KR102240470B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention comprises 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 10 to 50 parts by weight of a flame retardant excluding a phosphorus compound; 1 to 15 parts by weight of an aliphatic polyamide resin; 1 to 6 parts by weight of a polyether esteramide block copolymer; And 0.5 to 2.5 parts by weight of polyalkylene glycol having a weight average molecular weight of 10,000 to 40,000 g/mol. The thermoplastic resin composition is excellent in antistatic properties, flame retardancy, impact resistance, and balance of physical properties thereof.

Description

Thermoplastic resin composition and molded article formed therefrom TECHNICAL FIELD [THERMOPLASTIC RESIN COMPOSITION AND ARTICLE PRODUCED 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 excellent in antistatic properties, flame retardancy, and balance of properties thereof, and a molded article formed therefrom.

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

However, plastic products made from conventional thermoplastic resin compositions have little ability to absorb moisture in the air and accumulate without releasing generated static electricity, so dust in the air may be adsorbed, resulting in surface contamination and electrostatic shock, and malfunction of the device. Otherwise, it may cause a malfunction.

In order to secure the antistatic properties of the thermoplastic resin composition, an antistatic agent may be used, but an excessive amount of an antistatic agent is required to obtain an appropriate antistatic property. In this case, the flame retardancy, impact resistance, and compatibility of the thermoplastic resin composition There is a risk of deterioration.

Accordingly, there is a need to develop a thermoplastic resin composition excellent in antistatic properties, flame retardancy, impact resistance, and balance of properties thereof.

The background technology of the present invention is disclosed in Korean Patent Application Publication No. 10-2014-0135790 and the like.

An object of the present invention is to provide a thermoplastic resin composition excellent in antistatic properties, flame retardancy, impact resistance, and balance of properties thereof.

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

All of 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 includes 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 10 to 50 parts by weight of a flame retardant excluding a phosphorus compound; 1 to 15 parts by weight of an aliphatic polyamide resin; 1 to 6 parts by weight of a polyether esteramide block copolymer; And 0.5 to 2.5 parts by weight of polyalkylene glycol having a weight average molecular weight of 10,000 to 40,000 g/mol.

2. In the first embodiment, the rubber-modified aromatic vinyl-based copolymer resin may include a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.

3. In the above 1 or 2 embodiments, the rubber-modified vinyl-based graft copolymer may be obtained by graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a rubbery polymer.

4. In the above 1 to 3 embodiments, the rubber-modified vinyl-based graft copolymer is contained in an amount of 20 to 50% by weight of 100% by weight of the rubber-modified aromatic vinyl-based copolymer resin, and the aromatic vinyl-based copolymer resin is It may be included in 50 to 80% by weight of 100% by weight of the rubber-modified aromatic vinyl-based copolymer resin.

5. In the above 1 to 4 embodiments, the flame retardant may include a halogen-based flame retardant and an antimony-based flame retardant.

6. In the above 1-5 embodiments, the weight ratio of the halogen-based flame retardant and the antimony-based flame retardant may be 2:1 to 8:1.

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

8. In the above 1 to 7 embodiments, the weight ratio of the aliphatic polyamide resin and the polyether esteramide block copolymer may be 1.2:1 to 3:1.

9. In the above 1 to 8 embodiments, the weight ratio of the polyetheresteramide block copolymer and the polyalkylene glycol may be 1.1:1 to 8:1.

10. In the above embodiments 1 to 9, the thermoplastic resin composition may have a flame retardancy of V-0 of a 2 mm-thick injection specimen measured by the UL-94 vertical test method.

11. In the above 1-10 embodiments, the thermoplastic resin composition may have a surface resistance value of 1 × 10 ⁹ to 3 × 10 ¹¹ Ω/sq of a 3.2 mm-thick injection specimen measured according to ASTM D257.

12. In the 1 to 11 embodiments, the thermoplastic resin composition may have a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of 15 to 30 kgf·cm/cm.

13. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of the above 1 to 12.

The present invention has the effect of the present invention to provide a thermoplastic resin composition excellent in antistatic properties, flame retardancy, impact resistance, and balance of physical properties thereof, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention includes (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) flame retardants excluding phosphorus compounds; (C) aliphatic polyamide resin; (D) polyetheresteramide block copolymer; And (E) polyalkylene glycol.

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

(A) Rubber-modified aromatic vinyl copolymer resin

The rubber-modified aromatic vinyl-based copolymer resin according to an embodiment of the present invention may include (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.

(A1) Rubber-modified vinyl-based graft copolymer

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

In a specific embodiment, the rubbery polymer includes a diene-based rubber such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene), and a saturated rubber hydrogenated to the diene-based rubber, isoprene rubber, and 2 to carbon atoms. 10 alkyl (meth)acrylate rubber, a copolymer of alkyl (meth)acrylate and styrene having 2 to 10 carbon atoms, ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be exemplified. These may be applied alone or in combination of two or more. For example, diene rubber, (meth)acrylate rubber, and the like can be used, and specifically, butadiene rubber, butyl acrylate rubber, and the like can be used.

In a specific embodiment, the rubbery polymer (rubber particles) may have an average particle size of 0.05 to 6 µm, for example 0.15 to 4 µm, specifically 0.25 to 3.5 µm. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance properties. Here, the average particle size (z-average) of the rubbery polymer (rubber particle) can be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex is filtered through a mesh to remove coagulation generated during the rubbery polymer polymerization, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and filled with distilled water to prepare a sample. , 10 ml of a sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size meter (malvern, nano-zs).

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

In a specific embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like can be exemplified. These can be used alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be 10 to 90% by weight, for example, 40 to 90% by weight of 100% by weight of the monomer mixture. In the above range, the processability and impact resistance of the thermoplastic resin composition may be excellent.

In a specific embodiment, the vinyl cyanide-based monomer is copolymerizable with the aromatic vinyl-based, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. Can be illustrated. These can be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be 10 to 90% by weight, for example, 10 to 60% by weight of 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent chemical resistance and mechanical properties.

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

In a specific embodiment, the rubber-modified vinyl-based graft copolymer is a copolymer (g-ABS) in which an aromatic vinyl-based styrene monomer and an acrylonitrile monomer, a vinyl cyanide-based compound are grafted to a butadiene-based rubbery polymer, butadiene-based A copolymer (g-MBS) grafted with methyl methacrylate as a monomer copolymerizable with styrene monomer, which is an aromatic vinyl compound in a rubber polymer, and styrene monomer and vinyl cyanide, which are an aromatic vinyl compound in a butyl acrylate-based rubber polymer. An acrylate-styrene-acrylonitrile graft copolymer (g-ASA), which is a copolymer grafted with the compound acrylonitrile monomer, may be exemplified.

In a specific embodiment, the rubber-modified vinyl-based graft copolymer may be included in an amount of 20 to 50% by weight, for example, 25 to 45% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity (molding processability), appearance characteristics, and balance of physical properties thereof.

(A2) Aromatic vinyl copolymer resin

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

In a specific embodiment, the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer and a monomer copolymerizable with an aromatic vinyl-based monomer, and then polymerizing the same, and the polymerization is emulsion polymerization, suspension polymerization, bulk polymerization, etc. It can be carried out by a known polymerization method of.

In a specific embodiment, the aromatic vinyl-based monomer is styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinyl naphthalene, etc. can be used. These may be applied alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be 20 to 90% by weight, for example, 30 to 80% by weight of the total 100% by weight of the aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance and fluidity.

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

In a specific embodiment, the vinyl cyanide monomer may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc., but is not limited thereto. Does not. These can be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used.

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

In a specific embodiment, the content of the monomer copolymerizable with the aromatic vinyl-based monomer may be 10 to 80% by weight, for example, 20 to 70% by weight, based on the total 100% by weight of the aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance and fluidity.

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

In a specific embodiment, the aromatic vinyl-based copolymer resin may be included in 50 to 80% by weight, for example, 55 to 75% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity (molding processability), and the like.

(B) Flame retardant excluding phosphorus compounds

The flame retardant according to an embodiment of the present invention is capable of improving the flame retardancy of a thermoplastic resin composition including a rubber-modified aromatic vinyl-based copolymer resin, and a flame retardant other than a phosphorus-based compound, for example, a halogen-based flame retardant, an antimony-based Flame retardants, combinations thereof, and the like.

In a specific embodiment, the halogen-based flame retardant is decabromodiphenyl oxide, decabromodiphenylethane, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, brominated epoxy oligomer, octave Lomotrimethylphenylindane, ethylenebistetrabromophthalimide, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, etc. can be illustrated, Antimony trioxide and antimony pentoxide may be exemplified as the antimony-based flame retardant. These can be used alone or in combination of two or more.

In a specific embodiment, when the flame retardant is a combination of a halogen-based flame retardant and an antimony-based flame retardant, the weight ratio of the halogen-based flame retardant and the antimony-based flame retardant (halogen-based flame retardant: antimony-based flame retardant) is 2: 1 to 8: 1, for example 3 : It may be 1 to 7: 1. Even when a small amount of flame retardant is applied in the above range, the flame retardancy of the thermoplastic resin composition may be excellent.

In a specific embodiment, the flame retardant may be included in an amount of 10 to 50 parts by weight, for example, 15 to 40 parts by weight, specifically 20 to 35 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the content of the flame retardant is less than 10 parts by weight based on 100 parts by weight of the thermoplastic resin, there is a concern that the flame retardancy of the thermoplastic resin composition may be reduced, and if it exceeds 40 parts by weight, antistatic properties, impact resistance, etc. There is a concern.

(C) aliphatic polyamide resin

The aliphatic polyamide resin according to an embodiment of the present invention is capable of improving the antistatic properties of the thermoplastic resin composition even when a small amount of an antistatic agent (polyetheresteramide block copolymer) is applied, and a conventional aliphatic polyamide resin Can be used.

In a specific embodiment, the aliphatic polyamide resin may be polyamide 6, polyamide 11, polyamide 12, polyamide 4.6, polyamide 6.6, polyamide 6.10, a combination thereof, and the like. For example, polyamide 6, polyamide 6.6, and the like can be used.

In a specific example, the aliphatic polyamide resin has a relative viscosity (RV) of 2.0 to 3.5 dL/g, for example, 2.3 to 3.5, measured with an Ubbelodhde viscometer in a sulfuric acid solution (96%) at 25°C. It may be 3.2 dL/g. Within the above range, the thermoplastic resin composition may have excellent antistatic properties, heat resistance, and the like.

In a specific embodiment, the aliphatic polyamide resin may be included in an amount of 1 to 15 parts by weight, for example, 3 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the content of the aliphatic polyamide resin is less than 1 part by weight based on 100 parts by weight of the thermoplastic resin, there is a risk that the antistatic properties and impact strength of the thermoplastic resin composition may be lowered, and if it exceeds 15 parts by weight, flame retardancy, etc. There is a possibility that this may decrease.

(D) Polyetheresteramide block copolymer

The polyetheresteramide block copolymer according to an embodiment of the present invention is capable of improving the antistatic properties of the thermoplastic resin composition, and a polyetheresteramide block copolymer which is commonly used as an antistatic agent may be used, For example, an amino carboxylic acid, lactam, or diamine-dicarboxylate having 6 or more carbon atoms; And polyalkylene glycol; and, if necessary, a dicarboxylic acid having 4 to 20 carbon atoms;

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

In a specific embodiment, as the polyalkylene glycol, polyethylene glycol, poly(1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, block or random copolymer of ethylene glycol and propylene glycol 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 examples, examples of the dicarboxylic acid having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, and dodecanocarboxylic acid.

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

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

In a specific embodiment, the polyether esteramide block copolymer is 5 to 95% by weight of an amino carboxylic acid, lactam or diamine-dicarboxylic acid salt having 6 or more carbon atoms, for example, 35 to 65% by weight, and 5 to polyalkylene glycol. 95% by weight, for example, may be a polymer (block copolymer) of a reaction mixture containing 35 to 65% by weight, and if necessary, dicarboxylic acid having 4 to 20 carbon atoms is added to 100 parts by weight of the reaction mixture. , 70 parts by weight or less, for example, may be a polymer of the reaction mixture further comprising 5 to 65 parts by weight. Within the above range, antistatic properties and compatibility of the thermoplastic resin composition may be excellent.

In a specific embodiment, the polyetheresteramide block copolymer may have a weight average molecular weight of 3,000 to 70,000 g/mol, for example, 20,000 to 30,000 g/mol, as measured by gel permeation chromatography (GPC). . In the above range, the antistatic property of the thermoplastic resin composition may be excellent.

In a specific embodiment, the polyether esteramide block copolymer may be included in an amount of 1 to 6 parts by weight, for example, 2 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the content of the polyetheresteramide block copolymer is less than 1 part by weight based on 100 parts by weight of the thermoplastic resin, there is a concern that the antistatic properties of the thermoplastic resin composition may be deteriorated, and if it exceeds 6 parts by weight, the flame retardancy is lowered There is a risk of becoming.

In a specific embodiment, the weight ratio of the aliphatic polyamide resin and the polyether esteramide block copolymer (aliphatic polyamide resin: polyether esteramide block copolymer) is 1.2: 1 to 3: 1, for example, 1.25: 1 to It may be 2.5:1, specifically 1.5:1 to 2:1. In the above range, the antistatic property of the thermoplastic resin composition may be more excellent.

(E) polyalkylene glycol

The polyalkylene glycol of the present invention is applied to the aliphatic polyamide resin and polyether esteramide block copolymer without deteriorating the flame retardancy and impact resistance of the thermoplastic resin composition, antistatic property, flame retardancy, impact resistance, and balance of their physical properties. As a material capable of improving the like, polyalkylene glycol having a weight average molecular weight of 10,000 to 40,000 g/mol, for example, 15,000 to 30,000 g/mol measured by gel permeation chromatography (GPC) can be used. have. When the weight average molecular weight of the polyalkylene glycol is less than 10,000 g/mol, there is a concern that the flame retardancy, impact strength, and antistatic properties of the thermoplastic resin composition may be deteriorated, and when it exceeds 40,000 g/mol, flame retardancy and impact strength , There is a risk of deterioration of antistatic properties, etc.

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

In a specific embodiment, the polyalkylene glycol may be included in an amount of 0.5 to 2.5 parts by weight, for example, 0.5 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the polyalkylene glycol is less than 0.5 parts by weight based on 100 parts by weight of the thermoplastic resin, there is a risk that the antistatic property and flame retardancy of the thermoplastic resin composition may be deteriorated, and when it exceeds 2.5 parts by weight, the antistatic property , There is a risk of deterioration of flame retardancy and the like.

In a specific embodiment, the weight ratio of the polyether esteramide block copolymer and the polyalkylene glycol (polyether ester amide block copolymer: polyalkylene glycol) is 1.1: 1 to 8: 1, for example, 1.3: 1 to It can be 6: 1. In the above range, antistatic properties, flame retardancy, and balance of properties thereof of the thermoplastic resin composition may be more excellent.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. Examples of the additives include a lubricant, a nucleating agent, a stabilizer, a release agent, a pigment, a dye, and a mixture thereof, but are not limited thereto. When using the additive, the content may be 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, based on 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 obtained by mixing the above constituents and melt-extruding at 200 to 280°C, for example, 210 to 250°C using a conventional twin screw extruder.

In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 of a 2 mm thick injection specimen measured by the UL-94 vertical test method.

In a specific example, the thermoplastic resin composition has a surface resistance value of a 3.2 mm-thick injection specimen measured according to ASTM D257 of 1 × 10 ⁹ to 3 × 10 ¹¹ Ω/sq, for example, 1 × 10 ¹⁰ to 1 × 10 ^It may be 11 Ω/sq.

In a specific example, the thermoplastic resin composition may have a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of 15 to 30 kgf·cm/cm, for example, 17.5 to 25 kgf·cm/cm have.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the field to which the present invention belongs. The molded article has excellent antistatic properties, flame retardancy, impact resistance, and balance of properties thereof, and is useful as an interior/exterior material for electric/electronic products such as power boxes and multi-taps, interior/exterior materials for automobiles, exterior materials for buildings, and the like.

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

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) Rubber-modified aromatic vinyl copolymer resin

The following (A1) 25% by weight of a rubber-modified aromatic vinyl-based graft copolymer and (A2) 75% by weight of an aromatic vinyl-based copolymer resin were mixed and used.

(A1) Rubber-modified vinyl-based graft copolymer

A core-shell type graft prepared by graft copolymerization of 42% by weight of styrene and acrylonitrile (styrene/acrylonitrile: 75% by weight/25% by weight) to 58% by weight of a butadiene rubber having an average particle size of 0.3 μm Copolymer (g-ABS) was used.

(A2) Aromatic vinyl copolymer resin

A resin prepared by polymerizing 72% by weight of styrene and 28% by weight of acrylonitrile (weight average molecular weight: 135,000 g/mol) was used.

(B) flame retardant

(B1) Brominated epoxy oligomer (manufacturer: Kukdo Chemical, product name: YDB-406) was used.

(B2) Antimony trioxide (manufacturer: Ilsung antimony, product name: ANTIS W) was used.

(B3) As a phosphorus-based flame retardant, bisphenol-A diphosphate (manufacturer: DAIHACHI, product name: CR-741) was used.

(C) polyamide resin

(C1) As the aliphatic polyamide resin, polyamide 6 (manufacturer: KP CHEMTECH, product name: EN300) was used.

(C2) As the aromatic polyamide resin, polyamide 6T (manufacturer: Dupont, product name: ZYTEL HTN 501) was used.

(D) Polyetheresteramide block copolymer

PELECTRON AS (PA6-PEO, manufacturer: Sanyo) was used.

(E) polyalkylene glycol

(E1) Polyethylene glycol (manufacturer: Samjeon Chemical, product name: PEG20000) having a weight average molecular weight of 20,000 g/mol was used.

(E2) Polyethylene glycol (manufacturer: Samjeon Chemical, product name: PEG4000) having a weight average molecular weight of 4,000 g/mol was used.

(E3) Polyethylene glycol (manufacturer: Scientific polymer product, Inc., product name: poly(ethylene oxide) standard) having a weight average molecular weight of 50,000 g/mol was used.

Examples 1 to 6 and Comparative Examples 1 to 8

Each of the above constituents was added in an amount as shown in Tables 1 and 2 below, and then extruded at 210°C to prepare a pellet. Extrusion was performed using a twin-screw extruder with L/D=36 and diameter of 45 mm, and the prepared pellets were dried at 80°C for 2 hours or more, and then injected from a 6 Oz injection machine (molding temperature 230°C, mold temperature: 60°C) to test specimens. Was prepared. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1 and 2 below.

How to measure physical properties

(1) Flame retardancy: According to the UL-94 vertical test method, the flame retardancy of a 2 mm-thick injection specimen was measured.

(2) Surface resistance value (unit: Ω/sq): According to ASTM D257, surface resistance of a 3.2 mm thick injection specimen with a surface resistance measuring device (manufacturer: Mitsubishi Chemical, device name: Hiresta-UP (MCP-HT450)) The value was measured.

(3) Notched Izod impact strength (unit: kgf·cm/cm): According to ASTM D256, the notched Izod impact strength of a 1/8" thick specimen was measured.

Example One 2 3 4 5 6 (A) (parts by weight) 100 100 100 100 100 100 (B)
(Part by weight) (B1) 20 20 20 20 20 20 (B2) 4 4 4 4 4 4 (B3) - - - - - - (C)
(Part by weight) (C1) 5 5 5 5 5 5 (C2) - - - - - - (D) (parts by weight) 3 3 3 3 2 4 (E)
(Part by weight) (E1) 0.5 One 1.5 2 1.5 1.5 (E2) - - - - - - (E3) - - - - - - Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 Surface resistance value 1×10 ¹¹ 1×10 ¹¹ 1×10 ⁹ 1×10 ¹⁰ 1×10 ¹¹ 1×10 ¹¹ Notch Izod impact strength 17.8 18.2 18.9 19.6 19.1 18.5

Comparative example One 2 3 4 5 6 7 8 (A) (parts by weight) 100 100 100 100 100 100 100 100 (B)
(Part by weight) (B1) - 20 20 20 20 20 20 20 (B2) - 4 4 4 4 4 4 4 (B3) 24 - - - - - - - (C)
(Part by weight) (C1) 5 - 5 5 5 5 5 5 (C2) - 5 - - - - - - (D) (parts by weight) 3 3 0.5 7 3 3 3 3 (E)
(Part by weight) (E1) 1.5 1.5 1.5 1.5 - - 0.1 3 (E2) - - - - 1.5 - - - (E3) - - - - - 1.5 - - Flame retardancy V-2 V-2 V-0 V-2 V-1 V-1 V-0 V-2 Surface resistance value 1×10 ¹² 1×10 ¹¹ 1×10 ¹² 1×10 ¹¹ 1×10 ¹² 1×10 ¹² 1×10 ¹² 1×10 ¹² Notch izod
Impact strength 9.8 10.3 13.5 18.5 16.5 15.9 19.1 18.7

From the above results, it can be seen that the thermoplastic resin composition of the present invention has excellent antistatic properties, flame retardancy, impact resistance, and balance of physical properties thereof.

On the other hand, in the case of Comparative Example 1 in which the phosphorus-based flame retardant (B3) was applied instead of the flame retardant except for the phosphorus-based compound of the present invention, it can be seen that flame retardancy, impact resistance, antistatic properties, etc. are deteriorated, and aromatic polyamide instead of aliphatic polyamide resin In the case of Comparative Example 2 to which the resin (C2) is applied, it can be seen that flame retardancy and impact resistance are deteriorated, and in the case of Comparative Example 3 in which a small amount of the polyether esteramide block copolymer is applied, antistatic properties and impact resistance are deteriorated. It can be seen, and it can be seen that in the case of Comparative Example 4 in which an excessive amount of the polyether esteramide block copolymer was applied, flame retardancy and the like were deteriorated. In the case of Comparative Example 5 in which the polyalkylene glycol (E2) having a weight average molecular weight less than the range of the present invention was applied instead of the polyalkylene glycol of the present invention, it can be seen that flame retardancy, antistatic properties, etc. are deteriorated, and the weight average molecular weight In the case of Comparative Example 6 to which the polyalkylene glycol (E3) exceeding the scope of the present invention was applied, flame retardancy, antistatic properties, etc. were lowered, and impact resistance was relatively lowered compared to the examples. In addition, in the case of Comparative Example 7 in which a small amount of polyalkylene glycol is applied, it can be seen that antistatic properties, etc., are deteriorated, and in the case of Comparative Example 8 in which an excessive amount of polyalkylene glycol is applied, it can be seen that flame retardancy, antistatic properties, etc. have.

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (13)

100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin;
10 to 50 parts by weight of a flame retardant excluding phosphorus compounds;
1 to 15 parts by weight of an aliphatic polyamide resin;
1 to 6 parts by weight of a polyether esteramide block copolymer; And
A thermoplastic resin composition comprising: 0.5 to 2.5 parts by weight of polyalkylene glycol having a weight average molecular weight of 10,000 to 40,000 g/mol.
The thermoplastic resin composition of claim 1, wherein the rubber-modified aromatic vinyl-based copolymer resin comprises a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.
[3] The thermoplastic resin composition of claim 2, wherein the rubber-modified vinyl-based graft copolymer is obtained by graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a rubbery polymer.
The method of claim 2, wherein the rubber-modified vinyl-based graft copolymer is contained in an amount of 20 to 50% by weight of 100% by weight of the rubber-modified aromatic vinyl-based copolymer resin, and the aromatic vinyl-based copolymer resin is the rubber-modified aromatic A thermoplastic resin composition comprising 50 to 80% by weight of 100% by weight of the vinyl-based copolymer resin.
The thermoplastic resin composition of claim 1, wherein the flame retardant comprises a halogen-based flame retardant and an antimony-based flame retardant.
The thermoplastic resin composition according to claim 5, wherein the weight ratio of the halogen-based flame retardant and the antimony-based flame retardant is 2:1 to 8:1.
The method of claim 1, wherein the polyetheresteramide block copolymer is an amino carboxylic acid, lactam, or diamine-dicarboxylate having 6 or more carbon atoms; Polyalkylene glycol; And a dicarboxylic acid having 4 to 20 carbon atoms;
The thermoplastic resin composition according to claim 1, wherein a weight ratio of the aliphatic polyamide resin and the polyether esteramide block copolymer is 1.2:1 to 3:1.
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the polyetheresteramide block copolymer and the polyalkylene glycol is 1.1:1 to 8:1.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flame retardancy of V-0 of a 2 mm-thick injection specimen measured by a UL-94 vertical test method.
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a surface resistance value of 1 × 10 ⁹ to 3 × 10 ¹¹ Ω/sq of a 3.2 mm-thick injection specimen measured according to ASTM D257.
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of 15 to 30 kgf·cm/cm.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 12.