KR101980018B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

상기 화학식 1에서, R₁ 및 R₂는 각각 독립적으로 탄소수 1 내지 5의 알킬기이고, R₃ 및 R₄는 각각 독립적으로 탄소수 2 내지 15의 알킬렌기이고, A₁ 및 A₂는 각각 독립적으로 글리시독시기, 에폭시기, 또는 디알콕시아릴기이며, n의 평균값은 10 내지 80이다.The thermoplastic resin composition of the present invention comprises 100 parts by weight of a thermoplastic resin containing 20 to 65% by weight of an acrylate-based rubber-modified vinyl-based graft copolymer and 35 to 80% by weight of an aromatic vinyl-based copolymer resin; 0.3 to 6 parts by weight of a siloxane compound represented by the following formula (1); And 0.3 to 6 parts by weight of zinc oxide having an average particle size of 0.3 to 3 탆 and a specific surface area BET of 1 to 10 m ² / g. The thermoplastic resin composition is excellent in weather resistance (discoloration resistance), mar resistance, antibacterial property, impact resistance and the like.
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, R ₃ and R ₄ are each independently an alkylene group having 2 to 15 carbon atoms, A ₁ and A ₂ are each independently a gly An epoxy group, or a dialkoxyaryl group, and the average value of n is 10 to 80. [

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition and a molded article obtained from the thermoplastic resin composition.

The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in weather resistance (discoloration resistance), mar resistance, antibacterial property, impact resistance and the like, and a molded article produced therefrom.

As the thermoplastic resin, rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) and the like have excellent mechanical properties, processability, appearance and the like, Automobile interior / exterior materials, building exterior materials, and the like.

However, yellowing phenomenon and various life scratches may occur with the use of such an article made of rubber-modified aromatic styrenic copolymer resin over time, and there is a possibility that various microbes may propagate on the surface.

 Therefore, it is necessary to develop a thermoplastic resin composition excellent in weatherability (discoloration resistance), mar resistance, antimicrobial property and the like.

The background art of the present invention is disclosed in Korean Patent Registration No. 10-1399390.

An object of the present invention is to provide a thermoplastic resin composition excellent in weather resistance (discoloration resistance), mar resistance, antibacterial property, impact resistance 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.

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin containing 20 to 65% by weight of an acrylate-based rubber-modified vinyl-based graft copolymer and 35 to 80% by weight of an aromatic vinyl copolymer resin; 0.3 to 6 parts by weight of a siloxane compound represented by the following formula (1); And 0.3 to 6 parts by weight of zinc oxide having an average particle size of 0.3 to 3 탆 and a specific surface area BET of 1 to 10 m ² / g:

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, R ₃ and R ₄ are each independently an alkylene group having 2 to 15 carbon atoms, A ₁ and A ₂ are each independently a gly An epoxy group, or a dialkoxyaryl group, and the average value of n is 10 to 80. [

In an embodiment, the acrylate-based rubber-modified vinyl-based graft copolymer may be obtained by graft-polymerizing an acrylate-based rubbery polymer with a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer.

In an embodiment, the aromatic vinyl-based copolymer resin may be an aromatic vinyl-based monomer and a polymer of a monomer copolymerizable with the aromatic vinyl-based monomer.

In the specific examples, the siloxane compound represented by the formula (1) may be a dialkoxy aryl group in which A ₁ and A ₂ are each a halogen atom, and the average value of n may be 30 to 40.

In an embodiment, the siloxane compound comprises at least one of a compound represented by the following formula (1a), a compound represented by the following formula (1b), a compound represented by the following formula (1c), and a compound represented by the following formula Thermoplastic resin composition:

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above formulas (1a), (1b), (1c) and (1d), the average value of n is 20 to 60 and each R is independently an alkyl group having 1 to 10 carbon atoms.

In an embodiment, the zinc oxide may have a size ratio (B / A) of 0 to 1 between peak A in the region of 370 to 390 nm and peak B in the region of 450 to 600 nm in photo luminescence measurement.

In an embodiment, the zinc oxide has a peak position 2θ value in the range of 35 to 37 ° in the X-ray diffraction (XRD) analysis, and the crystallite size ) Value can be from 1,000 to 2,000 A:

[Formula 1]

Microcrystalline size (D) =

In the above formula 1, K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).

In embodiments, the weight ratio of the siloxane compound and the zinc oxide may be from 1: 0.1 to 1: 4.

In an embodiment, the thermoplastic resin composition may be prepared by measuring the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) using a colorimeter on a 50 mm × 90 mm × 3 mm sized injection specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test using a colorimeter, and then the color change calculated according to the following formula (2) ? E) can be less than or equal to 3.5:

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

In a specific example, the thermoplastic resin composition may have a difference in glossiness (ΔGloss (60 °)) according to the following formula 3: 17 or less:

[Formula 3]

ΔGloss (60 °) = | G ₁₀ - G ₀ |

In the above formula 3, G ₀ is a 60 ° specular gloss measured by a friction rubbing tester (crockmeter) according to ASTM D523 for a 10 cm × 15 cm specimen, and G ₁₀ is a ten- And then measured by the same method.

In the specific example, the thermoplastic resin composition was prepared by inoculating Staphylococcus aureus and Escherichia coli into a 5 cm x 5 cm size specimen and culturing it under the conditions of 35 ° C and RH 90% for 24 hours in accordance with JIS Z 2801 antibacterial evaluation method The antibacterial activity value may be 2 to 6 and 2 to 6, respectively.

Another aspect of the present invention relates to a molded article. And the molded article is formed from the thermoplastic resin composition.

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition excellent in weather resistance (discoloration resistance), mar resistance, antimicrobial property, impact resistance and the like, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a thermoplastic resin comprising (A1) an acrylate rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl copolymer resin; (B) a siloxane compound; And (C) zinc oxide.

(A) a thermoplastic resin

The thermoplastic resin of the present invention may be a rubber-modified vinyl-based copolymer resin comprising (A1) an acrylate rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl copolymer resin.

(A1) acrylate rubber-modified aromatic vinyl-based graft copolymer

The acrylate rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention is capable of improving the weather resistance, impact resistance, chemical resistance, etc. of the thermoplastic resin composition. The acrylic rubber- The monomer mixture containing the vinyl cyanide monomer may be graft-polymerized. For example, the acrylate-based rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing an acrylate-based rubbery polymer with a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer, The monomer mixture may further include a monomer that imparts processability and heat resistance to the graft polymerization. The polymerization may be carried out by a known polymerization method such as emulsion polymerization or suspension polymerization. The acrylate-based rubber-modified vinyl-based graft copolymer may form a core (rubbery polymer) -shell (copolymer of a monomer mixture) structure, but is not limited thereto.

In the specific examples, the acrylate-based rubbery polymer may include a copolymer of an alkyl (meth) acrylate rubber, an alkyl (meth) acrylate, and an aromatic vinyl compound. These may be used alone or in combination of two or more. Examples thereof include alkyl acrylate rubber having 2 to 10 carbon atoms, alkyl acrylate having 2 to 10 carbon atoms and copolymer of styrene, and combinations thereof. Specifically, butyl acrylate rubber, butyl acrylate and styrene Copolymers thereof, combinations thereof, and the like can be used. The copolymer of the alkyl (meth) acrylate and the aromatic vinyl compound may be a polymer obtained by polymerizing 70 to 90% by weight of an alkyl (meth) acrylate and 10 to 30% by weight of an aromatic vinyl compound, but is not limited thereto .

In an embodiment, the acrylate-based rubbery polymer (rubber particles) may have an average particle size (Z-average) of 0.1 to 0.5 탆, for example, 0.15 to 0.4 탆. Within the above range, the thermoplastic resin composition may have excellent weather resistance, impact resistance, chemical resistance, and the like.

In an embodiment, the acrylate-based rubbery polymer may be a mixture of two or more kinds of acrylate-based rubbery polymers having different average particle diameters. For example, a mixture of 40 to 80% by weight of a first acrylate-based rubbery polymer having an average particle size of 0.1 to 0.2 μm and 20 to 60% by weight of a second acrylate-based rubbery polymer having an average particle size of 0.2 to 0.5 μm But may be, but not limited to, a mixture having a modal particle size distribution. When the acrylate-based rubbery polymer in the form of a mixture is used, a thermoplastic resin composition having a uniform impact resistance property can be obtained.

In an embodiment, the content of the acrylate-based rubbery polymer may be 30 to 70% by weight, such as 40 to 60% by weight, based on 100% by weight of the entire acrylate-based rubber-modified vinyl-based graft copolymer, (Including aromatic vinyl monomers and vinyl cyanide monomers) may be 30 to 70% by weight, for example, 40 to 60% by weight, based on 100% by weight of the entire acrylate-based rubber-modified vinyl-based graft copolymer. Within the above range, the thermoplastic resin composition may have excellent weather resistance, impact resistance, chemical resistance, and the like.

In an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and may be selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer may be 10 to 90% by weight, for example, 40 to 90% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition can be excellent in workability, colorability, and the like.

In the specific examples, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, For example. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like can be used. The content of the vinyl cyanide monomer may be 10 to 90% by weight, for example, 10 to 60% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent chemical resistance and mechanical properties.

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

In an embodiment, the acrylate-based rubber-modified vinyl-based graft copolymer may be an acrylate-styrene-acrylonitrile graft copolymer (g-ASA).

In an embodiment, the acrylate-based rubber-modified vinyl-based graft copolymer comprises 20 to 60% by weight of the total thermoplastic resin (acrylate-based rubber-modified vinyl-based graft copolymer and aromatic vinyl-based copolymer resin) For example, 25 to 50% by weight. In the above range, the weather resistance, impact resistance, physical properties and balance of the thermoplastic resin composition can be excellent.

(A2) an aromatic vinyl-based copolymer resin

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

In an embodiment, the aromatic vinyl-based copolymer resin may be obtained by mixing aromatic vinyl-based monomers and aromatic vinyl-based monomers with a monomer copolymerizable therewith and the like, and the polymerization may be carried out by emulsion polymerization, suspension polymerization, Of the present invention.

In an embodiment, the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene and the like can be used. These may be used 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, based on 100% by weight of the total aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

Examples of the monomer copolymerizable with the aromatic vinyl-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile. Vinyl cyanide monomers, and the like. These monomers may be used singly or in combination of two or more. 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 100% by weight of the total aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In an embodiment, the aromatic vinyl-based copolymer resin may have 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. Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

In an embodiment, the aromatic vinyl-based copolymer resin may be contained in an amount of 35 to 80% by weight, for example, 50 to 75% by weight, based on 100% by weight of the total thermoplastic resin. The impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent in the above range.

(B) a siloxane compound

The siloxane compound according to one embodiment of the present invention can increase the mar resistance by lowering the surface friction coefficient of the thermoplastic resin composition (specimen). For example, it may be represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1), R ₁ and R ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group and the like. R ₃ and R ₄ each independently represent an alkylene group having 2 to 15 carbon atoms, for example, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and the like. A ₁ and A ₂ each independently may be a glycidoxy group, an epoxy group, or a dialkoxyaryl group. The average value of n may be from 10 to 80, for example from 20 to 60.

In a specific example, the siloxane compound represented by the formula (1) may be a siloxane compound in which A ₁ and A ₂ are dialkoxy aryl groups and the average value of n is 30 to 40. The siloxane compound may have a weight average molecular weight of 2,500 to 4,000 g / mol and a polydispersion index (PDI) of 1.5 to 2.5.

In a specific example, the siloxane compound can be prepared by reacting a siloxane compound (precursor) represented by the following formula (2) with a compound represented by the following formula (3) (functional group).

(2)

In Formula 2, the average value of R ₁ , R _2, and n is as defined in Formula 1.

The siloxane compound of Formula 2 may be prepared by reacting a linear siloxane of which n is 0 with a cyclic siloxane or the like, but is not limited thereto.

(3)

In formula (3), A ₃ may be a glycidoxy group, an epoxy group, or a dialkoxyaryl group, and R ₅ may be a hydrocarbon group having 2 to 15 carbon atoms, for example, a vinyl group (CH ₂ ═CH- ), allyl group _{(CH 2 = CH-CH 2} -) and the like.

Herein, as the compound represented by the general formula (3), two or more compounds in which A ₃ and R ₅ are different from each other may be used. After the reaction, A ₃ and R ₅ are the same as those of the siloxane compounds A ₁ and A ₂ And R < ₃ > and R < ₄ >.

In embodiments, the reaction may be carried out in the presence of a catalyst. As the catalyst, a catalyst containing platinum may be used. For example, the catalyst may be a platinum element itself or a compound containing platinum, and specifically, H ₂ PtCl ₆ , Pt ₂ {[(CH ₂ ═CH) Me ₂ Si] ₂ O} ₃ , Rh [ (cod) ₂ ] BF ₄ , Rh (PPh ₃ ) ₄ Cl, Pt / C, or the like, alone or in combination. More specifically, Pt / C, for example, 10% Pt / C can be used. The amount of the catalyst to be used may be, for example, 10 to 500 ppm, for example, 50 to 150 ppm with respect to the whole reactant.

The reaction may be carried out in an organic solvent, and examples of the organic solvent include 1,2-dichloroethane, toluene, xylene, dichlorobenzene, a mixed solvent thereof, and the like, but the present invention is not limited thereto. For example in toluene.

In addition, the reaction can control the reaction temperature and the reaction time according to the reactivity of the reactants (Formula 2 and Formula 3). For example, the reaction can be carried out at a reaction temperature of 60 to 140 ° C, specifically 110 to 120 ° C, for 2 to 12 hours, for example 3 to 5 hours, but is not limited thereto.

In an embodiment, the siloxane compound may be represented by the following general formulas (1a) to (1d), but is not limited thereto.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above formulas (1a), (1b), (1c) and (1d), the average value of n is 10 to 80, for example, 20 to 60, specifically 30 to 40, and each R is independently an alkyl group having 1 to 10 carbon atoms.

In an embodiment, the siloxane compound may be contained in an amount of 0.3 to 6 parts by weight, for example, 0.5 to 5 parts by weight, specifically 1 to 3 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the siloxane compound is contained in an amount of less than 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin, fog resistance of the thermoplastic resin composition may be lowered. If the siloxane compound is more than 6 parts by weight, the impact resistance, weather resistance, There is a possibility that the antibacterial properties and the like are lowered.

(C) Zinc oxide

The zinc oxide of the present invention is capable of improving the antibacterial properties, weather resistance, etc. of the thermoplastic resin composition, and may have an average particle size of 0.3 to 3 탆, for example, 0.5 to 2 탆, as measured by a particle size analyzer, 1 to 10 m ² / g, for example, 1 to 7 m ² / g, and the purity may be 99% or more. Outside of the above range, the antibacterial properties, weather resistance, etc. of the thermoplastic resin composition may be lowered.

In embodiments, the zinc oxide may have a size ratio (B / A) of a peak A in the region of 370 to 390 nm and a peak B in the region of 450 to 600 nm of 0 to 1, for example, 0.1 to 1. The weather resistance of the thermoplastic resin composition may be more excellent in the above range.

In an embodiment of the present invention, the zinc oxide has a peak position 2θ value in the range of 35 to 37 ° in X-ray diffraction (XRD) analysis, and the measured FWHM value (Full of diffraction peak the crystallite size value calculated by applying Scherrer's equation (Equation 1) based on the width at half maximum may be 1,000 to 2,000 A, for example, 1,200 to 1,800 A. Within the above range, the thermoplastic resin composition may have excellent initial color, weather resistance, antimicrobial properties, and the like.

[Formula 1]

Microcrystalline size (D) =

In Equation 1, K is a shape factor,? Is an X-ray wavelength,? Is a FWHM value, and? Is a peak position degree.

In an embodiment, the zinc oxide is obtained by melting zinc in the form of a metal, heating it to 850 to 1,000 ° C, for example, 900 to 950 ° C to vaporize it, injecting oxygen gas, cooling the mixture to 20 to 30 ° C, If necessary, heat treatment may be carried out at 700 to 800 ° C for 30 minutes to 150 minutes while nitrogen / hydrogen gas is injected into the reactor, followed by cooling to room temperature (20 to 30 ° C).

In an embodiment, the zinc oxide may be contained in an amount of 0.3 to 6 parts by weight, for example, 0.5 to 5 parts by weight, specifically 0.5 to 2.5 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the zinc oxide is contained in an amount of less than 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin, antimicrobial properties and weather resistance of the thermoplastic resin composition may be lowered. When the zinc oxide is more than 6 parts by weight, There is a risk of degradation.

In a specific example, the weight ratio of the siloxane compound and the zinc oxide (siloxane compound: zinc oxide) is from 1: 0.1 to 1: 4, such as from 1: 0.17 to 1: 4, specifically from 1: 0.4 to 1: . In the above range, the thermoplastic resin composition may have better antimicrobial activity, scratch resistance, and the like.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition. Examples of the additives include, but are not limited to, a flame retardant, a filler, an antioxidant, a dripping inhibitor, a lubricant, a releasing agent, a nucleating agent, an antistatic agent, a stabilizer, a pigment, a dye and mixtures thereof. When the additive is used, the content thereof 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 one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding the above components at a temperature of 200 to 280 DEG C, for example 220 to 250 DEG C, using a conventional twin-screw extruder.

In an embodiment, the thermoplastic resin composition may be prepared by measuring the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) using a colorimeter on a 50 mm × 90 mm × 3 mm sized injection specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test using a colorimeter, and then the color change calculated according to the following formula (2) ? E) is 3.5 or less, for example, 0.5 to 3.5, specifically 2.0 to 3.3.

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

In a specific example, the thermoplastic resin composition may have a difference in glossiness (ΔGloss (60 °)) according to the following formula 3: 17 or less, for example, 0 to 15.

[Formula 3]

ΔGloss (60 °) = | G ₁₀ - G ₀ |

In the above formula 3, G ₀ is a 60 ° specular gloss measured by a friction rubbing tester (crockmeter) according to ASTM D523 for a 10 cm × 15 cm specimen, and G ₁₀ is a ten- And then measured by the same method.

In the specific example, the thermoplastic resin composition was prepared by inoculating Staphylococcus aureus and Escherichia coli into a 5 cm x 5 cm size specimen and culturing it under the conditions of 35 ° C and RH 90% for 24 hours in accordance with JIS Z 2801 antibacterial evaluation method The antibacterial activity value may be 2 to 6 and 2 to 6, such as 2.5 to 6 and 2.5 to 6, specifically 4.5 to 6 and 4.5 to 6, respectively.

In an embodiment, the thermoplastic resin composition may have a notch Izod impact strength of a 1/8 "thick specimen measured according to ASTM D256 of 30 to 40 kgf · cm / cm, for example, 32 to 40.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be produced in the form of pellets, and the produced pellets may be manufactured into various molded products through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded article is excellent in weather resistance, antimicrobial resistance, flaw resistance, impact resistance, fluidity (molding processability) and physical properties balance thereof, and therefore is useful as an internal / external material for electric / electronic products such as an internal material for a refrigerator.

Hereinafter, the present invention will be described in more detail by way of 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) a thermoplastic resin

Modified vinyl copolymer resin comprising 40% by weight of the following (A1) acrylate rubber-modified aromatic vinyl-based graft copolymer and 60% by weight of (A2) an aromatic vinyl-based copolymer resin.

(A1) acrylate rubber-modified aromatic vinyl-based graft copolymer

G-ASA in which 55 wt% of styrene and acrylonitrile (weight ratio: 75/25) were graft copolymerized with butyl acrylate rubber having a Z-average of 310 nm of 45 wt% was used.

 (A2) an aromatic vinyl-based copolymer resin

SAN resin (weight average molecular weight: 130,000 g / mol) in which 68 wt% of styrene and 32 wt% of acrylonitrile were polymerized was used.

(B) a siloxane compound

A siloxane compound (R: methyl group, average value of n: 20) represented by the following formula (1b) was used.

[Chemical Formula 1b]

(C) Zinc oxide

(C1) The ratio (B / A) of the peak A in the region of 370 to 390 nm and the peak B in the region of 450 to 600 nm (B / A) in the measurement of the average particle size, BET surface area, purity, And zinc oxide having a crystallite size value were used.

(C2) The ratio (B / A) of the peak A in the region of 370 to 390 nm and the peak B in the region of 450 to 600 nm (B / A) in the measurement of the average particle size, BET surface area, purity, And zinc oxide having a crystallite size value were used.

(C3) The ratio (B / A) of the peak A in the region of 370 to 390 nm and the peak B in the region of 450 to 600 nm (B / A) in the measurement of the average particle size, the BET surface area, the purity and the photo- And zinc oxide having a crystallite size value were used.

(C1) (C2) (C3) Average particle size (占 퐉) 0.6 1.1 1.1 BET surface area (m ² / g) 6 40 15 Purity (%) 99 96 99 PL size ratio (B / A) 0.28 1.17 6.49 The crystallite size (A) 1467 141 1027

How to measure property

(1) Average Particle Size (unit: 占 퐉): The average particle size was measured using a particle size analyzer (Beckman coulter LS 13 320 Particle size analyzer).

(2) BET surface area (unit: m ² / g): BET surface area was measured using a nitrogen gas adsorption method.

(3) Purity (unit:%): Purity was measured using TGA thermal analysis at a temperature of 800 ° C.

(4) PL size ratio (B / A): According to the photoluminescence measurement method, the spectrum emitted from a He-Cd laser (KIMMON company, 30 mW) having a wavelength of 325 nm at room temperature is measured by a CCD detector The temperature of the CCD detector was maintained at -70 ℃. (B / A) of the peak A in the 370 to 390 nm region and the peak B in the 450 to 600 nm region was measured. The injection specimen was subjected to PL analysis by injecting a laser into the specimen without any additional treatment. The zinc oxide powder was placed in a pelletizer having a diameter of 6 mm and pressed to form a flat specimen. Respectively.

(5) Crystallite size (unit: Å): A high resolution X-ray diffractometer (manufacturer: X'pert, device name: PRO-MRD) position 2θ value is in the range of 35 to 37 ° and is calculated by applying Scherrer's equation (Equation 1) based on the measured FWHM value (full width at half maximum of the diffraction peak). In this case, both the powder shape and the injection specimen can be measured. For the more accurate analysis, the injection specimen was subjected to heat treatment at 600 ° C. and air for 2 hours to remove the polymer resin, and then XRD analysis was carried out.

[Formula 1]

Microcrystalline size (D) =

In Equation 1, K is a shape factor,? Is an X-ray wavelength,? Is a FWHM value, and? Is a peak position degree.

Example  1 to 5 and Comparative Example  1 to 6

The above components were added in the amounts shown in Tables 2 and 3, and then extruded at 230 캜 to prepare pellets. The pellets were extruded at a temperature of 230 DEG C and a mold temperature of 60 DEG C for 6 hours at 80 DEG C for 4 hours or more, . The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Tables 2 and 3 below.

How to measure property

(L ₀ ^* , a ₀ ^* , and A ₀ ^* ) were measured using a colorimeter (KONICA MINOLTA, CM-3700A) with respect to an injection sample having a size of 50 mm × 90 mm × 3 mm. b ₀ ^* ) was measured. The injection specimen was subjected to weather resistance test for 3,000 hours according to SAE J 1960, and the color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter Next, the color change (? E) was calculated according to the following formula (2).

[Formula 2]

Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

(2) Evaluation of mar resistance The difference in glossiness (ΔGloss (60 °)) of 60 ° before and after the friction was calculated according to the following formula 3.

[Formula 3]

ΔGloss (60 °) = | G ₁₀ - G ₀ |

In the above formula 3, G ₀ is a 60 ° specular gloss measured by a friction rubbing tester (crockmeter) according to ASTM D523 for a 10 cm × 15 cm specimen, and G ₁₀ is a ten- And then measured by the same method.

(3) Antibacterial activity value: Staphylococcus aureus and E. coli were inoculated on a 5 cm × 5 cm specimen according to JIS Z 2801 antibacterial evaluation method, and then cultured at 35 ° C. and RH 90% for 24 hours.

(4) Notch Izod impact strength (unit: kgf cm / cm): According to ASTM D256, the notched Izod impact strength was measured on 1/8 "thick specimens.

Example One 2 3 4 5 (A) (parts by weight) 100 100 100 100 100 (B) (parts by weight) 3 5 0.5 3 3 (C)
(Parts by weight) (C1) 2 2 2 5 0.5 (C2) - - - - - (C3) - - - - - (B) :( C) (weight ratio) 1: 0.67 1: 0.4 1: 4 1: 1.67 1: 0.17 Color change (ΔE) 2.2 3.2 2.4 2.2 3.3 Gloss degree difference
(ΔGloss (60 °)) 2 0 15 10 0 Antimicrobial activity value
(E. coli) 6 6 6 6 2.5 Antimicrobial activity value
(Staphylococcus aureus) 6 4.5 6 6 2.5 Notch Izod impact strength 35 33 37 32 37

Comparative Example One 2 3 4 5 6 (A) (parts by weight) 100 100 100 100 100 100 (B) (parts by weight) 3 3 3 3 0.2 7 (C)
(Parts by weight) (C1) - - 0.1 7 2 2 (C2) 2 - - - - - (C3) - 2 - - - - (B) :( C) (weight ratio) 1: 0.67 1: 0.67 1: 0.03 1: 2.33 1:10 1: 0.29 Color change (ΔE) 4.5 2.3 3.6 2.1 2.2 2.5 Gloss degree difference
(ΔGloss (60 °)) 5 3 0 18 20 0 Antimicrobial activity value
(E. coli) 1.5 1.5 0.5 6 6 5 Antimicrobial activity value
(Staphylococcus aureus) 1.5 1.5 0.5 6 6 4 Notch Izod impact strength 35 35 37 29 37 28

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in weather resistance (discoloration resistance), mar resistance, antibacterial property, impact resistance and the like.

On the other hand, in the case of Comparative Example 1 using zinc oxide (C2) in which the BET surface area or the like is outside the range of the present invention, it is found that the weather resistance and antimicrobial property are lowered, and the zinc oxide (C3 ) In the case of Comparative Example 2, the antimicrobial activity and the like are lowered. It can be seen that when the content of zinc oxide is small (Comparative Example 3), antimicrobial properties and weather resistance are lowered, and when the content of zinc oxide is large (Comparative Example 4), scratch resistance and the like are lowered. In addition, when the content of the siloxane compound is small (Comparative Example 5), the fleece resistance and the like are lowered, and when the content of the siloxane compound is large (Comparative Example 6), the impact resistance and the like are lowered.

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 (12)

100 parts by weight of a thermoplastic resin comprising 20 to 65% by weight of an acrylate rubber-modified vinyl-based graft copolymer and 35 to 80% by weight of an aromatic vinyl copolymer resin;
0.3 to 6 parts by weight of a siloxane compound represented by the following formula (1); And
0.3 to 6 parts by weight of zinc oxide having an average particle size of 0.3 to 3 탆 and a specific surface area BET of 1 to 10 m ² / g,
The zinc oxide has a peak position 2θ value in the range of 35 to 37 ° and a crystallite size value according to the following formula 1 is 1,000 (X-ray diffraction (XRD) To 2,000 ANGSTROM.
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, R ₃ and R ₄ are each independently an alkylene group having 2 to 15 carbon atoms, A ₁ and A ₂ are each independently a gly An epoxy group, or a dialkoxyaryl group, and the average value of n is 10 to 80;
[Formula 1]
Microcrystalline size (D) =

In the above formula 1, K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).
The thermoplastic resin composition according to claim 1, wherein the acrylate-based rubber-modified vinyl-based graft copolymer is obtained by graft-polymerizing an acrylate-based rubbery polymer and a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer Composition.
The thermoplastic resin composition according to claim 1, wherein the aromatic vinyl-based copolymer resin is a polymer of an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer.
The thermoplastic resin composition according to claim 1, wherein the siloxane compound represented by the formula (1) is a dialkoxy aryl group in which A ₁ and A ₂ are each a halogen atom, and the average value of n is 30 to 40.
The siloxane compound according to claim 1, wherein the siloxane compound comprises at least one compound selected from the group consisting of a compound represented by the following formula (1a), a compound represented by the following formula (1b), a compound represented by the following formula (1c) and a compound represented by the following formula Wherein the thermoplastic resin composition comprises:
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above formulas (1a), (1b), (1c) and (1d), the average value of n is 20 to 60 and each R is independently an alkyl group having 1 to 10 carbon atoms.
The zinc oxide according to claim 1, wherein the zinc oxide has a size ratio (B / A) of 0 to 1 between peak A in the region of 370 to 390 nm and peak B in the region of 450 to 600 nm during photoluminescence measurement Wherein the thermoplastic resin composition is a thermoplastic resin composition.
delete The thermoplastic resin composition according to claim 1, wherein the weight ratio of the siloxane compound and the zinc oxide is 1: 0.1 to 1: 4.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) measured using a colorimeter on a 50 mm × 90 mm × 3 mm size injection mold, The specimens were subjected to weather resistance test for 3,000 hours in accordance with SAE J 1960, and the color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter and the color Wherein the change (? E) is 3.5 or less.
[Formula 2]
Color change (ΔE) =

In the formula 2, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a gloss difference (ΔGloss (60 °)) according to the following formula 3: 17 or less:
[Formula 3]
ΔGloss (60 °) = | G ₁₀ - G ₀ |
In the above formula 3, G ₀ is a 60 ° specular gloss measured by a friction rubbing tester (crockmeter) according to ASTM D523 for a 10 cm × 15 cm specimen, and G ₁₀ is a ten- And then measured by the same method.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is inoculated with a Staphylococcus aureus strain and a Escherichia coli strain in a 5 cm x 5 cm size specimen according to JIS Z 2801 antibacterial evaluation method and cultured for 24 hours at 35 ° C and RH 90% Wherein the measured antibacterial activity values are 2 to 6 and 2 to 6, respectively.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 6 and 8 to 11.