a vinyl cyanide compound, including? -Methylstyrene, phenyl N-substituted maleimide, or a combination thereof; And
(D) a polyalkyl (meth) acrylate having a weight average molecular weight of 20,000 to 30,000 g / mol,
Wherein said polyalkyl (meth) acrylate (D) comprises a homopolymer of alkyl (meth) acrylate, a copolymer of alkyl acrylate and alkyl methacrylate, or a mixture of said homopolymer and said copolymer, Is a substituted or unsubstituted C1 to C10 alkyl
Acrylic resin composition.
The acrylic resin composition
10 to 50% by weight of the first acrylic copolymer (A);
10 to 30% by weight of the second acrylic copolymer (B);
30 to 70% by weight of the heat-resistant copolymer (C) of the aromatic vinyl compound and the vinyl cyanide compound; And
2 to 4 parts by weight of the polyalkyl (meth) acrylate (D) based on 100 parts by weight of the total of the components (A), (B) and (C)
The weight percentages of each of the components (A), (B) and (C) are based on the total weight of the components (A), (B)
Based resin composition.
Wherein the double-layer rubber has an average particle diameter of 0.1 to 0.5 mu m.
Wherein the double-layer rubber comprises an inner layer comprising a copolymer of an acrylic compound and an aromatic vinyl compound, and an outer layer comprising an acrylic compound.
Wherein the single layer rubber comprises a first rubber having an average particle diameter of 0.5 to 1.0 mu m and a second rubber having an average particle diameter of 0.1 to 0.3 mu m.
Wherein the single-layer rubber comprises an acrylic compound.
Wherein the first acrylic copolymer (A) and the second acrylic copolymer (B) are contained in a weight ratio of 80:20 to 20:80.
Wherein the polyalkyl (meth) acrylate (D) is contained in an amount of 2 to 3 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C).
Wherein the acrylic resin composition further comprises (E) a copolymer of an aromatic vinyl compound and a vinyl cyanide compound,
Wherein the aromatic vinyl compound includes styrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, halogen-substituted styrene, or a combination thereof.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100134928A KR101466152B1 (en) | 2010-12-24 | 2010-12-24 | Acrylic based resin composition and molded product using the same |
| PCT/KR2011/006969 WO2012086901A1 (en) | 2010-12-24 | 2011-09-21 | Acrylic resin composition and molded articles using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100134928A KR101466152B1 (en) | 2010-12-24 | 2010-12-24 | Acrylic based resin composition and molded product using the same |
Publications (2)
| Publication Number | Publication Date |
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| KR20120072972A KR20120072972A (en) | 2012-07-04 |
| KR101466152B1 true KR101466152B1 (en) | 2014-11-27 |
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| KR1020100134928A KR101466152B1 (en) | 2010-12-24 | 2010-12-24 | Acrylic based resin composition and molded product using the same |
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| Country | Link |
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| KR (1) | KR101466152B1 (en) |
| WO (1) | WO2012086901A1 (en) |
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| KR20150002267A (en) | 2013-06-28 | 2015-01-07 | 제일모직주식회사 | Thermoplastic resin composition and molded article using the same |
| KR101681212B1 (en) | 2013-09-03 | 2016-11-30 | 롯데첨단소재(주) | Molded article for automobile using thermoplastic resin composition |
| KR101993516B1 (en) * | 2017-05-12 | 2019-06-26 | 롯데첨단소재(주) | Thermoplastic resin composition with excellent colorability and mechanical properties |
| EP3632938B1 (en) * | 2018-10-05 | 2023-05-03 | Trinseo Europe GmbH | Vinylidene substituted aromatic monomer and cyclic (meth)acrylate ester polymers |
| KR102298296B1 (en) | 2018-10-31 | 2021-09-07 | 주식회사 엘지화학 | Thermoplastic resin composition |
| KR102332344B1 (en) * | 2018-11-13 | 2021-11-30 | 주식회사 엘지화학 | Thermoplastic resin composition |
| WO2020101326A1 (en) * | 2018-11-13 | 2020-05-22 | 주식회사 엘지화학 | Thermoplastic resin composition |
| JP7123471B2 (en) * | 2018-11-13 | 2022-08-23 | エルジー・ケム・リミテッド | Thermoplastic resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100515592B1 (en) * | 2003-06-18 | 2005-09-20 | 주식회사 엘지화학 | Thermoplastic resin composition |
| KR100530567B1 (en) * | 1999-02-04 | 2005-11-22 | 제일모직주식회사 | Thermoplastic resin composition with good impact strength |
| KR20070117315A (en) * | 2006-06-08 | 2007-12-12 | 제일모직주식회사 | Acrylate-styrene- acrylonitrile grafted copolymer with excellent impact strength at low and room temperature, coloring, and weatherability, and thermoplastic resin composition containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100282964B1 (en) * | 1994-01-10 | 2001-03-02 | 나가이 야타로 | Maleimide Copolymer and Resin Compositions thereof |
| KR100585942B1 (en) * | 1999-06-24 | 2006-06-01 | 제일모직주식회사 | Thermoplastic resin composition with good heat resistance and elongation property |
| KR100433572B1 (en) * | 2001-10-23 | 2004-06-02 | 제일모직주식회사 | Thermoplastic Resin Composition Having Good Surface Gloss, High Impact Strength and High Flowability |
| KR100497169B1 (en) * | 2002-07-31 | 2005-06-23 | 주식회사 엘지화학 | Method for preparing rubber-copolymer and abs resin comprising thereof |
| WO2006071097A1 (en) * | 2004-12-31 | 2006-07-06 | Lg Chem, Ltd. | Plastic resin composition having improved heat resistance, weld strength, chemical resistance, impact strength, elongation, and wettability |
| KR101211341B1 (en) * | 2008-06-30 | 2012-12-11 | 주식회사 엘지화학 | Thermoplastic resin |
| KR101151108B1 (en) * | 2008-10-20 | 2012-06-01 | 주식회사 엘지화학 | Thermoplastic resin and method for manufacturing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100530567B1 (en) * | 1999-02-04 | 2005-11-22 | 제일모직주식회사 | Thermoplastic resin composition with good impact strength |
| KR100515592B1 (en) * | 2003-06-18 | 2005-09-20 | 주식회사 엘지화학 | Thermoplastic resin composition |
| KR20070117315A (en) * | 2006-06-08 | 2007-12-12 | 제일모직주식회사 | Acrylate-styrene- acrylonitrile grafted copolymer with excellent impact strength at low and room temperature, coloring, and weatherability, and thermoplastic resin composition containing same |
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| Publication number | Publication date |
|---|---|
| WO2012086901A1 (en) | 2012-06-28 |
| KR20120072972A (en) | 2012-07-04 |
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