WO2022114589A1 - Thermoplastic resin composition and molded product produced therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; about 4-23 parts by weight of a polyetheresteramide block copolymer; about 0.03-1 parts by weight of a silver (Ag)-based compound; and about 0.05-4 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 about 1-50 nm, and the average particle size (D50) of the secondary particles is about 0.1-10 µm. The thermoplastic resin composition has excellent antibacterial properties, transparency, antistatic properties, impact resistance, and the like.

Description

Thermoplastic resin composition and molded article prepared therefrom

The present invention relates to a thermoplastic resin composition and a molded article prepared therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent antibacterial properties, transparency, antistatic properties, impact resistance, and the like, and a molded article prepared therefrom.

Recently, with interest in personal health and hygiene and the improvement of income level, the demand for thermoplastic resin products with antibacterial and sanitation functions is increasing. Accordingly, the number of thermoplastic resin products that have been treated with antibacterial treatment to remove or inhibit germs from the surface of household goods and electronic products is increasing, and the development of stable and reliable functional antibacterial materials (antibacterial thermoplastic resin composition) is very important. It is a task.

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

Organic antibacterial agents are relatively inexpensive and have good antibacterial effects even in small amounts, but sometimes they are toxic to the human body and are only effective against specific bacteria, and there is a risk of decomposition and loss of antibacterial effect during high-temperature processing. have. In addition, it may cause discoloration after processing, and there is a disadvantage in that the antibacterial durability is short due to the dissolution problem, so the range of the organic antimicrobial agent that can be applied to the antimicrobial thermoplastic resin composition is extremely limited.

Inorganic antibacterial agents are antibacterial agents containing metal components such as silver (Ag) and copper (Cu). They have excellent thermal stability and are widely used in the production of antibacterial thermoplastic resin compositions (antibacterial resins). Excessive input is required, and there are disadvantages such as a relatively high price, a problem of uniform dispersion during processing, and discoloration due to metal components, so there are many restrictions on its use.

Therefore, there is a need for the development of a thermoplastic resin composition having excellent antibacterial properties, transparency, antistatic properties, impact resistance, and the like.

Background art of the present invention is disclosed in Korean Patent No. 10-0696385 and the like.

It is an object of the present invention to provide a thermoplastic resin composition having excellent antibacterial properties, transparency, antistatic properties, 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 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 comprises about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; about 4 to about 23 parts by weight of a polyetheresteramide block copolymer; about 0.03 to about 1 part by weight of a silver (Ag)-based compound; and about 0.05 to about 4 parts by weight of zinc oxide, wherein the zinc oxide consists of primary particles and secondary particles, and the primary particles have an average particle size (D50) of about 1 to about 50 nm, wherein the 2 It is characterized in that the average particle size (D50) of the tea particles is about 0.1 to about 10 μm.

2. In the above embodiment 1, 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 about 1: 0.01 to about 1 : It may be 0.5.

3. In embodiments 1 or 2, the weight ratio of the silver-based compound and the zinc oxide (silver-based compound:zinc oxide) may be from about 1:0.5 to about 1:60.

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

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

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

7. In the above embodiments 1 to 6, 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 a reaction mixture comprising a.

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

9. In the above 1 to 8 embodiments, the thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli into a 5 cm × 5 cm size specimen, based on the JIS Z 2801 antibacterial evaluation method, and 24 at 35° C., RH 90% condition After time incubation, the antibacterial activity calculated according to the following formula 1 may be about 2 to about 7, respectively:

[Equation 1]

Antibacterial activity = log(M1/M2)

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

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

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

12. In embodiments 1 to 11, the thermoplastic resin composition may have a notch Izod impact strength of about 5 to about 20 kgf·cm/cm of a specimen having a thickness of 1/8″ measured according to ASTM D256.

13. Another aspect of the 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 1 to 12.

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

The present invention has the effect of providing a thermoplastic resin composition excellent in antibacterial properties, transparency, antistatic properties, impact resistance, and the like, 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 comprises (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) a polyetheresteramide block copolymer; (C) a silver (Ag)-based compound; and (D) zinc oxide.

In the present specification, "a to b" representing 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 conventional 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 transparency, impact resistance, fluidity, etc. of the thermoplastic resin composition, and includes alkyl (meth)acrylate, aromatic vinyl-based monomer and A vinyl cyanide-based monomer may be graft copolymerized. For example, the rubber-modified vinyl-based graft copolymer may be obtained by graft copolymerizing a monomer mixture including an alkyl (meth)acrylate, an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer, and if necessary , may be graft-polymerized by further including a monomer that imparts processability and heat resistance to the monomer mixture. The polymerization may be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, and bulk polymerization.

In a specific embodiment, the rubbery polymer includes a diene-based rubber such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), and saturated rubber, isoprene rubber, and polybutylacrylic acid obtained by adding hydrogen to the diene-based rubber. Acrylic rubber, such as ethylene-propylene-diene monomer terpolymer (EPDM), etc. can be illustrated. These may be used individually or in mixture of 2 or more types. For example, a diene-based rubber may be used, and specifically, a butadiene-based rubber may be used.

In an embodiment, the average particle size (Z-average) of the rubbery polymer (rubber particles) may be about 0.1 to about 0.5 μm, for example, about 0.2 to about 0.4 μm. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, and the like, without lowering the transparency of the composition. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex is filtered through a mesh to remove the coagulation that occurs during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000ml flask, filled with distilled water to prepare a sample, and then , 10 ml of the 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 analyzer (malvern, nano-zs).

In an embodiment, the content of the rubbery polymer may be about 5 to about 65% by weight, for example, about 10 to about 60% by weight, of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, and the monomer mixture (alkyl The content of (meth)acrylate, aromatic vinyl-based monomer, and vinyl cyanide-based monomer) is about 35 to about 95% by weight, for example, about 40 to about 90% by weight, based on 100% by weight of the total rubber-modified vinyl-based graft copolymer. It can be %. In the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, and the like.

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

In an embodiment, the aromatic vinyl-based monomer may be graft copolymerized to the rubber copolymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene. , vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like can be used. These may be used individually or in mixture of 2 or more types. The content of the aromatic vinyl-based monomer may be about 10 to about 40% by weight, for example, about 15 to about 35% by weight based on 100% by weight of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, heat resistance, fluidity, and the like.

In a specific embodiment, the cyanide-based monomer is copolymerizable with the aromatic vinyl-based monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. may be exemplified, but is not limited thereto. These may be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be from about 1 to about 30% by weight, for example, from about 5 to about 25% by weight of 100% by weight of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, and the like.

In a specific embodiment, as the monomer for imparting the processability and heat resistance, (meth)acrylic acid, maleic anhydride, N-substituted maleimide, and the like may be exemplified. When the monomer for imparting the processability and heat resistance is used, the content thereof may be about 15% by weight or less, for example, about 0.1 to about 10% by weight based on 100% by weight of the monomer mixture. Within the above range, processability and heat resistance may be imparted to the thermoplastic resin composition without deterioration of other physical properties.

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

In an embodiment, the rubber-modified vinyl-based graft copolymer may be included in an amount of about 5 to about 50% by weight, for example, about 10 to about 45% by weight of 100% by weight of the rubber-modified aromatic vinyl-based copolymer resin. In the above range, the thermoplastic resin composition may have excellent transparency, impact resistance, fluidity, 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 is capable of improving the impact resistance and transparency of the thermoplastic resin composition, and includes an alkyl (meth)acrylate, an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. It may be a polymer of a monomer mixture. For example, the aromatic vinyl-based copolymer resin may be obtained by reacting the monomer mixture according to a known polymerization method. In addition, if necessary, a monomer that imparts processability and heat resistance to the monomer mixture may be further included.

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

In an embodiment, the aromatic vinyl-based monomer may be graft copolymerized to the rubber copolymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene. , vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like can be used. These may be used individually or in mixture of 2 or more types. The content of the aromatic vinyl-based monomer may be about 10 to about 40% by weight, for example, about 15 to about 35% by weight based on 100% by weight of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, and the like.

In a specific embodiment, the cyanide-based monomer is copolymerizable with the aromatic vinyl-based monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. may be exemplified, but is not limited thereto. These may be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be from about 1 to about 30% by weight, for example, from about 5 to about 25% by weight of 100% by weight of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent impact resistance, transparency, fluidity, and the like.

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

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

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

In a specific embodiment, as the rubber-modified aromatic vinyl-based copolymer resin (base resin), methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS) and methyl methacrylate-styrene-acrylonitrile Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (MABS resin) in the form of a mixture of copolymer resin (MSAN) may be exemplified, but is not limited thereto. Here, the MABS resin may be in a form in which g-MABS is dispersed in MSAN.

(B) polyetheresteramide block copolymer

The polyetheresteramide block copolymer according to an 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, and while maintaining appropriate transparency of the thermoplastic resin composition, antibacterial and antistatic properties As one capable of improving properties, polyetheresteramide block copolymers commonly used as antistatic agents may be used, for example, aminocarboxylic acids having 6 or more carbon atoms, lactams or diamine-dicarboxylates; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms; a block copolymer of a reaction mixture containing may be used.

In an embodiment, the salt of the amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms is ω-aminocaproic acid, ω-aminoenanthoic acid, ω-aminocaprylic acid, ω-aminopelconic acid. aminocarboxylic acids such as acid, ω-aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid and the like; lactams such as caprolactam, enanthlactam, caprylactam and lauryllactam; and a salt of diamine and dicarboxylic acid such as a salt of hexamethylenediamine-adipic acid, a salt of hexamethylenediamine-isophthalic acid, and the like. For example, 1,2-aminododecanoic acid, caprolactam, a salt of hexamethylenediamine-adipic acid, and the like can be used.

In an embodiment, the polyalkylene glycol is 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 of ethylene glycol and tetrahydrofuran, and the like. For example, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, etc. can be used.

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

In an embodiment, the combination 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 diamine having 6 or more carbon atoms, or 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; It may be an ester bond.

In an embodiment, the polyetheresteramide 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 an embodiment, the polyetheresteramide block copolymer may include 10 to 95% by weight of the polyether-ester block. In the above range, antistatic properties, heat resistance, etc. of the thermoplastic resin composition may be excellent.

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

In an embodiment, the polyether esteramide block copolymer is based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, from about 4 to about 23 parts by weight, for example from about 5 to about 20 parts by weight, specifically It may be included in an amount of about 8 to about 20 parts by weight. When the content of the polyetheresteramide block copolymer is less than about 4 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, the antibacterial, antistatic, and impact resistance of the thermoplastic resin composition may be lowered. There is a concern, and when it exceeds about 23 parts by weight, there is a possibility that the transparency, heat resistance, etc. of the thermoplastic resin composition may decrease.

(C) silver (Ag)-based compound

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

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

In an embodiment, the silver-based compound may be included in an amount of about 0.03 to about 1 part by weight, for example, about 0.05 to about 0.7 part by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the content of the silver-based compound is less than about 0.03 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a fear that the antibacterial properties of the thermoplastic resin composition may decrease, and when it exceeds about 1 part by weight, There exists a possibility that transparency, impact resistance, etc. of a thermoplastic resin composition may fall.

(D) zinc oxide

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

In an embodiment, the zinc oxide may be included in an amount of about 0.05 to about 4 parts by weight, for example, about 0.1 to about 3 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the content of the zinc oxide is less than about 0.05 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a fear that the antibacterial properties of the thermoplastic resin composition may be lowered, and when it exceeds about 4 parts by weight, There exists a possibility that transparency, impact resistance, etc. of a thermoplastic resin composition may fall.

In an embodiment, the weight ratio of the polyetheresteramide block copolymer, the silver compound, and the zinc oxide (polyetheresteramide block copolymer:silver compound+zinc oxide) is about 1: 0.01 to about 1: 0.5, yes For example, it may be about 1: 0.01 to about 1: 0.25. In the above range, antibacterial properties, transparency, antistatic properties, impact resistance, etc. of the thermoplastic resin composition may be more excellent.

In an embodiment, the weight ratio of the silver-based compound and the zinc oxide (silver-based compound:zinc oxide) may be from about 1:0.5 to about 1:60, for example, from about 1:0.6 to about 1:30. In the above range, antibacterial properties, transparency, etc. 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. The additive may include, but is not limited to, a flame retardant, a filler, an antioxidant, an anti-drip agent, a lubricant, a release agent, a nucleating agent, a stabilizer, a pigment, a dye, and mixtures thereof. When the additive is used, its content may be from about 0.001 to about 40 parts by weight, for example, from about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.

The thermoplastic resin composition according to an embodiment of the present invention is in the form of pellets that are melt-extruded at about 200 to about 280°C, for example, about 220 to about 250°C, by mixing the above components and using a conventional twin-screw extruder. can

In an embodiment, the thermoplastic resin composition has an antibacterial effect against various bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Salmonella, Pneumonia, and MRSA (Methicillin-Resistant Staphylococcus Aureus). Thus, after inoculating Staphylococcus aureus and Escherichia coli in a specimen having a size of 5 cm × 5 cm, and after culturing for 24 hours at 35° C. and 90% RH, the antibacterial activity values calculated according to the following formula 1 are each independently about 2 to about 7 , for example from about 3 to about 6.5.

[Equation 1]

Antibacterial activity = log(M1/M2)

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

Here, the "blank specimen" is a control specimen of the test specimen (thermoplastic resin composition specimen). Specifically, in order to check whether the inoculated bacteria have grown normally, the bacteria were inoculated on an empty petri dish and then cultured for 24 hours in the same way as the test specimen. to judge In addition, the "number of bacteria" can be counted by inoculating each specimen with the bacteria and then oriented for 24 hours, recovering the inoculated bacterial solution and diluting it, and growing it again as a colony in a culture dish. When it is difficult to count because the growth of colonies is too large, it can be divided into divisions and counted and converted into the actual number.

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

In an embodiment, the thermoplastic resin composition has a surface resistance value of about 1 × 10 ⁸ to about 5 × 10 ¹² Ω/sq (square) of a 3.2 mm thick injection specimen measured according to ASTM D257, for example, about 1 × 10 ⁸ to about 1×10 ¹¹ Ω/sq.

In an embodiment, the thermoplastic resin composition has a notch Izod impact strength of about 5 to about 20 kgf·cm/cm, for example, about 6 to about 15 kgf·cm, of a 1/8″ thick specimen measured according to ASTM D256. It can be /cm.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (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 art to which the present invention pertains.

In a specific embodiment, the molded article is useful as an antibacterial film with frequent physical contact, etc., because it has excellent antibacterial properties, transparency, antistatic properties, impact resistance, and balance of physical properties thereof.

In embodiments, the antimicrobial film may have a thickness of about 0.1 to about 3 mm, for example, about 0.2 to about 2 mm. In 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 Examples and Comparative Examples are as follows.

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

A rubber-modified aromatic vinyl-based copolymer resin (A) comprising 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

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

(A2) Aromatic vinyl copolymer resin

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

(B) block copolymer

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

(B2) A 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) having an average particle size (D50) of primary particles of 10 nm and an average particle size (D50) of secondary particles of 1.7 μm was used.

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

Examples 1 to 7 and Comparative Examples 1 to 8

After adding each of the components in an amount as shown in Tables 1 and 2 below, it was 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, and the manufactured pellets were dried at 80°C for 2 hours or more, and then injected in a 6 Oz injection machine (molding temperature: 230°C, mold temperature: 60°C). Specimens were 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) Antibacterial activity: Based on the JIS Z 2801 antibacterial evaluation method, Staphylococcus aureus and Escherichia coli were inoculated into a 5 cm × 5 cm specimen, and after 24 hours of incubation at 35° C., RH 90%, according to Equation 1 below calculated.

[Equation 1]

Antibacterial activity = log(M1/M2)

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

(2) Haze and light transmittance (unit: %): Haze and light transmittance (total light transmittance) of a 1 mm thick specimen were measured using a Haze meter NDH 2000 equipment manufactured by Nippon Denshoku in accordance with ASTM D1003.

(3) Surface resistance value (unit: Ω/sq): 10 mm × 10 mm × 3.2 mm with 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): According to ASTM D256, the notched Izod impact strength of a 1/8″ thick specimen was measured.

	Example
	One	2	3	4	5	6	7
(A) (parts by weight)	100	100	100	100	100	100	100
(B1) (parts 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 level (E. coli)	6.4	6.4	6.4	6.4	6.4	6.4	6.4
Antibacterial activity level (Staphylococcus aureus)	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) (parts 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 level (E. coli)	2.2	6.4	6.4	0.8	6.4	0.8	6.4	1.8
Antibacterial activity level (Staphylococcus aureus)	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 has excellent antibacterial properties, transparency, antistatic properties, impact resistance, and the like.

On the other hand, in the case of Comparative Example 1 in which the content of the polyether ester amide block copolymer is less than the range of the present invention, it can be seen that antibacterial properties, antistatic properties, impact resistance, etc. are lowered, and the content of the polyether ester amide block copolymer is this In the case of Comparative Example 2 exceeding the scope of the invention, it can be seen that transparency and the like are lowered. In addition, in the case of Comparative Example 3 in which the polypropylene-polyethylene oxide block copolymer (B2) was applied instead of the polyether esteramide block copolymer of the present invention, the impact resistance and the like were lowered, and the transparency was relatively lower than that of the Examples. can be known It can be seen that in Comparative Example 4 in which the content of the silver-based compound is less than the range of the present invention, antibacterial properties and the like are lowered, and in Comparative Example 5, in which the content of the silver-based compound exceeds the range of the present invention, it can be seen that the transparency is reduced. In the case of Comparative Example 6 in which the content of zinc oxide is less than the range of the present invention, it can be seen that antibacterial properties and the like are lowered, and in Comparative Example 7 in which the content of zinc oxide exceeds the range of the present invention, transparency, impact resistance, etc. It can be seen that this decreases. 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 can be seen that antibacterial properties, transparency, and the like were lowered.

Up to now, the present invention has been mainly examined in the examples. Those of ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in modified forms without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (14)

1. About 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin;

   about 4 to about 23 parts by weight of a polyetheresteramide block copolymer;

   about 0.03 to about 1 part by weight of a silver (Ag)-based compound; and

   from about 0.05 to about 4 parts by weight of zinc oxide;

   The zinc oxide consists of primary particles and secondary particles, and the primary particle has an average particle size (D50) of about 1 to about 50 nm, and the secondary particle has an average particle size (D50) of about 0.1 to about 0.1 to about 50 nm. A thermoplastic resin composition, characterized in that it is about 10 μm.
2. According to claim 1, wherein the weight ratio of the sum of the polyetheresteramide block copolymer and the silver compound and the zinc oxide (polyetheresteramide block copolymer: silver compound + zinc oxide) is about 1: 0.01 to about 1: 0.5 A thermoplastic resin composition, characterized in that
3. The thermoplastic resin composition of claim 1 or 2, wherein a weight ratio of the silver-based compound and the zinc oxide (silver-based compound:zinc oxide) ranges from about 1:0.5 to about 1:60.
4. The method according to any one of claims 1 to 3, wherein the rubber-modified aromatic vinyl-based copolymer resin is about 5 to about 50 wt% of the rubber-modified vinyl-based graft copolymer, and about 50 to about 50 wt% of the aromatic vinyl-based copolymer resin. A thermoplastic resin composition comprising about 95% by weight.
5. [Claim 5] The thermoplastic resin composition of claim 4, wherein the rubber-modified vinyl-based graft copolymer is graft copolymerized with an alkyl (meth)acrylate, an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer.
6. The thermoplastic resin composition according to claim 4, wherein the aromatic vinyl-based copolymer resin is copolymerized with an alkyl (meth)acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer.
7. The method according to any one of claims 1 to 6, wherein the polyetheresteramide block copolymer is an amino carboxylic acid having 6 or more carbon atoms, lactam or diamine-dicarboxylate; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms; a thermoplastic resin composition comprising a block copolymer of a reaction mixture comprising.
8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the silver-based compound comprises at least one of metallic silver, silver oxide, silver halide, and a carrier containing silver ions.
9. The method according to any one of claims 1 to 8, wherein the thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm × 5 cm specimen based on JIS Z 2801 antibacterial evaluation method, 35° C., RH 90 After culturing for 24 hours under % condition, the thermoplastic resin composition, characterized in that the antibacterial activity value calculated according to the following formula 1 is about 2 to about 7, respectively:

   [Equation 1]

   Antibacterial activity = log(M1/M2)

   In Equation 1, M1 is the number of bacteria after culturing for 24 hours on a blank specimen, and M2 is the number of bacteria after culturing for 24 hours on a thermoplastic resin composition specimen.
10. 10. The method of any one of claims 1 to 9, wherein the thermoplastic resin composition has a haze of about 1 to about 13%, and a light transmittance of about 82 to about 13% of a 0.1 mm thick specimen measured according to ASTM D1003. A thermoplastic resin composition, characterized in that about 95%.
11. 11. The method of any one of claims 1 to 10, wherein the thermoplastic resin composition has a surface resistance value of about 1 × 10 ⁸ to about 5 × 10 ¹² Ω/sq of a 3.2 mm thick injection specimen measured according to ASTM D257. A thermoplastic resin composition, characterized in that
12. 12. The method of any one of claims 1 to 11, wherein the thermoplastic resin composition has a notch Izod impact strength of about 5 to about 20 kgf·cm/cm of a 1/8″ thick specimen measured according to ASTM D256. Thermoplastic resin composition characterized in that.
13. A molded article, characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 12.
14. 14. The molded article of claim 13, wherein the molded article is an antimicrobial film having a thickness of about 0.1 to about 3 mm.