KR102653539B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention includes 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 4 to 23 parts by weight of polyetheresteramide block copolymer; 0.03 to 1 part by weight of a silver (Ag)-based compound; and 0.05 to 4 parts by weight of zinc oxide, wherein the zinc oxide consists of primary particles and secondary particles, the average particle size (D50) of the primary particles is 1 to 50 nm, and the average particle size of the secondary particles is 1 to 50 nm. It is characterized by a particle size (D50) of 0.1 to 10 ㎛. The thermoplastic resin composition has excellent antibacterial properties, transparency, antistatic properties, impact resistance, etc.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE PRODUCED THEREFROM}

The present invention relates to thermoplastic resin compositions and molded articles made therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent antibacterial properties, transparency, antistatic properties, impact resistance, etc., and molded articles manufactured therefrom.

Recently, as interest in personal health and hygiene and income levels have improved, the demand for thermoplastic resin products containing antibacterial hygiene functions is increasing. Accordingly, the number of thermoplastic resin products with antibacterial treatment that can remove or suppress bacteria from the surfaces of household goods and electronic products is increasing, and the development of stable and reliable functional antibacterial materials (antibacterial thermoplastic resin compositions) is very important. It's a task.

In order to manufacture such an antibacterial thermoplastic resin composition, the addition of an antibacterial agent is essential, and the antibacterial agent can be divided into an organic antibacterial agent and an inorganic antibacterial agent.

Organic antibacterial agents are relatively cheap and have good antibacterial effects even in small amounts, but they are sometimes toxic to the human body, are effective only against specific bacteria, and have a risk of decomposing and losing the antibacterial effect when processed at high temperatures. there is. In addition, it may cause discoloration after processing and has short antibacterial persistence due to dissolution problems, so the range of organic antibacterial agents that can be applied to antibacterial thermoplastic resin compositions is extremely limited.

Inorganic antibacterial agents are antibacterial agents containing metal components such as silver (Ag) and copper (Cu) and have excellent thermal stability, so they are often used in the production of antibacterial thermoplastic resin compositions (antibacterial resins), but they lack antibacterial activity compared to organic antibacterial agents. It requires excessive input, and has disadvantages such as relatively high price, problems with uniform dispersion during processing, and discoloration due to metal components, so there are many restrictions on its use.

Therefore, there is a need to develop a thermoplastic resin composition with excellent antibacterial properties, transparency, antistatic properties, and impact resistance.

The background technology of the present invention is disclosed in Korean Patent Registration No. 10-0696385, etc.

The purpose of the present invention is to provide a thermoplastic resin composition with excellent antibacterial properties, transparency, antistatic properties, impact resistance, etc.

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 all 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; 4 to 23 parts by weight of polyetheresteramide block copolymer; 0.03 to 1 part by weight of a silver (Ag)-based compound; and 0.05 to 4 parts by weight of zinc oxide, wherein the zinc oxide consists of primary particles and secondary particles, the average particle size (D50) of the primary particles is 1 to 50 nm, and the average particle size of the secondary particles is 1 to 50 nm. It is characterized by a particle size (D50) of 0.1 to 10 ㎛.

2. In the first embodiment, the weight ratio of the sum of the polyetheresteramide block copolymer, the silver compound, and the zinc oxide (polyetheresteramide block copolymer: silver compound + zinc oxide) is 1:0.01 to 1:0.5. It can be.

3. In the first or second embodiment, the weight ratio of the silver-based compound and the zinc oxide (silver-based compound: zinc oxide) may be 1:0.5 to 1:60.

4. In embodiments 1 to 3, the rubber-modified aromatic vinyl-based copolymer resin may include 5 to 50% by weight of the rubber-modified vinyl-based graft copolymer and 50 to 95% by weight of the aromatic vinyl-based copolymer resin. there is.

5. In embodiments 1 to 4, the rubber-modified vinyl-based graft copolymer may be a graft-copolymer of an alkyl (meth)acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer on a rubber polymer.

6. In embodiments 1 to 5 above, the aromatic vinyl-based copolymer resin may be a copolymerization of alkyl (meth)acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer.

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

8. In embodiments 1 to 7, the silver-based compound may include one or more of metallic silver, silver oxide, silver halide, and a carrier containing silver ions.

9. In embodiments 1 to 8, the thermoplastic resin composition was inoculated with Staphylococcus aureus and Escherichia coli in a 5 cm After culturing for a time, the antibacterial activity values calculated according to Equation 1 below may be 2 to 7, respectively:

[Equation 1]

Antibacterial activity value = log(M1/M2)

In Equation 1, M1 is the number of bacteria after culturing the blank specimen for 24 hours, and M2 is the number of bacteria after culturing the thermoplastic resin composition specimen for 24 hours.

10. In embodiments 1 to 9, the thermoplastic resin composition may have a haze of 1 to 13% and a light transmittance of 82 to 95% of a 0.1 mm thick specimen measured according to ASTM D1003.

11. In embodiments 1 to 10, the thermoplastic resin composition may have a surface resistance value of 1 × 10 ⁸ to 5 × 10 ¹² Ω/sq of a 3.2 mm thick injection specimen measured according to ASTM D257.

12. In embodiments 1 to 11, the thermoplastic resin composition may have a notched Izod impact strength of 5 to 20 kgf·cm/cm for a 1/8" thick specimen measured according to ASTM D256.

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

14. In the 13th embodiment above, the molded article may be an antibacterial film with a thickness of 0.1 to 3 mm.

The present invention has the effect of providing a thermoplastic resin composition with excellent antibacterial properties, transparency, antistatic properties, impact resistance, etc., and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail as follows.

The thermoplastic resin composition according to the present invention includes (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) polyetheresteramide block copolymer; (C) Silver (Ag)-based compound; and (D) zinc oxide.

In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

(A) Rubber-modified aromatic vinyl-based copolymer resin

As the rubber-modified aromatic vinyl-based copolymer resin of the present invention, a rubber-modified aromatic vinyl-based copolymer resin used in ordinary transparent thermoplastic resin compositions can be used, for example, (A1) 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 can improve the transparency, impact resistance, and fluidity of a thermoplastic resin composition, and includes alkyl (meth)acrylate, aromatic vinyl-based monomer, and It may be a graft copolymerization of a vinyl cyanide-based monomer. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft-copolymerizing a monomer mixture containing an alkyl (meth)acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer to a rubber polymer, if necessary. , graft polymerization can be performed by further including monomers that provide processability and heat resistance to the monomer mixture. The polymerization may be performed by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization.

In specific examples, the rubbery polymer includes diene-based rubbers such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene), and saturated rubber obtained by adding hydrogen to the diene-based rubber, isoprene rubber, and polybutyl acrylic acid. Examples include acrylic rubber and ethylene-propylene-diene monomer terpolymer (EPDM). These can be used individually or in combination of two or more types. For example, diene-based rubber can be used, and specifically, butadiene-based rubber can be used.

In a specific example, the average particle size (Z-average) of the rubbery polymer (rubber particles) may be 0.1 to 0.5 ㎛, for example, 0.2 to 0.4 ㎛. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, etc. without decreasing transparency. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) can be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex was filtered through a mesh to remove coagulum generated during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water was poured into a 1,000 ml flask and filled with distilled water to prepare a sample. , 10 ml of sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured using a light scattering particle size meter (Malvern, nano-zs).

In a specific example, the content of the rubbery polymer may be 5 to 65% by weight, for example, 10 to 60% by weight, based on 100% by weight of the total rubber-modified vinyl graft copolymer, and the monomer mixture (alkyl (meth)acrylic) The content (including aromatic vinyl monomers and vinyl cyanide monomers) may be 35 to 95 wt%, for example, 40 to 90 wt%, based on 100 wt% of the total rubber-modified vinyl graft copolymer. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, etc.

In a specific example, the alkyl (meth)acrylate may be graft-copolymerized with the rubbery copolymer or copolymerized with an aromatic vinyl monomer, such as methyl (meth)acrylate, ethyl (meth)acrylate, Alkyl (meth)acrylates having 1 to 10 carbon atoms, such as propyl (meth)acrylate and butyl (meth)acrylate, can be used, and specifically, methyl (meth)acrylate can be used. The content of the alkyl (meth)acrylate may be 55 to 85% by weight, for example, 60 to 80% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, etc.

In a specific example, the aromatic vinyl monomer can be graft copolymerized into a rubbery copolymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene. , vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be used. These can be used individually or in combination of two or more types. The content of the aromatic vinyl monomer may be 10 to 40% by weight, for example, 15 to 35% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, heat resistance, fluidity, etc.

In a specific example, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. Examples may be given, but are not limited thereto. These can be used individually or in combination of two or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer may be 1 to 30% by weight, for example, 5 to 25% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, etc.

In specific examples, monomers for imparting processability and heat resistance may include (meth)acrylic acid, maleic anhydride, N-substituted maleimide, etc. When using a monomer to provide the processability and heat resistance, its content 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, processability and heat resistance can be imparted to the thermoplastic resin composition without deterioration of other physical properties.

In a specific example, the rubber-modified vinyl-based graft copolymer may include methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS). Here, the g-MABS may be composed of polybutadiene (PBD), a rubbery polymer (core), and a methyl methacrylate-acrylonitrile-styrene copolymer shell graft-copolymerized to the core, The shell may include, but is not limited to, an inner shell made of acrylonitrile-styrene resin and an outer shell made of polymethyl methacrylate.

In a specific example, the rubber-modified vinyl-based graft copolymer may be included in 5 to 50% by weight, for example, 10 to 45% by weight, based on 100% by weight of the rubber-modified aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent transparency, impact resistance, fluidity, and balance of physical properties.

(A2) Aromatic vinyl copolymer resin

The aromatic vinyl-based copolymer resin according to one embodiment of the present invention is capable of improving the impact resistance and transparency of the thermoplastic resin composition, and includes alkyl (meth)acrylate, aromatic vinyl-based monomer, and vinyl cyanide-based monomer. It may be a polymer of a mixture of monomers. For example, the aromatic vinyl-based copolymer resin can be obtained by reacting the monomer mixture according to a known polymerization method. Additionally, if necessary, monomers that provide processability and heat resistance may be further included in the monomer mixture.

In a specific example, the alkyl (meth)acrylate may be graft-copolymerized with the rubbery copolymer or copolymerized with an aromatic vinyl monomer, such as methyl (meth)acrylate, ethyl (meth)acrylate, Alkyl (meth)acrylates having 1 to 10 carbon atoms, such as propyl (meth)acrylate and butyl (meth)acrylate, can be used, and specifically, methyl (meth)acrylate can be used. The content of the alkyl (meth)acrylate may be 55 to 85% by weight, for example, 60 to 80% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, etc.

In a specific example, the aromatic vinyl monomer can be graft copolymerized into a rubbery copolymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene. , vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be used. These can be used individually or in combination of two or more types. The content of the aromatic vinyl monomer may be 10 to 40% by weight, for example, 15 to 35% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, etc.

In a specific example, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. Examples may be given, but are not limited thereto. These can be used individually or in combination of two or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer may be 1 to 30% by weight, for example, 5 to 25% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, etc.

In specific examples, monomers for imparting processability and heat resistance may include (meth)acrylic acid, maleic anhydride, and N-substituted maleimide, but are not limited thereto. When using a monomer to provide the processability and heat resistance, its content 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, processability and heat resistance can be imparted to the thermoplastic resin composition without deterioration of other physical properties.

In a specific example, the aromatic vinyl-based copolymer resin may have a weight average molecular weight measured by gel permeation chromatography (GPC) of 50,000 to 200,000 g/mol, for example, 100,000 to 180,000 g/mol. Within the above range, the thermoplastic resin composition may have excellent impact resistance, processability (fluidity), etc.

In a specific example, the aromatic vinyl-based copolymer resin may be included in 50 to 95% by weight, for example, 55 to 90% by weight, based on 100% by weight of the base resin. Within the above range, the thermoplastic resin composition may have excellent transparency, impact resistance, fluidity, and balance of physical properties.

In a specific example, the rubber-modified aromatic vinyl-based copolymer resin (base resin) includes methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS) and methyl methacrylate-styrene-acrylonitrile. Examples include, but are not limited to, methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (MABS resin), which is a mixture of copolymer resins (MSAN). Here, the MABS resin may be in the form of g-MABS dispersed in MSAN.

(B) polyetheresteramide block copolymer

The polyetheresteramide block copolymer according to one embodiment of the present invention is applied to the rubber-modified aromatic vinyl-based copolymer resin together with a silver-based compound and zinc oxide to provide antibacterial and antistatic properties while maintaining appropriate transparency of the thermoplastic resin composition. As an agent that can improve properties, polyetheresteramide block copolymers commonly used as antistatic agents can be used, for example, amino carboxylic acids with 6 or more carbon atoms, lactams, or diamine-dicarboxylic acid salts; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms. A block copolymer of a reaction mixture containing a dicarboxylic acid may be used.

In a specific example, salts of amino carboxylic acids, lactams, or diamine-dicarboxylic acids having 6 or more carbon atoms include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, and ω-aminopelcone. acids, aminocarboxylic acids such as ω-aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc.; Lactams such as caprolactam, enantlactam, capryllactam, and lauryllactam; and salts of diamine and dicarboxylic acid, such as the salt of hexamethylenediamine-adipic acid and the salt of hexamethylenediamine-isophthalic acid. For example, salts of 1,2-aminododecanoic acid, caprolactam, and hexamethylenediamine-adipic acid can be used.

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

In specific examples, dicarboxylic acids having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, and dodecanocarboxylic acid.

In an embodiment, the bond between 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 dicarboxylic acid having 6 or more carbon atoms. The bond between the diamine-dicarboxylic acid salt and the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, and the bond between the polyalkylene glycol and the dicarboxylic acid having 4 to 20 carbon atoms is It may be an ester bond.

In a specific example, the polyetheresteramide block copolymer may be prepared by a known synthetic method, for example, prepared according to the synthetic method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Application Publication No. 55-133424. It can be.

In a specific example, the polyetheresteramide block copolymer may include 10 to 95% by weight of polyether-ester block. Within the above range, the thermoplastic resin composition may have excellent antistatic properties, heat resistance, etc.

In a specific example, the polyetheresteramide block copolymer has a refractive index of 1.49 to 1.52 for a 2.5 mm thick specimen measured at a temperature of 20°C using a refractive index meter (manufacturer: ATAGO, device name: Abbe refractometer DR-A1), e.g. For example, it may be 1.50 to 1.51, and the difference in refractive index with the rubber-modified aromatic vinyl-based copolymer resin may be 0.01 or less, for example, 0.005 or less, specifically 0.001 to 0.002. Within the above range, the thermoplastic resin composition (molded article) may have appropriate transparency.

In a specific example, the polyetheresteramide block copolymer is present in an amount of 4 to 23 parts by weight, for example 5 to 20 parts by weight, specifically 8 to 20 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. may be included. If the content of the polyetheresteramide block copolymer is less than 4 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, there is a risk that the antibacterial properties, antistatic properties, and impact resistance of the thermoplastic resin composition may be reduced. If it exceeds 23 parts by weight, there is a risk that the transparency and heat resistance of the thermoplastic resin composition may decrease.

(C) Silver (Ag)-based compound

The silver-based compound according to one embodiment of the present invention is mixed with the polyetheresteramide block copolymer and zinc oxide to improve the antibacterial properties, transparency, etc. of the thermoplastic resin composition based on the rubber-modified aromatic vinyl-based copolymer resin, even in a small amount. It can be done. The silver-based compound is an antibacterial agent and is not particularly limited as long as it is a compound containing a silver component, and may include, for example, metallic silver, silver oxide, silver halide, a carrier containing silver ions, and combinations thereof. Among these, a carrier containing silver ions can be used. Examples of the carrier include zeolite, silica gel, calcium phosphate, zirconium phosphate, sodium-zirconium phosphate, sodium-hydrogen-zirconium phosphate, and the like. The carrier preferably has a porous structure. Since the carrier with a porous structure can retain the silver component even inside it, not only can the content of the silver component be increased, but also the sustainability performance (retention performance) of the silver component is improved. Specifically, silver sodium hydrogen zirconium phosphate, etc. may be used as the silver-based compound.

In a specific example, the silver-based compound may have an average particle size (D50) of 1.5 ㎛ or less, for example, 0.1 to 1 ㎛, as measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 equipment). .

In a specific example, the silver-based compound may be included in an amount of 0.03 to 1 part by weight, for example, 0.05 to 0.7 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. If the content of the silver-based compound is less than 0.03 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a risk that the antibacterial properties of the thermoplastic resin composition may be reduced, and if it exceeds 1 part by weight, the thermoplastic resin composition There is a risk that transparency, impact resistance, etc. may be reduced.

(D) Zinc oxide

The zinc oxide of the present invention can be mixed with the polyetheresteramide block copolymer and the silver-based compound to improve the antibacterial properties, transparency, antistatic properties, etc. of the thermoplastic resin composition based on the rubber-modified aromatic vinyl-based copolymer resin, even in a small amount. It consists of primary particles (single particles) and secondary particles formed by agglomerating the primary particles, and the primary particles measured with a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 equipment) The average particle size (D50) may be 1 to 50 nm, for example, 1 to 30 nm, and the average particle size (D50) of the secondary particles may be 0.1 to 10 μm, for example, 0.5 to 5 μm. If the average particle size of the zinc oxide primary particles is less than 1 nm, there is a risk that the antibacterial properties of the thermoplastic resin composition may be reduced, and if it exceeds 50 nm, there is a risk that the transparency, etc. of the thermoplastic resin composition may be reduced. In addition, if the average particle size of the zinc oxide secondary particles is less than 0.1 ㎛, there is a risk that the antibacterial properties of the thermoplastic resin composition may decrease, and if it exceeds 10 ㎛, the transparency and mechanical properties of the thermoplastic resin composition may decrease. There are concerns.

In a specific example, the zinc oxide may be included in an amount of 0.05 to 4 parts by weight, for example, 0.1 to 3 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. If the content of zinc oxide is less than 0.05 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a risk that the antibacterial properties of the thermoplastic resin composition may be reduced, and if it exceeds 4 parts by weight, the thermoplastic resin composition There is a risk that transparency, impact resistance, etc. may be reduced.

In an embodiment, the weight ratio of the sum of the polyetheresteramide block copolymer and the silver-based compound and the zinc oxide (polyetheresteramide block copolymer: silver-based compound + zinc oxide) is 1:0.01 to 1:0.5, for example. It may be 1:0.01 to 1:0.25. Within the above range, the thermoplastic resin composition may have excellent antibacterial properties, transparency, antistatic properties, impact resistance, etc.

In a specific example, the weight ratio of the silver-based compound and the zinc oxide (silver-based compound: zinc oxide) may be 1:0.5 to 1:60, for example, 1:0.6 to 1:30. Within the above range, the antibacterial properties, transparency, etc. of the thermoplastic resin composition may be more excellent.

The thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additives include, but are not limited to, flame retardants, fillers, antioxidants, anti-dripping agents, lubricants, mold release agents, nucleating agents, stabilizers, pigments, dyes, and mixtures thereof. When using the additive, its 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 rubber-modified aromatic vinyl-based copolymer resin.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of a pellet obtained by mixing the above components and melt-extruding the mixture at 200 to 280°C, for example, 220 to 250°C using a conventional twin-screw extruder.

In a specific example, the thermoplastic resin composition has an antibacterial effect against various bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Salmonella, pneumoniae, and MRSA (Methicillin-Resistant Staphylococcus Aureus), according to the JIS Z 2801 antibacterial evaluation method. Therefore, Staphylococcus aureus and Escherichia coli were inoculated into a 5 cm For example, it may be 3 to 6.5.

[Equation 1]

Antibacterial activity value = log(M1/M2)

In Equation 1, M1 is the number of bacteria after culturing the blank specimen for 24 hours, and M2 is the number of bacteria after culturing the thermoplastic resin composition specimen for 24 hours.

Here, the “blank specimen” is a control specimen of the test specimen (thermoplastic resin composition specimen). Specifically, to check whether the inoculated bacteria grew normally, bacteria were inoculated on an empty Petri dish and cultured for 24 hours in the same manner as the test specimen. The antibacterial performance of the test specimen was determined by comparing the number of cultured bacteria. judge. In addition, the “bacterial count” can be counted by inoculating each specimen with bacteria, orienting the specimen for 24 hours, recovering the inoculated bacterial solution, going through a dilution process, and growing it again into a colony in a culture dish. When the growth of colonies is so large that it is difficult to count them, you can divide them into sections, count them, and then convert them to the actual number.

In a specific example, the thermoplastic resin composition has a haze of 1 to 13%, for example, 1 to 10%, and a light transmittance of 82 to 95%, for example, of a 1 mm thick specimen measured according to ASTM D1003. For example, it may be 85 to 92%.

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 ⁸ to 5 × 10 ¹² Ω/sq (square), for example, 1 × 10 8 to 1 × 10 ⁸ It may be 1 × 10 ¹¹ Ω/sq.

In an embodiment, the thermoplastic resin composition may have a notched Izod impact strength of 5 to 20 kgf·cm/cm, for example, 6 to 15 kgf·cm/cm, for a 1/8" thick specimen measured according to ASTM D256. there is.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition can be manufactured in the form of pellets, and the manufactured pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. This forming method is well known to those skilled in the art.

In a specific example, the molded article has excellent antibacterial properties, transparency, antistatic properties, impact resistance, and a balance of these properties, and is therefore useful as an antibacterial film that is in frequent physical contact.

In a specific example, the antibacterial film may have a thickness of 0.1 to 3 mm, for example, 0.2 to 2 mm. Within the above range, transparency, antibacterial properties, antistatic properties, mechanical properties, etc. may be excellent.

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, the specifications of each component used in the examples and comparative examples are as follows.

(A) Rubber-modified aromatic vinyl-based copolymer resin

A rubber-modified aromatic vinyl-based copolymer resin (A) containing 30% by weight of the following rubber-modified vinyl-based graft copolymer (A1) and 70% by weight of the following aromatic vinyl-based copolymer resin was used.

(A1) Rubber-modified vinyl-based graft copolymer

55% by weight of butadiene rubber with an average particle size of 0.28 ㎛, 45% by weight of styrene, acrylonitrile and methyl methacrylate (styrene/acrylonitrile/methyl methacrylate: 20% by weight/10% by weight/70% by weight) A core-shell type graft copolymer (g-MABS) prepared by graft copolymerization was used.

(A2) Aromatic vinyl copolymer resin

A resin (weight average molecular weight: 160,000 g/mol) prepared by polymerizing 70% by weight of methyl methacrylate, 20% by weight of styrene, and 10% by weight of acrylonitrile was used.

(B) Block copolymer

(B1) Polyamide 6-polyethylene oxide block copolymer (PA6-b-PEO, manufacturer: Sanyo chemical, product name: PELECTRON AS, refractive index: 1.51) was used.

(B2) Polypropylene-polyethylene oxide block copolymer (PP-b-PEO, manufacturer: Sanyo chemical, product name: PELECTRON PVL, refractive index: 1.50) was used.

(C) Silver (Ag)-based compound

Silver sodium hydrogen zirconium phosphate (manufacturer: Toa Gosei Co., LTD, product name: Novaron AGZ030) was used.

(D) Zinc oxide

(D1) Zinc oxide (manufacturer: SH evergy & chemical, product name: ANYZON) with an average particle size (D50) of primary particles of 10 nm and an average particle size (D50) of secondary particles of 1.7 ㎛ was used.

(D2) Zinc oxide (manufacturer: PJ Chemtech, product name: KS-1) consisting of single particles and having an average particle size (D50) of 1 ㎛ was used.

Examples 2 to 7 and Comparative Examples 1 to 9

Each of the components was added in the amounts shown in Tables 1 and 2 below, and then extruded at 230°C to prepare pellets. For extrusion, a twin-screw extruder with L/D = 36 and a diameter of 45 mm was used. The manufactured pellets were dried at 80℃ for more than 2 hours and then injected in a 6 Oz injection machine (molding temperature: 230℃, mold temperature: 60℃). Specimens were prepared. The physical properties of the manufactured specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

How to measure physical properties

(1) Antibacterial activity value: In accordance with the JIS Z 2801 antibacterial evaluation method, Staphylococcus aureus and Escherichia coli were inoculated into a 5 cm Calculated.

[Equation 1]

Antibacterial activity value = log(M1/M2)

In Equation 1, M1 is the number of bacteria after culturing the blank specimen for 24 hours, and M2 is the number of bacteria after culturing the thermoplastic resin composition specimen for 24 hours.

(2) Haze and light transmittance (unit: %): The haze and light transmittance (total light transmittance) of the 1 mm thick specimen were measured using Nippon Denshoku's Haze meter NDH 2000 equipment according to ASTM D1003.

(3) Surface resistance value (unit: Ω/sq): 10 mm × 10 mm × 3.2 mm using a surface resistance measuring device (manufacturer: Mitsubishi Chemical, device name: Hiresta-UP (MCP-HT450)) according to ASTM D257. The surface resistance value of the size injection specimen was measured.

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

Comparative example Example 9 2 3 4 5 6 7 (A) (parts by weight) 100 100 100 100 100 100 100 (B1) (part by weight) 5 15 20 15 15 15 15 (B2) (parts by weight) - - - - - - - (C) (parts by weight) 0.1 0.1 0.1 0.05 0.7 0.1 0.1 (D1) (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.1 3 (D2) (parts by weight) - - - - - - - Antibacterial activity (E. coli) 6.4 6.4 6.4 6.4 6.4 6.4 6.4 Antibacterial activity (staphylococcus) 2.2 4.6 4.6 4.6 4.6 4.6 4.6 Haze (%) 1.5 2 9 1.5 10 1.5 10 Light transmittance (%) 91 90 86 90 86 91 86 surface resistance value 5×10 ¹² 1×10 ¹⁰ 1×10 ⁸ 1×10 ¹⁰ 1×10 ¹⁰ 1×10 ¹⁰ 1×10 ¹⁰ Notched Izod Impact Strength 6 8 10 8 8 8 6

Comparative example One 2 3 4 5 6 7 8 (A) (parts by weight) 100 100 100 100 100 100 100 100 (B1) (part by weight) 3 25 - 15 15 15 15 15 (B2) (parts by weight) - - 15 - - - - - (C) (parts by weight) 0.1 0.1 0.1 0.01 1.3 0.1 0.1 0.1 (D1) (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.03 5 - (D2) (parts by weight) - - - - - - - 0.5 Antibacterial activity (E. coli) 2.2 6.4 6.4 0.8 6.4 0.8 6.4 1.8 Antibacterial activity (staphylococcus) 0.8 4.6 4.6 4.6 4.6 2.2 4.6 4.6 Haze (%) 1.5 18 11 1.5 25 1.5 15 20 Light transmittance (%) 90 80 85 90 78 90 78 83 surface resistance value 1×10 ¹³ 1×10 ⁸ 1×10 ¹² 1×10 ¹⁰ 1×10 ¹⁰ 1×10 ¹⁰ 1×10 ¹⁰ 1×10 ¹⁰ Notched Izod Impact Strength 4 12 4 8 8 8 3 8

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in antibacterial properties, transparency, antistatic properties, impact resistance, etc.

On the other hand, in the case of Comparative Example 1 where the content of the polyetheresteramide block copolymer is less than the range of the present invention, it can be seen that antibacterial properties, antistatic properties, impact resistance, etc. are reduced, and the content of the polyetheresteramide block copolymer is lower than the range of the present invention. In the case of Comparative Example 2, which exceeded the scope of the invention, it can be seen that transparency, etc. deteriorated. In addition, in the case of Comparative Example 3 in which polypropylene-polyethylene oxide block copolymer (B2) was applied instead of the polyetheresteramide block copolymer of the present invention, impact resistance, etc. decreased, and transparency, etc. decreased relatively compared to the Examples. can be seen. In the case of Comparative Example 4, where the content of the silver-based compound is less than the range of the present invention, it can be seen that antibacterial properties, etc. are reduced, and in the case of Comparative Example 5, where the content of the silver-based compound exceeds the range of the present invention, it can be seen that transparency, etc. is reduced. In the case of Comparative Example 6, where the zinc oxide content is less than the range of the present invention, it can be seen that antibacterial properties, etc. are reduced, and in the case of Comparative Example 7, where the zinc oxide content exceeds the range of the present invention, transparency, impact resistance, etc. It can be seen that this is deteriorating. In addition, in the case of Comparative Example 8 in which zinc oxide (D2) was applied instead of the zinc oxide of the present invention, it was found that antibacterial properties, transparency, etc. were reduced.

So far, the present invention has been examined focusing on the embodiments. A person skilled in the art to which the present invention pertains will understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the equivalent scope should be construed as being included in the present invention.

Claims (14)

100 parts by weight of rubber-modified aromatic vinyl-based copolymer resin;
8 to 23 parts by weight of polyetheresteramide block copolymer;
0.03 to 1 part by weight of a silver (Ag)-based compound; and
Contains 0.05 to 4 parts by weight of zinc oxide,
The zinc oxide consists of primary particles and secondary particles, and the average particle size (D50) of the primary particles is 1 to 50 nm, and the average particle size (D50) of the secondary particles is 0.1 to 10 ㎛, ,
The weight ratio of the sum of the polyetheresteramide block copolymer, the silver compound, and the zinc oxide (polyetheresteramide block copolymer: silver compound + zinc oxide) is 1:0.01 to 1:0.5,
Based on the JIS Z 2801 antibacterial evaluation method, Staphylococcus aureus and Escherichia coli were inoculated into a 5 cm 3 to 6.5,
The haze of the 0.1 mm thick specimen measured according to ASTM D1003 is 1 to 13%, and the light transmittance is 85 to 92%,
Thermoplastic resin composition, characterized in that the surface resistance value of the 3.2 mm thick injection specimen measured according to ASTM D257 is 1 × 10 ⁸ to 5 × 10 ¹² Ω/sq:
[Equation 1]
Antibacterial activity value = log(M1/M2)
In Equation 1, M1 is the number of bacteria after culturing the blank specimen for 24 hours, and M2 is the number of bacteria after culturing the thermoplastic resin composition specimen for 24 hours.
delete The thermoplastic resin composition according to claim 1, wherein a weight ratio of the silver-based compound and the zinc oxide (silver-based compound: zinc oxide) is 1:0.5 to 1:60.
The thermoplastic material according to claim 1, wherein the rubber-modified aromatic vinyl-based copolymer resin comprises 5 to 50% by weight of a rubber-modified vinyl-based graft copolymer and 50 to 95% by weight of an aromatic vinyl-based copolymer resin. Resin composition.
The thermoplastic resin composition according to claim 4, wherein the rubber-modified vinyl-based graft copolymer is a rubber polymer grafted with an alkyl (meth)acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer.
The thermoplastic resin composition according to claim 4, wherein the aromatic vinyl-based copolymer resin is a copolymerization of an alkyl (meth)acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer.
According to claim 1, wherein the polyetheresteramide block copolymer is an amino carboxylic acid, lactam, or diamine-dicarboxylic acid salt having 6 or more carbon atoms; polyalkylene glycol; And a dicarboxylic acid having 4 to 20 carbon atoms; A thermoplastic resin composition, characterized in that it is a block copolymer of a reaction mixture containing.
The thermoplastic resin composition according to claim 1, wherein the silver-based compound includes at least one of metallic silver, silver oxide, silver halide, and a carrier containing silver ions.
delete delete delete The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of 5 to 20 kgf·cm/cm for a 1/8" thick specimen measured according to ASTM D256.
A molded article formed from the thermoplastic resin composition according to any one of claims 1, 3 to 8, and 12.
The molded article according to claim 13, wherein the molded article is an antibacterial film with a thickness of 0.1 to 3 mm.