KR20140099609A - Thermoplastic Resin Composition Having Excellent Appearance Quality and Antistaticity - Google Patents
Thermoplastic Resin Composition Having Excellent Appearance Quality and Antistaticity Download PDFInfo
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- KR20140099609A KR20140099609A KR1020130012223A KR20130012223A KR20140099609A KR 20140099609 A KR20140099609 A KR 20140099609A KR 1020130012223 A KR1020130012223 A KR 1020130012223A KR 20130012223 A KR20130012223 A KR 20130012223A KR 20140099609 A KR20140099609 A KR 20140099609A
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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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- 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
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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- 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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Abstract
The thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl-based graft copolymer, (B) 75 to 90% by weight of an aromatic vinyl monomer and 10 to 25% by weight of an unsaturated nitrile monomer, A modified aromatic vinyl-based Vigreft copolymer obtained by polymerization of an acrylic monomer, an aromatic vinyl monomer and an unsaturated nitrile monomer, and (D) a polymeric amine-based antistatic agent, And is excellent in not only coloring property but also antistatic property.
Description
The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition which is excellent in appearance quality and antistatic property and is suitable for use as a raw material for an exterior material of electric and electronic products.
Acrylonitrile-butadiene-styrene resin (hereinafter referred to as " ABS resin ") is an acrylonitrile-butadiene-styrene resin which is obtained by graft-polymerizing an aromatic vinyl compound styrene monomer and an unsaturated nitrile-based acrylonitrile monomer in the presence of a butadiene- Styrene graft copolymer resin (hereinafter referred to as 'g-ABS resin') and styrene-acrylonitrile copolymer resin (hereinafter referred to as 'SAN resin'). At this time, by controlling physical properties of the g-ABS resin and SAN resin to be used, an ABS resin having desired properties can be obtained.
ABS resin has excellent impact resistance, chemical resistance, heat resistance and mechanical strength and is widely used for parts of electric and electronic products, interior and exterior materials, automobile parts and general merchandise because of easy molding and processing.
In recent years, there has been an increase in demand for electric and electronic products having excellent appearance and gloss, and as the molded products of electric and electronic products have become increasingly smaller, thinner, and lighter, ABS resins having excellent appearance and excellent appearance There is a growing need.
In order to improve the appearance of the ABS resin, a post-injection process has been applied to a product which has been subjected to an injection process. Typical post-processing processes include a coating process for coating an injection molded article. If there is no affinity between the resin and the chemical solvent in such a coating process, a paint appearance defect such as pinhole or coating unevenness may occur. Further, if the affinity between the resin and the chemical solvent does not exist during the coating process, the coating may be repeated several times. These problems cause waste of chemical solvents and complaints of workers. Also, in the case of the coating process, the chemical solvent is thickly applied, which may cause defective appearance of the coating after the drying process.
Korean Patent Laid-Open Publication No. 2006-0018688 refers to an ABS resin composition having excellent appearance quality, but ultimately requires a coating step as a post-process.
Korean Patent Laid-Open Publication No. 2007-0108008 proposes an impact modifier having a core-shell structure for improving the appearance of an ABS resin and blending it into a resin containing an alkyl methacrylate ester or an alkyl acrylate component, And a resin composition having excellent but excellent injection moldability. However, the resin composition is expensive as compared with the ABS resin, and there is a problem that the dust adhering to the molded article using the resin composition becomes conspicuous.
Accordingly, the present inventors have found that by adding an antistatic agent to a thermoplastic resin composition comprising an aromatic vinyl-based graft copolymer and a rubber-modified aromatic vinyl-based graft copolymer in which the content of an unsaturated nitrile monomer is controlled, not only appearance and colorability but also antistatic Leading to development of an excellent thermoplastic resin composition.
The thermoplastic resin composition of the present invention can be used as an exterior material for a TV set that requires excellent appearance quality and antistatic property, and as an exterior material for various electrical and electronic products.
An object of the present invention is to provide a thermoplastic resin composition excellent in appearance quality and antistatic property.
Another object of the present invention is to provide a thermoplastic resin composition excellent in coloring property.
It is still another object of the present invention to provide a thermoplastic resin composition suitable for use as a jacket of a TV set, which requires excellent appearance quality and antistatic property, as a jacket of various electrical and electronic products.
The above and other objects of the present invention can be achieved by the present invention described below.
The thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl-based graft copolymer, (B) 75 to 90% by weight of an aromatic vinyl monomer and 10 to 25% by weight of an unsaturated nitrile monomer, (C) a modified aromatic vinyl-based graft copolymer obtained by polymerizing an acrylic monomer, an aromatic vinyl monomer and an unsaturated nitrile monomer, and (D) a polymeric amine-based antistatic agent.
The thermoplastic resin composition according to the present invention comprises 10 to 30% by weight of the rubber-modified aromatic vinyl-based graft copolymer (A), 40 to 80% by weight of the aromatic vinyl-based graft copolymer (B) (D) 3 to 10 parts by weight of a polymeric amine-based antistatic agent per 100 parts by weight of the base resin composition containing 10 to 30% by weight of the copolymer (C).
The rubber-modified aromatic vinyl-based graft copolymer (A) according to the present invention comprises 30 to 70% by weight of a rubbery polymer, 10 to 60% by weight of an aromatic vinyl monomer and 5 to 30% by weight of a monomer copolymerizable with an aromatic vinyl monomer Graft polymerization.
The rubber-modified aromatic vinyl-based graft copolymer (A) of the present invention comprises (a1) 65 to 100% by weight of a first rubber-modified aromatic vinyl-based graft copolymer having a particle diameter of the rubbery polymer of 0.20 to 0.35 ) 0 to 35% by weight of a second rubber-modified aromatic vinyl-based graft copolymer having a particle diameter of the rubbery polymer of not less than 0.05 m and not more than 0.20 m.
The rubbery polymer of the present invention is selected from the group consisting of a diene rubber, a saturated rubber in which hydrogen is added to a diene rubber, an acrylate rubber, an ethylene-propylene-diene monomer ternary copolymer, a silicone rubber and a mixture thereof.
The aromatic vinyl-based monomer of the present invention may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, Naphthalene, and mixtures thereof.
The monomer copolymerizable with the aromatic vinyl monomer of the present invention may be any of unsaturated nitrile monomer, acrylic acid alkyl ester monomer, methacrylic acid alkyl ester monomer, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, maleimide monomer, ≪ / RTI >
The weight average molecular weight of one aromatic vinyl-based graft copolymer (B) of the present invention is 100,000 to 180,000 g / mol.
The aromatic vinyl-based monomer constituting the aromatic vinyl-based graft copolymer (B), the modified aromatic vinyl-based graft copolymer (C), or both of them may be styrene, Is selected from the group consisting of methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and mixtures thereof.
The unsaturated nitrile monomer constituting the aromatic vinyl-based graft copolymer (B), the modified aromatic vinyl-based graft copolymer (C), or both of the aromatic vinyl-based graft copolymer and the unsaturated nitrile-based monomer of the present invention may be acrylonitrile, methacrylonitrile, And mixtures thereof.
The acrylic monomer of the present invention may be at least one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate Acrylic acid, methacrylic acid, and a mixture thereof, such as acrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, cyclohexyl acrylate, cyclohexyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, glycidyl acrylate, glycidyl methacrylate .
The polymeric amine-based antistatic agent (D) of the present invention is an N-hydroxyethyl-N- (2-hydroxyalkyl) amine polymer.
The molded article produced from the thermoplastic resin composition of the present invention had a notched Izod impact strength of 15 to 35 kgf · cm / cm measured in accordance with ASTM D256, a thickness of 3.175 mm, a temperature of 220 ° C. under ASTM D1238 and a load of 10 kg The melt flow index (MI) measured is 20 to 60 g / 10 min. The Vickers softening point (VST) measured under a load of 5 kg according to ISO 306 is 90 to 99 ° C. And a surface resistance of 10 12 to 10 13 Ω / □.
The molded article produced from one thermoplastic resin composition of the present invention is free of weld dichroism and unevenness, and is excellent in coloring property.
The thermoplastic resin composition of the present invention is excellent in appearance quality and antistatic property, and has the effect of providing a resin composition suitable for use as a jacket of various electrical and electronic products including exterior materials of TV sets that require these properties.
1 is a photograph showing a result of an experiment for attaching a practical dust according to Example 1 of the present invention.
2 is a photograph showing the results of an experiment for attaching a practical dust according to Comparative Example 6 of the present invention.
The present invention relates to a thermoplastic resin composition which is excellent in appearance quality and antistatic property and is suitable for use as a raw material for an exterior material of electric and electronic products.
The thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl-based graft copolymer, (B) an aromatic vinyl-based graft copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated nitrile monomer, and (C) , Aromatic vinyl monomers, and unsaturated nitrile monomers, and (D) a polymeric amine-based antistatic agent.
Each component constituting the thermoplastic resin composition of the present invention will be described in detail as follows.
(A) a rubber-modified aromatic vinyl-based graft copolymer
The rubber-modified aromatic vinyl-based graft copolymer (A) of the present invention can be produced by a method known to those skilled in the art.
The rubber-modified aromatic vinyl-based copolymer (A) can be produced by graft-copolymerizing a rubbery polymer with a monomer copolymerizable with an aromatic vinyl monomer and an aromatic vinyl monomer.
The rubber-modified aromatic vinyl copolymer (A) is prepared by graft-polymerizing 30 to 70% by weight of a rubbery polymer, 10 to 60% by weight of an aromatic vinyl monomer and 5 to 30% by weight of a monomer copolymerizable with an aromatic vinyl monomer . Preferably, it is prepared by graft polymerizing 40 to 60% by weight of a rubbery polymer, 25 to 45% by weight of an aromatic vinyl monomer and 5 to 20% by weight of a monomer copolymerizable with an aromatic vinyl monomer. For example, the rubber-modified aromatic vinyl-based copolymer (A) is prepared by graft-polymerizing 58% by weight of a rubbery polymer, 32% by weight of an aromatic vinyl monomer and 10% by weight of a monomer copolymerizable with an aromatic vinyl monomer. The rubber-modified aromatic vinyl-based copolymer (A) is prepared by graft-polymerizing 45% by weight of a rubbery polymer, 40% by weight of an aromatic vinyl monomer and 15% by weight of a monomer copolymerizable with an aromatic vinyl monomer.
The rubber-modified aromatic vinyl-based graft copolymer (A) comprises (a1) a first rubber-modified aromatic vinyl-based graft copolymer having a particle diameter of 0.20 탆 or more and 0.35 탆 or less and (a2) And a second rubber-modified aromatic vinyl-based graft copolymer having a diameter of not less than 0. < RTI ID = 0.0 > For example, the rubber-modified aromatic vinyl-based graft copolymer may preferably be a rubber-modified aromatic vinyl-based graft copolymer (a1) having a particle diameter of 0.25 to 0.32 m, And a second rubber-modified aromatic vinyl-based graft copolymer (a2) having a thickness of 0.15 m or less. When only the first rubber-modified aromatic vinyl-based graft copolymer (a1) is used, the impact strength of the thermoplastic resin composition can be maintained to be excellent. However, in order to improve the appearance, the second rubber-modified aromatic vinyl-based graft copolymer (a2) may be used together.
The rubber-modified aromatic vinyl-based graft copolymer (A) contains 65 to 100% by weight of the first rubber-modified aromatic vinyl-based graft copolymer (a1) and 0 to 35 % ≪ / RTI > by weight. When the content ratio of the first rubber-modified aromatic vinyl-based graft copolymer (a1) to the second rubber-modified aromatic vinyl-based graft copolymer (a2) is within the range of the present invention, both the impact resistance and the appearance are excellent . For example, a rubber-modified aromatic vinyl-based graft copolymer comprising 66.67 wt% of the first rubber-modified aromatic vinyl-based graft copolymer (a1) and 33.33 wt% of the second rubber-modified aromatic vinyl-based graft copolymer (a2) Coalescence can be used. The weight ratio of the first rubber-modified aromatic vinyl-based graft copolymer (a1) to the second rubber-modified aromatic vinyl-based graft copolymer (a2) is from 2: 1 to 4: 1, for example, 3: 1.
Examples of the rubbery polymer include diene rubber, saturated rubber in which hydrogen is added to diene rubber, acrylate rubber, ethylene-propylene-diene monomer ternary copolymer, silicone rubber, and the like. These may be used singly or in combination of two or more.
The diene rubbers may be selected from the group consisting of polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), polyisoprene, and mixtures thereof.
The acrylate-based rubber may be at least one selected from the group consisting of polymethyl acrylate, polyethylacrylate, poly-n-propyl acrylate, poly-n-butyl acrylate, poly 2-ethylhexyl acrylate, polyhexyl methacrylate, And mixtures thereof, but are not necessarily limited thereto.
The silicone-based rubbers may be selected from the group consisting of polyhexamethylcyclotrisiloxane, polyoctamethylcyclosiloxane, polydecamethylcyclosiloxane, polydodecamethylcyclosiloxane, polytrimethyltriphenylcyclosiloxane, polytetramethyltetraphenylcyclotetrasiloxane, polyoctaphenylcyclotetra Siloxane, and mixtures thereof, but is not necessarily limited thereto.
The rubbery polymer may be selected from the group consisting of ethylene / propylene rubbers, terpolymers of ethylene-propylene-diene, and mixtures thereof.
As the rubber polymer, a diene rubber can be preferably used, and more preferably a butadiene rubber can be used.
The aromatic vinyl monomer may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene and , And is not necessarily limited to these. Styrene may be preferably used.
The monomer copolymerizable with the aromatic vinyl monomer is at least one monomer selected from the group consisting of an unsaturated nitrile monomer, an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a maleimide monomer, And the present invention is not limited thereto.
The unsaturated nitrile-based monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof, but is not limited thereto.
The acrylic acid alkyl ester monomer may be selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, cyclohexyl acrylate, n-hexyl acrylate, But is not limited thereto.
The methacrylic acid alkyl ester monomer may be a monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, And the present invention is not limited thereto.
The unsaturated carboxylic acid may be selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, and mixtures thereof, but is not necessarily limited thereto.
The unsaturated carboxylic acid anhydride may be selected from the group consisting of maleic anhydride, fumaric anhydride, and mixtures thereof, but is not necessarily limited thereto.
The maleimide-based monomer is selected from the group consisting of maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-dichlorohexylmaleimide, N-phenylmaleimide and N- , And is not necessarily limited thereto.
These unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimide-based monomers, and mixtures thereof can impart heat resistance and processability to the rubber-modified aromatic vinyl-based graft copolymer.
As the monomer copolymerizable with the aromatic vinyl monomer, an unsaturated nitrile monomer can be preferably used, and acrylonitrile can be more preferably used.
In the present invention, the rubber-modified aromatic vinyl-based graft copolymer (A) is obtained by copolymerizing the rubber-modified aromatic vinyl-based graft copolymer (A), the aromatic vinyl-based graft copolymer (B) and the modified aromatic vinyl- It is preferably used in an amount of 10 to 30% by weight based on 100% by weight of the base resin composition comprising the copolymer (C).
(B) an aromatic vinyl-based Vigreft copolymer
The aromatic vinyl-based graft copolymer (B) of the present invention is obtained by polymerizing 75 to 90% by weight of an aromatic vinyl-based monomer and 10 to 25% by weight of an unsaturated nitrile-based monomer. The aromatic vinyl-based graft copolymer can be easily manufactured or commercially available by those skilled in the art. Examples of the Vigreft copolymer include alternating copolymers, random copolymers, block copolymers and the like, and the Vigreft copolymer does not include a graft copolymer.
The aromatic vinyl-based graft copolymer (B) polymerizes 75 to 90% by weight of an aromatic vinyl-based monomer and 10 to 25% by weight of an unsaturated nitrile-based monomer. For example, the aromatic vinyl-based graft copolymer (B) polymerizes 82% by weight of an aromatic vinyl-based monomer and 18% by weight of an unsaturated nitrile-based monomer. When the content of the unsaturated nitrile monomer is less than 10% by weight, other properties such as impact resistance or toughness may be deteriorated. When the content of the unsaturated nitrile monomer is more than 25% by weight, the flowability may deteriorate and the appearance may be deteriorated. The polarity is increased and the compatibility with the following modified aromatic vinyl-based Vigreft copolymer may be lowered.
The aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, And the present invention is not limited thereto. Of these, styrene is preferable.
The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof, but is not limited thereto. Of these, acrylonitrile is preferable.
The aromatic vinyl-based graft copolymer (B) has a weight average molecular weight of 100,000 to 180,000 g / mol. Preferably 100,000 to 150,000 g / mol, for example 140,000 g / mol. If the weight average molecular weight is less than 100,000 g / mol, physical properties such as toughness of the thermoplastic resin composition may be deteriorated.
The aromatic vinyl-based graft copolymer (B) may contain 0 to 15% by weight of a monomer selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a maleimide monomer and a mixture thereof to impart heat resistance and processability, . ≪ / RTI >
The unsaturated carboxylic acid may be selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, and mixtures thereof, but is not necessarily limited thereto.
The unsaturated carboxylic acid anhydride may be selected from the group consisting of maleic anhydride, fumaric anhydride, and mixtures thereof, but is not necessarily limited thereto.
The maleimide-based monomer is selected from the group consisting of maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-dichlorohexylmaleimide, N-phenylmaleimide and N- , And is not necessarily limited thereto.
In the present invention, the aromatic vinyl-based graft copolymer (B) is a rubber-modified aromatic vinyl graft copolymer (A), an aromatic vinyl graft copolymer (B) and a modified aromatic vinyl graft copolymer By weight based on 100% by weight of the base resin composition.
(C) a modified aromatic vinyl-based Vigreft copolymer
The modified aromatic vinyl-based graft copolymer (C) is obtained by polymerizing an acrylic monomer, an aromatic vinyl monomer and an unsaturated nitrile monomer. Examples of the modified aromatic graft copolymer (C) include alternating copolymers, random copolymers and block copolymers, and the modified aromatic non-graft copolymer (C) does not contain a graft copolymer.
The modified aromatic vinyl-based graft copolymer (C) has a weight average molecular weight of 5,000 to 15,000 g / mol. Preferably 7,000 to 12,000 g / mol, for example 10,000 g / mol. When the weight average molecular weight of the modified aromatic vinyl-based graft copolymer (C) is in the above range, the flowability of the thermoplastic resin composition is increased and the moldability can be improved.
The acrylic monomer may be at least one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, cyclohexyl Acrylic acid, methacrylic acid, and mixtures thereof, which is selected from the group consisting of acrylic acid, methacrylic acid, methacrylic acid, acrylate, cyclohexyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, glycidyl acrylate, glycidyl methacrylate . Of these, methyl methacrylate is preferable.
The aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, And the present invention is not limited thereto. Of these, styrene is preferable.
The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof, but is not limited thereto. Of these, acrylonitrile is preferable.
In order to impart heat resistance and processability, the modified aromatic vinyl-based non-graft copolymer (C) is a copolymer of a monomer selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a maleimide monomer, May be further polymerized.
The unsaturated carboxylic acid excluding the acrylic monomer may be selected from the group consisting of maleic acid, fumaric acid, and mixtures thereof, but is not limited thereto.
The unsaturated carboxylic acid anhydride may be selected from the group consisting of maleic anhydride, fumaric anhydride, and mixtures thereof, but is not necessarily limited thereto.
The maleimide-based monomer is selected from the group consisting of maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-dichlorohexylmaleimide, N-phenylmaleimide and N- , And is not necessarily limited thereto.
The modified aromatic vinyl-based graft copolymer (C) may be obtained by polymerizing 10 to 30% by weight of an acrylic monomer, 60 to 80% by weight of an aromatic vinyl monomer, and 5 to 20% by weight of an unsaturated nitrile monomer. For example, the modified aromatic vinyl-based graft copolymer (C) is obtained by polymerizing 20% by weight of an acrylic monomer, 70% by weight of an aromatic vinyl monomer, and 10% by weight of an unsaturated nitrile monomer.
The modified aromatic vinyl-based graft copolymer (C) contains 0 to 25% by weight of a monomer selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a maleimide monomer and a mixture thereof except for the acrylic monomer May be further polymerized.
In the present invention, the modified aromatic vinyl-based graft copolymer (C) is a rubber-modified aromatic vinyl-based graft copolymer (A), an aromatic vinyl-based graft copolymer (B), and a modified aromatic vinyl-based graft copolymer By weight based on 100% by weight of the base resin composition.
(D) High molecular weight amine-based antistatic agent
An antistatic agent refers to an additive that acts to reduce or remove static electricity formed on the surface of a product by being added to the thermoplastic resin or treated on the surface of the finished product.
In order to improve the electrostatic charging property, there are a method of introducing hydrophilicity by chemically treating the surface, a method of grafting a hydrophilic monomer, a method of adding a material of a positive electrode such as a powder, etc. However, The most commonly used method due to problems is the use of antistatic agents.
The antistatic agent is mainly a fast-acting antistatic agent and a permanent antistatic agent. The fast-acting antistatic agent forms a conductive film on the surface of the resin molded article and bonds with moisture in the air to exhibit antistatic property. Permanent antistatic agents are used to blend an antistatic block copolymer with a resin and thus exhibit antistatic properties permanently. In the present invention, a permanent antistatic agent is used for permanent antistatic property.
The antistatic agent used in the present invention is an amine compound generally used as a polymer type antistatic agent and can be easily selected by those skilled in the art. In the case of the amine compound, since the polarity of the amine group is high and the static electricity is low, the dust is not adhered to the surface of the molded article containing the amine compound. A representative example of the amine-based compound is N-hydroxyethyl-N (2-hydroxyalkyl) amine represented by the following formula 1:
≪ Formula 1 >
The antistatic property is measured by a half-life method and a surface resistance method. The half-life technique measures the time for which the charge amount is reduced by half after a given charge is given to the resin molded article, and it is possible to grasp the characteristics of the chargeability although there is no specific range. The surface resistance measuring method measures the surface resistance of the resin molded article itself. The surface resistance of a general non-electrification resistant resin molded article is about 10 15 Ω / □. The surface resistance indicates the time when electricity flows out. When the resistance is 10 times The time required is also 10 times.
The thermoplastic resin according to the present invention has a surface resistance of 10 12 to 10 13 Ω / □ measured according to ASTM D257.
In the present invention, the polymeric amine-based antistatic agent (D) is a copolymer of a rubber-modified aromatic vinyl-based graft copolymer (A), an aromatic vinyl- based graft copolymer (B) and a modified aromatic vinyl- based graft copolymer It is preferably used in an amount of 3 to 10 parts by weight based on 100 parts by weight of the basic resin composition. When the content of the polymeric amine-based antistatic agent (D) is less than 3 parts by weight, the antistatic property of the thermoplastic resin composition is not excellent. When the content of the polymeric amine-based antistatic agent (D) The appearance of the display device is deteriorated.
(E) Additive
The thermoplastic resin composition may further include additives according to the respective applications. The thermoplastic resin composition is selected from the group consisting of a flame retardant, a flame retardant aid, an impact modifier, a dripping inhibitor, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weathering stabilizer, a pigment, a dye, a colorant, But it is not necessarily limited thereto.
The additive is added to 100 parts by weight of the base resin composition comprising the rubber-modified aromatic vinyl-based graft copolymer (A), the aromatic vinyl-based graft copolymer (B), and the modified aromatic vinyl-based graft copolymer (C) By weight or less, preferably 0.0001 to 10 parts by weight.
The thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be simultaneously mixed and then melt-extruded in an extruder to produce pellets or chips.
The present invention also provides a molded article produced from the thermoplastic resin composition. In one embodiment of the present invention, there is no particular limitation on the method of molding the molded article, and extrusion, injection, hollow, compression, vacuum or cast molding methods can be applied. Such molding can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.
The Izod notch impact strength of the 3.175 mm thick specimen measured according to ASTM D256 is 15 to 35 kgf · cm / cm in the molded article produced from the thermoplastic resin composition according to the present invention. For example, the thermoplastic resin composition has Izod notch impact strength of 3.175 mm thick measured according to ASTM D256 of 16 kgf · cm / cm, 23 kgf · cm / cm, 27 kgf · cm / cm, or 33.4 kgf · cm / cm.
The molded article produced from the thermoplastic resin composition according to the present invention has a melt flow index (MI) of 20 to 60 g / 10 min measured at a temperature of 220 캜 and a load of 10 kg in accordance with ASTM D1238. For example, the thermoplastic resin composition has a melt flow index of 22 g / 10 min, 30 g / 10 min, 51 g / 10 min, or 58 g / 10 min as measured according to ASTM D1238 at a temperature of 220 ° C. and a load of 10 kg.
The molded article produced from the thermoplastic resin composition according to the present invention has a Vickert softening point (VST) of 90 to 99 DEG C measured under a load of 5 kg in accordance with ISO 306. For example, the thermoplastic resin composition has 90 ° C, 95.2 ° C, 95.6 ° C or 96.5 ° C beetle softening points measured under a load of 5 kg according to ISO 306.
The molded article produced from the thermoplastic resin composition according to the present invention has a surface resistance of 10 12 to 10 13 Ω / □ measured according to ASTM D257. For example, the thermoplastic resin composition has a surface resistance of 10 12 Ω / □ measured according to ASTM D257.
The molded article produced from the thermoplastic resin composition according to the present invention is free of weld color and unevenness, and is excellent in coloring property.
The thermoplastic resin composition according to the present invention can be suitably applied to the molding of various products because it has excellent properties such as impact resistance, fluidity and heat resistance, appearance and colorability as well as antistatic property. Can be widely used in the manufacture of housings for electrical and electronic products whose appearance is important, such as TV, audio, cellular phone, digital camera, navigation, washing machine, computer, monitor, MP3, video player, CD player, Further, since the thermoplastic resin composition according to the present invention is excellent in appearance and colorability by itself, a separate coating step is not required.
The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.
Example
The specifications of each component used in the following examples and comparative examples are as follows:
(A) a rubber-modified aromatic vinyl-based graft copolymer
(a1) graft acrylonitrile-butadiene-styrene copolymer obtained by graft polymerizing 11.04% by weight of acrylonitrile monomer and 36.96% by weight of styrene monomer in 52% by weight of polybutadiene and having a particle diameter of not less than 0.25 m and not more than 0.32 m (G-ABS) was used.
(a2) graft acrylonitrile-butadiene-styrene copolymer obtained by graft-polymerizing 15.4% by weight of acrylonitrile monomer and 39.6% by weight of styrene monomer in 45% by weight of polybutadiene and having a particle diameter of not less than 0.10 m and not more than 0.15 m (G-ABS) was used.
(B) an aromatic vinyl-based Vigreft copolymer
(b1) A styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 90,000 g / mol and polymerizing 74% by weight of styrene monomer and 26% by weight of acrylonitrile monomer was used.
(b2) A styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 130,000 g / mol and polymerizing 74% by weight of styrene monomer and 26% by weight of acrylonitrile monomer was used.
(b3) A styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 140,000 g / mol and polymerizing 18% by weight of acrylonitrile monomer with 82% by weight of styrene monomer was used.
(C) a modified aromatic vinyl-based Vigreft copolymer
(c1) a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 10,000 g / mol and polymerizing 70% by weight of styrene monomer and 10% by weight of acrylonitrile monomer and 20% by weight of methyl methacrylate MSAN) was used.
(D) Antistatic agent: NC6321 of Sanyo Chemical Industries, Ltd. was used.
The properties of the following examples and comparative examples were determined by the following method:
(1) Impact resistance: Izod notch impact strength was measured according to ASTM D256 for specimens having a thickness of 3.175 mm (1/8 ").
(2) Flowability: According to ASTM D1238, the melt flow index was measured at a temperature of 220 캜 and a load of 10 kg.
(3) Heat resistance: The beak softening point was measured under a load of 5 kg according to ISO 306.
(4) Weld two-color: Welds were produced at the time of manufacturing a molded article using a high-hardness mold and observed and evaluated by visual observation.
?: Very excellent,?: Excellent,?: Fair, X: poor
(5) Smear: A molded article was manufactured using a high-hardness mold, and the presence or absence of a line and the transverse line visibility were visually evaluated.
?: Very excellent,?: Excellent,?: Fair, X: poor
(6) Colorability: A molded article was manufactured using a high-hardness mold, and color deviations of each part were visually evaluated.
?: Very excellent,?: Excellent,?: Fair, X: poor
(7) Surface resistance: The surface resistance was measured according to ASTM D257 for a molded article manufactured using a hardened surface mold.
(8) Attachment of practical dust: A molded product was manufactured using a high-hardness mold, left for two weeks in the room, and the appearance was visually evaluated.
X: No dust attached, O: Dust adhered
Example 1-4 and Comparative Example 1-6
Each component was mixed in a conventional mixer with the compositions shown in Tables 1 and 2 below. After mixing, the mixture was fed into a twin-screw extruder having L / D = 32 and ø = 45 mm. The mixture was made into a thermoplastic resin composition in the form of pellets through an extruder, and specimens for evaluation of physical properties were prepared at an injection temperature of 220 ° C to 240 ° C using a 15 oz injection machine.
In the following table, the contents of (A), (B) and (C) are shown in terms of% by weight based on 100% by weight of the total of (A), (B) and (C) (B) and (C).
(kgf · cm / cm)
(g / 10 min)
(° C)
Impact strength
(kgf · cm / cm)
(° C)
As can be seen from Table 1, Examples 1 to 4 exhibit excellent antistatic properties while exhibiting excellent impact resistance, flowability and heat resistance, exhibiting excellent appearance and coloring property. Also, even though the content of g-ABS increases from 1 to 4 in Example 1, even if the fluidity is lowered, SAN and MSAN having a small amount of acrylonitrile are used, thereby exhibiting excellent appearance and colorability.
From Table 2, it can be seen that Comparative Example 1 can not exhibit the appearance and colorability at the level of Example 1 or 2 even when the particle diameter of the gum polymer of g-ABS and the weight average molecular weight of SAN are adjusted. In Comparative Example 2, the appearance and coloring property were remarkably lowered by using a larger amount of g-ABS than a g-ABS having a smaller particle diameter and using a high molecular weight SAN having a high acrylonitrile content instead of MSAN. In Comparative Examples 3 and 4, antistatic agents were not used and antistatic properties were deteriorated. In Comparative Example 5, the antistatic property was lowered by using the antistatic agent in less than the preferable range. In Comparative Example 6, the antistatic agent was used in a larger amount than the preferable range, but the appearance such as weld dichroism and coloring property was deteriorated Able to know.
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 invention as defined by the appended claims.
Claims (15)
(B) an aromatic vinyl-based graft copolymer obtained by polymerizing 75 to 90% by weight of an aromatic vinyl monomer and 10 to 25% by weight of an unsaturated nitrile monomer;
(C) a modified aromatic vinyl-based Vigreft copolymer obtained by polymerizing an acrylic monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer; And
(D) a polymeric amine-based antistatic agent;
And a thermoplastic resin composition.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017099410A1 (en) * | 2015-12-10 | 2017-06-15 | (주) 엘지화학 | Thermoplastic resin composition and molded product |
| WO2018124505A1 (en) * | 2016-12-28 | 2018-07-05 | (주) 엘지화학 | Thermoplastic resin composition, preparation method therefor, and injection molded product comprising same |
| WO2021080201A1 (en) * | 2019-10-23 | 2021-04-29 | (주) 엘지화학 | Thermoplastic resin composition, preparation method therefor, and molded product comprising same |
| US11718745B2 (en) | 2019-10-23 | 2023-08-08 | Lg Chem, Ltd. | Thermoplastic resin composition, method of preparing the same, and molded article including the same |
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2013
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017099410A1 (en) * | 2015-12-10 | 2017-06-15 | (주) 엘지화학 | Thermoplastic resin composition and molded product |
| CN107207824A (en) * | 2015-12-10 | 2017-09-26 | 株式会社Lg化学 | Thermoplastic resin composition and mechanograph |
| US10189984B2 (en) | 2015-12-10 | 2019-01-29 | Lg Chem, Ltd. | Thermoplastic resin composition and molded article |
| WO2018124505A1 (en) * | 2016-12-28 | 2018-07-05 | (주) 엘지화학 | Thermoplastic resin composition, preparation method therefor, and injection molded product comprising same |
| US11084921B2 (en) | 2016-12-28 | 2021-08-10 | Lg Chem, Ltd. | Thermoplastic resin composition, method of preparing the same, and injection-molded article including the same |
| WO2021080201A1 (en) * | 2019-10-23 | 2021-04-29 | (주) 엘지화학 | Thermoplastic resin composition, preparation method therefor, and molded product comprising same |
| US11718745B2 (en) | 2019-10-23 | 2023-08-08 | Lg Chem, Ltd. | Thermoplastic resin composition, method of preparing the same, and molded article including the same |
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