WO2019190067A1 - Thermoplastic resin composition and molded article formed therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention comprises: a rubber-modified aromatic vinyl-based copolymer resin; an aliphatic polyamide resin; a polyether ester amide block copolymer; a saturated fatty acid bisamide; and an aliphatic carboxylic acid ester compound. The thermoplastic resin composition is excellent in static resistance, surface hydrophobicity, and the like.

Description

Thermoplastic resin composition and molded article formed therefrom

The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent antistatic property, surface hydrophobicity, and the like, and a molded article formed therefrom.

As the thermoplastic resin, rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) are excellent in mechanical properties, processability, appearance characteristics, etc. It is widely used as interior / exterior materials for automobiles and exterior materials for construction.

However, since the plastic products prepared from the conventional thermoplastic resin composition have little moisture absorbing power in the air and accumulate without generating the generated static electricity, dust in the air may be adsorbed, causing surface contamination and electrostatic shock, and malfunction of the device. This may cause a malfunction.

In order to secure the antistatic property of the thermoplastic resin composition, an antistatic agent may be used, but in order to obtain appropriate antistatic property, an excessive amount of antistatic agent is required, and in this case, deterioration in compatibility, mechanical properties, etc. of the thermoplastic resin composition It may occur.

In addition, when the thermoplastic resin composition is applied to a product installed outdoors such as a building exterior material, the surface may be modified to have hydrophobicity in order to reduce contamination, dust adhesion due to precipitation, snowfall, and the like.

In order to have a hydrophobic surface of the thermoplastic resin composition, a method such as adding a hydrophobic film coating or the like is used, but such a method has disadvantages such as an increase in cost and a decrease in productivity due to the addition of the process. In addition, a method of adding various additives capable of imparting hydrophobicity may be used, but conventionally used silica-based, fluorine-based, and ionic-based additives may cause problems such as deterioration in color, appearance, physical properties, etc. due to excessive addition. There is a risk of rising issues.

Accordingly, there is a need for development of thermoplastic resin compositions having excellent antistatic property, surface hydrophobicity, balance of physical properties thereof, and the like without these problems.

Background art of the present invention is disclosed in, for example, Patent Publication No. 2014-0135790.

An object of the present invention is to provide a thermoplastic resin composition excellent in antistatic property, surface hydrophobicity and the like.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition may be a rubber-modified aromatic vinyl copolymer resin; Aliphatic polyamide resins; Polyetheresteramide block copolymers; Saturated fatty acid bis amide; And aliphatic carboxylic acid ester compounds.

2. The thermoplastic resin composition of embodiment 1, wherein the thermoplastic resin composition comprises about 60 to about 95 wt% of the rubber-modified aromatic vinyl copolymer resin and about 100 wt% of the base resin including about 5 to about 40 wt% of the aliphatic polyamide resin. To about 1 part by weight to about 15 parts by weight of the polyetheresteramide block copolymer, about 0.1 to about 5 parts by weight of the saturated fatty acid bisamide, and about 0.1 to about 10 parts by weight of the aliphatic carboxylic acid ester compound. Can be.

3. In one or two embodiments, the rubber modified aromatic vinyl copolymer resin may include a rubber modified vinyl graft copolymer and an aromatic vinyl copolymer resin.

4. In the above 1 to 3 embodiments, the rubber-modified vinyl graft copolymer may be a graft polymerized monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in the rubbery polymer.

5. In the above 1 to 4 embodiments, the polyetheresteramide block copolymer is an amino carboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms; Polyalkylene glycols; And it may be a block copolymer of the reaction mixture comprising a dicarboxylic acid having 4 to 20 carbon atoms.

6. In the above 1 to 5, the saturated fatty acid bis amide is one of methylene bis stearamide, methylene bis oleamide, ethylene bis stearamide, ethylene bis oleamide, hexamethylene bis stearamide and hexamethylene bis oleamide It may contain the above.

7. In the above 1 to 6 embodiments, the aliphatic carboxylic acid ester compound may be a dehydration product of an aliphatic carboxylic acid having 10 to 100 carbon atoms and a monovalent or polyhydric alcohol having 2 to 50 carbon atoms.

8. In the above 1 to 7 embodiments, the weight ratio of the saturated fatty acid bis amide and the aliphatic carboxylic acid ester compound may be about 1: 2 to about 1: 8.

9. In the above 1 to 8 embodiments, the thermoplastic resin composition may have a surface resistance value of about 1 × 10 ⁹ to about 2 × 10 ¹⁰ Ω / sq. Measured according to ASTM D257.

10. In the above 1 to 9 embodiments, the thermoplastic resin composition may have a half-life of about 0.1 seconds to about 2 seconds as measured according to KS K 0555.

11. In the above 1 to 10 embodiments, the thermoplastic resin composition may drop 3 μl of distilled water into a 100 mm × 100 mm size specimen, and the contact angle of the water droplet on the surface of the specimen measured by a contact angle measuring instrument may be about 92 to about 105 °. have.

12. Another aspect of the invention relates to a molded article. The molded article is formed from the thermoplastic resin composition according to any one of 1 to 11.

This invention has the effect of the invention which provides the thermoplastic resin composition excellent in antistatic property, surface hydrophobicity, etc., and the molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention is (A) rubber-modified aromatic vinyl copolymer resin; (B) aliphatic polyamide resins; (C) polyetheresteramide block copolymers; (D) saturated fatty acid bis amide; And (E) aliphatic carboxylic acid ester compounds.

In the present specification, "a to b" indicating a numerical range is defined as "≥a and <b".

(A) Rubber Modified Aromatic Vinyl Copolymer Resin

The rubber modified aromatic vinyl copolymer resin of the present invention may include (A1) rubber modified vinyl graft copolymer and (A2) aromatic vinyl copolymer resin.

(A1) rubber-modified vinyl-based graft copolymer

Rubber-modified vinyl graft copolymer according to an embodiment of the present invention may be a graft polymerized monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in the rubber polymer. For example, the rubber-modified vinyl graft copolymer may be obtained by graft polymerization of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer, and, if necessary, processability and The monomer which gives heat resistance can be further included and graft-polymerized. The polymerization may be carried out by known polymerization methods such as emulsion polymerization and suspension polymerization. In addition, the rubber-modified vinyl graft copolymer may form a core (rubber polymer) -shell (copolymer of monomer mixture) structure, but is not limited thereto.

In an embodiment, the rubbery polymer may be a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), or a saturated rubber hydrogenated to the diene rubber, isoprene rubber, C 2 to C 10 alkyl (meth) acrylate rubbers, copolymers of alkyl (meth) acrylates having 2 to 10 carbon atoms and styrene, ethylene-propylene-diene monomer terpolymers (EPDM), and the like. These can be applied individually or in mixture of 2 or more types. For example, a diene rubber, (meth) acrylate rubber, etc. can be used, Specifically, butadiene rubber, butyl acrylate rubber, etc. can be used.

In embodiments, the rubbery polymer (rubber particles) has an average particle size (D50) measured by particle size analyzer of about 0.05 to about 6 μm, for example about 0.15 to about 4 μm, specifically about 0.25 to about 3.5 μm Can be. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.

In embodiments, the content of the rubbery polymer may be about 20 to about 70% by weight, for example about 25 to about 60% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, the monomer mixture (aromatic The vinyl monomer and the vinyl cyanide monomer) may be about 30 to about 80 wt%, for example about 40 to about 75 wt%, of 100 wt% of the total rubber-modified vinyl graft copolymer. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.

In an embodiment, the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be illustrated. These may be used alone or in combination of two or more thereof. The aromatic vinyl monomer may be included in an amount of about 10 wt% to about 90 wt%, for example, about 40 wt% to about 90 wt% in 100 wt% of the monomer mixture. In the above range, the processability, impact resistance, and the like of the thermoplastic resin composition may be excellent.

In one embodiment, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. It can be illustrated. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer may be about 10 wt% to about 90 wt%, for example about 10 wt% to about 60 wt%, in 100 wt% of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.

In a specific example, monomers for imparting processability and heat resistance may include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like. When using the monomer to impart the processability and heat resistance, the content may be about 15% by weight or less, for example about 0.1 to about 10% by weight of 100% by weight of the monomer mixture. In the above range, processability and heat resistance can be imparted to the thermoplastic resin composition without deteriorating other physical properties.

In one embodiment, the rubber-modified vinyl graft copolymer is a copolymer in which a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, are grafted to a butadiene rubber polymer, and butyl acryl. An acrylate-styrene-acrylonitrile graft copolymer (g-ASA) which is a copolymer in which the styrene monomer which is an aromatic vinyl type compound, and the acrylonitrile monomer which is a vinyl cyanide compound is grafted to a latex rubbery polymer can be illustrated. have.

In embodiments, the rubber-modified vinyl graft copolymer is about 10 to about 50 weight in 100% by weight of the total rubber-modified aromatic vinyl copolymer resin (rubber modified vinyl graft copolymer and aromatic vinyl copolymer copolymer resin) %, For example from about 25 to about 45% by weight. In the above range, the impact resistance, fluidity (molding processability), appearance properties, balance of physical properties, and the like of the thermoplastic resin composition may be excellent.

(A2) aromatic vinyl copolymer resin

The aromatic vinyl copolymer resin according to one embodiment of the present invention may be an aromatic vinyl copolymer resin used in a conventional rubber-modified vinyl copolymer resin. For example, the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.

In an embodiment, the aromatic vinyl copolymer resin may be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and then polymerizing them, and the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, or the like. It can be carried out by a known polymerization method of.

In embodiments, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinylnaphthalene and the like can be used. These can be applied individually or in mixture of 2 or more types. The content of the aromatic vinyl monomer may be about 20 to about 90 wt%, for example about 30 to about 80 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

In embodiments, the monomer copolymerizable with the aromatic vinyl monomer may include at least one of a vinyl cyanide monomer and an alkyl (meth) acrylic monomer. For example, it may be a vinyl cyanide monomer or a vinyl cyanide monomer and an alkyl (meth) acrylic monomer, specifically, a vinyl cyanide monomer and an alkyl (meth) acrylic monomer.

In an embodiment, examples of the vinyl cyanide monomer may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like, but are not limited thereto. Do not. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used.

In specific embodiments, examples of the alkyl (meth) acrylic monomer may include (meth) acrylic acid and / or alkyl (meth) acrylate having 1 to 10 carbon atoms. These may be used alone or in combination of two or more thereof. For example, methyl methacrylate, methyl acrylate, etc. can be used.

In embodiments, when the monomer copolymerizable with the aromatic vinyl monomer is a mixture of a vinyl cyanide monomer and an alkyl (meth) acrylic monomer, the content of the vinyl cyanide monomer may be 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer. About 1 to about 40% by weight, for example about 2 to about 35% by weight, and the content of the alkyl (meth) acrylic monomer is about 60 to about 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer. 99 weight percent, for example about 65 to about 98 weight percent. In the above range, the thermoplastic resin composition may have excellent transparency, heat resistance, processability, and the like.

In an embodiment, the content of the monomer copolymerizable with the aromatic vinyl monomer may be about 10 to about 80 wt%, for example about 20 to about 70 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

In embodiments, the aromatic vinyl copolymer resin has a weight average molecular weight (Mw) of about 10,000 to about 300,000 g / mol, for example, about 15,000 to about 150,000 g / mol, as measured by gel permeation chromatography (GPC). Can be. In the above range, the mechanical strength, moldability, and the like of the thermoplastic resin composition may be excellent.

In embodiments, the aromatic vinyl copolymer resin may be included in about 50 to about 90% by weight, for example about 55 to about 75% by weight of 100% by weight of the total rubber-modified aromatic vinyl copolymer resin. Impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition in the above range may be excellent.

In an embodiment, the rubber-modified aromatic vinyl copolymer resin (A) is about 60% by weight of 100% by weight of the base resin (A + B) including the rubber-modified aromatic vinyl copolymer resin and the aliphatic polyamide resin. To about 95 weight percent, such as about 65 to about 85 weight percent. In the above range, the mechanical properties, antistatic properties, surface hydrophobicity, etc. of the thermoplastic resin composition may be excellent.

(B) aliphatic polyamide resin

The aliphatic polyamide resin according to one embodiment of the present invention can improve the antistatic properties of the thermoplastic resin composition even when a small amount of the antistatic agent is used, and a conventional aliphatic polyamide resin can be used.

In an embodiment, the aliphatic polyamide resin can be polyamide 6, polyamide 11, polyamide 12, polyamide 4.6, polyamide 6.6, polyamide 6.10, combinations thereof, and the like. For example, polyamide 6, polyamide 6.6 and the like can be used.

In embodiments, the aliphatic polyamide resin has a relative viscosity (RV) of about 2.0 to about 3.5, such as about 2.3 to about 3.5, as measured by a Ubbelodhde viscometer in a sulfuric acid solution (96%) at 25 ° C. About 3.2. It may be excellent in the antistatic property, heat resistance and the like of the thermoplastic resin composition in the above range.

In embodiments, the aliphatic polyamide resin (B) is about 5 to about 40 weight of 100% by weight of the total base resin (A + B) comprising the rubber-modified aromatic vinyl copolymer resin and the aliphatic polyamide resin %, For example from about 15 to about 35% by weight. In the above range, the mechanical properties of the thermoplastic resin composition may be excellent in antistatic properties.

(C) polyetheresteramide block copolymer

Polyetheresteramide block copolymer according to an embodiment of the present invention is to improve the antistatic properties of the thermoplastic resin composition (test piece), etc., a polyetheresteramide block copolymer commonly used as an antistatic agent Aminocarboxylic acids, lactams or diamine-dicarboxylates having 6 or more carbon atoms; Polyalkylene glycols; And a block copolymer of a reaction mixture containing dicarboxylic acid having 4 to 20 carbon atoms.

In embodiments, the salt of the amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms, ω-aminocapronic acid, ω-aminoenanthate, ω-aminocaprylic acid, ω-aminofelcon Aminocarboxylic acids such as acid, ω-aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid and the like; Lactams such as caprolactam, enanthlactam, capryllactam, lauryl lactam and the like; And salts of diamines and dicarboxylic acids such as salts of hexamethylenediamine-adipic acid, salts of hexamethylenediamine-isophthalic acid, and the like. For example, 1,2-aminododecanoic acid, caprolactam, salts of hexamethylenediamine-adipic acid, and the like can be used.

In an embodiment, the polyalkylene glycol may include polyethylene glycol, poly (1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, a block of ethylene glycol and propylene glycol or random air. A copolymer, a copolymer of ethylene glycol and tetrahydrofuran, etc. can be illustrated. For example, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, etc. can be used.

In specific embodiments, examples of the dicarboxylic acid having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, dodecanoic acid, and the like.

In embodiments, the bond of the amino carboxylic acid, lactam or diamine-dicarboxylic acid salt of 6 or more carbon atoms; and the polyalkylene glycol; may be an ester bond, the amino carboxylic acid, lactam or of 6 or more carbon atoms The combination of the diamine-dicarboxylic acid salt and the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, and the combination of the polyalkylene glycol; and the dicarboxylic acid having 4 to 20 carbon atoms; It may be an ester bond.

In an embodiment, the polyetheresteramide block copolymer may be prepared by a known synthesis method, for example, according to the synthesis method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Publication No. 55-133424. Can be.

In an embodiment, the polyetheresteramide block copolymer can comprise about 10 to about 95 weight percent of the polyether-ester block. It may be excellent in the antistatic property, heat resistance and the like of the thermoplastic resin composition in the above range.

In embodiments, the polyetheresteramide block copolymer may be included in an amount of about 1 to about 15 parts by weight, such as about 2 to about 10 parts by weight, based on about 100 parts by weight of the base resin (A + B). In the above range, the antistatic property, impact resistance (impact strength) and the like of the thermoplastic resin composition may be excellent.

(D) saturated fatty acid bisamide

Saturated fatty acid bis amide according to one embodiment of the present invention, together with the aliphatic carboxylic acid ester compound, can improve the surface hydrophobicity, mold release property, etc., without deterioration of the antistatic properties of the thermoplastic resin composition, and the like Bis amides can be used.

In embodiments, the saturated fatty acid bisamide is methylene bis stearamide, methylene bis oleamide, ethylene bis stearamide, ethylene bis oleamide, Hexamethylene bis stearamide, hexamethylene bis oleamide, combinations thereof, and the like.

In embodiments, the saturated fatty acid bis amide may be included from about 0.1 to about 5 parts by weight, for example from about 0.1 to about 2 parts by weight, based on about 100 parts by weight of the base resin (A + B). In the above range, the surface hydrophobicity, mold release property and the like of the thermoplastic resin composition may be excellent.

(E) aliphatic carboxylic acid ester compound

The aliphatic carboxylic acid ester compound according to one embodiment of the present invention is capable of improving surface hydrophobicity, mold release property, and the like, together with a saturated fatty acid bis amide, without deterioration of antistatic properties of the thermoplastic resin composition, and having 10 to 100 carbon atoms. It may be a dehydration product of an aliphatic carboxylic acid of and a monovalent or polyhydric alcohol having 2 to 50 carbon atoms.

In an embodiment, as the aliphatic carboxylic acid ester compound, pentaerythritol tetrastearate, glycerol monostearate, palmityl palmitate, stearyl stearate, or a combination thereof may be used.

In embodiments, the aliphatic carboxylic acid ester compound may be included in about 0.1 to about 10 parts by weight, for example about 1 to about 7 parts by weight, based on about 100 parts by weight of the base resin (A + B). In the above range, the surface hydrophobicity, mold release property and the like of the thermoplastic resin composition may be excellent.

In an embodiment, the weight ratio (C: (D + E)) of the polyetheresteramide block copolymer (C) and the saturated fatty acid bis amide (D) and aliphatic carboxylic acid ester compound (E) is from about 1: 0.2 to About 1: 1, for example, about 1: 0.43 to about 1: 0.75. In the above range, the thermoplastic resin composition may have better antistatic property, surface hydrophobicity, release property, and the like.

In embodiments, the weight ratio (D: E) of the saturated fatty acid bis amide (D) and the aliphatic carboxylic acid ester compound (E) is about 1: 2 to about 1: 8, for example about 1: 2 to about 1: 6, specifically about 1: 3 to about 1: 5. In the above range, the surface hydrophobicity, mold release property, and the like of the thermoplastic resin composition may be more excellent.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. The additives may include, but are not limited to, flame retardants, fillers, antioxidants, anti drip agents, lubricants, mold release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, and the like. When using the additive, the content may be about 0.001 to about 40 parts by weight, for example about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition according to an embodiment of the present invention may be in the form of pellets mixed with the components and melt-extruded at about 200 to about 280 ° C, for example, about 220 to about 250 ° C, using a conventional twin screw extruder. Can be.

In an embodiment, the thermoplastic resin composition has a surface resistance value measured in accordance with ASTM D257 of about 1 × 10 ⁹ to about 2 × 10 ¹⁰ Ω / sq. (Square), for example about 7 × 10 ⁹ to about 1 X 10 ¹⁰ Ω / sq.

In an embodiment, the thermoplastic resin composition may have a half-life of about 0.1 to about 2 seconds, for example about 0.5 to about 1 second, as measured by KS K 0555.

In an embodiment, the thermoplastic resin composition is prepared by dropping 3 μl of distilled water into a 100 mm × 100 mm size specimen based on a water drop shape analysis method, and then measuring the surface of the specimen by using a drop shape analyzer (DSA 100). The droplet contact angle of may be about 92 to about 105 degrees, for example about 95 to about 100 degrees.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in a pellet form, and the prepared pellet may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art. Since the molded article is excellent in antistatic property, surface hydrophobicity, mechanical properties, balance of these properties, etc., it is useful as interior / exterior materials, interior / exterior materials for automobiles, building exterior materials, etc. of electrical / electronic products.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, the specification of each component used in the Example and the comparative example is as follows.

(A) Rubber Modified Aromatic Vinyl Copolymer Resin

The following (A1) rubber-modified aromatic vinyl graft copolymer 30% by weight and (A2) aromatic vinyl copolymer resin 70% by weight were used in combination.

(A1) rubber modified aromatic vinyl graft copolymer

45-wt% butadiene rubber (average particle size: 310 nm) was used g-ABS graft copolymerized with 55 wt% styrene and acrylonitrile (weight ratio 75/25).

(A2) aromatic vinyl copolymer resin

SAN resin (weight average molecular weight: 130,000 g / mol) polymerized with 75% by weight of styrene and 25% by weight of acrylonitrile was used.

(B) polyamide resin

As the aliphatic polyamide resin (B1), polyamide 6 (manufactured by Kepitchemtech, product name: EN-300) was used.

(B2) As the aromatic polyamide resin, polyamide 6T (manufacturer: DuPont, product name: HTN 501) was used.

(C) polyetheresteramide block copolymer

PELECTRON AS (PA6-PEO, manufactured by Sanyo) was used.

(D) saturated fatty acid bisamide

Ethylene bis stearamide (manufacturer: Shin-Won Chem, product name: HI-LUB B-50) was used.

(E) aliphatic carboxylic acid ester compound

LOXIOL P861 (long chain (C15 ~ C25) ester of pentaerythritol, manufacturer: Emery oleochemicals) was used.

(F) antistatic agent

PP-PEO olefin antistatic agent (manufacturer: Sanyo, product name: UC) was used.

Example  1 to 4 and Comparative example  1 to 4

Each of the components was added in an amount as described in Table 1 below, followed by extrusion at 230 ° C. to prepare pellets. Extrusion was performed using a twin screw extruder having a diameter of L / D = 36 and 45 mm, and the prepared pellets were dried at 80 ° C. for at least 2 hours, and then injected into a specimen at a 6 Oz injection machine (molding temperature 230 ° C., mold temperature: 60 ° C.). Was prepared. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Table 1 below.

Property measurement method

(1) Surface resistance value (unit: ohm / sq.): Based on ASTMD257, it measured by the surface resistance measuring apparatus (manufacturer: Mitsubishi Chemical, apparatus name: Hiresta-UP (MCP-HT450)).

(2) Half life (unit: second): Based on KS K 0555, the half life of the large voltage was measured with the following method about five 4.5 cm x 4.5 cm sized specimens.

① Connect the half-life meter and synchrocorp or recorder.

② Set the applied voltage as (+) 10,000V.

③ Adjust the distance from the tip of the settling pole to the face of the turntable to 20 mm and the distance from the electrode plate to the face of the turntable to 15 mm.

④ Remove the electricity by attaching one specimen to the attachment frame with the surface facing up.

⑤ Start the application of 10,000 V while rotating the turntable, and after 30 seconds, finish the application and measure the time (seconds) until the counter voltage decays in half while rotating the turntable in that state.

(3) Contact angle (unit: °): Based on the Water Drop Shape Analysis method, 3 μl of distilled water was dropped into a 100 mm × 100 mm size specimen, and then the water droplet contact angle was measured using a drop shape analyzer (DSA 100). It measured 6 times and calculated the average value.

	Example				Comparative example
	One	2	3	4	One	2	3	4
(A) (% by weight)	85	85	70	70	70	70	70	70
(B1) (wt%)	15	15	30	30	-	30	30	30
(B2) (wt%)	-	-	-	-	30	-	-	-
(C) (parts by weight)	8	8	8	8	8	-	8	8
(D) (parts by weight)	0.5	One	0.5	One	One	One	6	-
(E) (parts by weight)	3	5	3	5	5	5	-	6
(F) (parts by weight)	-	-	-	-	-	8	-	-
Surface resistance value (Ω / sq.)	8 × 10 9	8 × 10 9	8 × 10 9	8 × 10 9	4 × 10 11	5 × 10 11	1 × 10 10	9 × 10 9
Half-life (seconds)	0.2	0.2	0.2	0.2	4	4	0.5	0.4
Contact angle (°)	98	103	97	98	98	105	88	85

* Parts by weight: parts by weight based on 100 parts by weight of the base resin (A + B)

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in both antistatic property and surface hydrophobicity.

On the other hand, when the aliphatic polyamide resin (B1) is not used (Comparative Example 1) or the polyetheresteramide block copolymer is not used (Comparative Example 2), antistatic properties (surface resistance and Half-life) and the like, and it is understood that the surface hydrophobicity and the like decrease when the saturated fatty acid bisamide (D) or the aliphatic carboxylic acid ester compound (E) is not applied (Comparative Examples 3 and 4).

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (12)

1. Rubber modified aromatic vinyl copolymer resins;

   Aliphatic polyamide resins;

   Polyetheresteramide block copolymers;

   Saturated fatty acid bis amide; And

   Aliphatic carboxylic acid ester compound; thermoplastic resin composition comprising a.
2. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises about 60 to about 95 wt% of the rubber-modified aromatic vinyl copolymer resin and about 5 to about 40 wt% of the aliphatic polyamide resin. And about 1 to about 15 parts by weight of the polyetheresteramide block copolymer, about 0.1 to about 5 parts by weight of the saturated fatty acid bisamide, and about 0.1 to about 10 parts by weight of the aliphatic carboxylic acid ester compound. Thermoplastic resin composition.
3. The thermoplastic resin composition of claim 1 or 2, wherein the rubber modified aromatic vinyl copolymer resin comprises a rubber modified vinyl graft copolymer and an aromatic vinyl copolymer resin.
4. The thermoplastic resin composition of claim 3, wherein the rubber-modified vinyl graft copolymer is a graft polymerized monomer mixture including an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer.
5. The method of claim 1, wherein the polyetheresteramide block copolymer is selected from the group consisting of amino carboxylic acids, lactams or diamine-dicarboxylates having 6 or more carbon atoms; Polyalkylene glycols; And a dicarboxylic acid having 4 to 20 carbon atoms; and a block copolymer of a reaction mixture comprising a thermoplastic resin composition.
6. 6. The saturated fatty acid bisamide according to any one of claims 1 to 5, wherein the saturated fatty acid bisamide is methylene bis stearamide, methylene bis oleamide, ethylene bis stearamide, ethylene bis oleamide, hexamethylene bis stearamide and hexamethylene bis oleate. A thermoplastic resin composition comprising at least one of amides.
7. The aliphatic carboxylic acid ester compound is a dehydration product of an aliphatic carboxylic acid having 10 to 100 carbon atoms and a monovalent or polyhydric alcohol having 2 to 50 carbon atoms. Thermoplastic resin composition.
8. 8. The thermoplastic resin composition of claim 1, wherein the weight ratio of the saturated fatty acid bis amide and the aliphatic carboxylic acid ester compound is from about 1: 2 to about 1: 8. 9.
9. 9. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a surface resistance value of about 1 × 10 ⁹ to about 2 × 10 ¹⁰ Ω / sq. Measured according to ASTM D257. Thermoplastic resin composition.
10. 10. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a half-life of about 0.1 seconds to about 2 seconds as measured by KS K 0555. 11.
11. The water droplet contact angle of any one of claims 1 to 10, wherein the thermoplastic resin composition has 3 μl of distilled water dropped into a 100 mm × 100 mm size specimen, and the contact angle of the water droplet on the surface of the specimen measured by a contact angle measuring instrument is about 92 to about. It is 105 degrees, The thermoplastic resin composition characterized by the above-mentioned.
12. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 11.