WO2023054916A1 - Thermoplastic resin composition and molded product manufactured therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention comprises: about 100 parts by weight of an aromatic vinyl-vinyl cyanide-based copolymer resin; about 4 to about 20 parts by weight of an aliphatic polyamide resin; about 20 to about 60 parts by weight of glass fibers; about 4 to about 20 parts by weight of a polyetheresteramide block copolymer; about 0.1 to about 2 parts by weight of a silver (Ag)-based compound; and about 1 to about 20 parts by weight of zinc oxide, wherein the weight ratio of the polyetheresteramide block copolymer and the sum of the silver-based compound and the zinc oxide (polyetheresteramide block copolymer:silver-based compound+zinc oxide) is about 1:0.2 to about 1:3. The thermoplastic resin composition has excellent antiviral properties, creep properties, rigidity, thermal stability, and fluidity.

Description

Thermoplastic resin composition and molded articles produced therefrom

The present invention relates to a thermoplastic resin composition and a molded article made therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent antiviral properties, creep properties, stiffness, thermal stability, fluidity, etc., and a molded article manufactured therefrom.

After the coronavirus pandemic, demand for thermoplastic resin products with antiviral properties is increasing. In particular, cases of applying it to exterior materials such as home appliances used indoors are increasing. Specifically, refrigerator handles, exteriors of small home appliances (air purifiers, humidifiers, etc.), remote controls, and the like correspond to the above uses.

Copper (Cu) compounds are widely known as materials capable of exhibiting antiviral performance. When such a copper compound is applied to a thermoplastic resin composition, it is difficult to process, there are problems such as deterioration in thermal stability, discoloration due to oxidation, etc., and applicable products are very limited. In addition, the thermoplastic resin composition to which the existing inorganic antibacterial agent or the like is applied has excellent antibacterial performance, but it has not been confirmed whether antiviral performance is expressed.

Therefore, there is a need to develop a thermoplastic resin composition having excellent antiviral properties, creep properties, stiffness, thermal stability, fluidity, and the like.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2020-0065139 and the like.

An object of the present invention is to provide a thermoplastic resin composition having excellent antiviral properties, creep properties, stiffness, thermal stability, fluidity, 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 may include about 100 parts by weight of an aromatic vinyl-vinyl cyanide-based copolymer resin; about 4 to about 20 parts by weight of an aliphatic polyamide resin; about 20 to about 60 parts by weight of glass fibers; about 4 to about 20 parts by weight of a polyetheresteramide block copolymer; about 0.1 to about 2 parts by weight of a silver (Ag) compound; and about 1 to about 20 parts by weight of zinc oxide, wherein the weight ratio of the polyetheresteramide block copolymer and the sum of the silver-based compound and the zinc oxide (polyetheresteramide block copolymer: silver-based compound + zinc oxide) is about 1 : 0.2 to about 1:3.

2. In the first embodiment, the aromatic vinyl-vinyl cyanide-based copolymer resin is a polymer of a monomer mixture containing about 50 to about 80% by weight of an aromatic vinyl-based monomer and about 20 to about 50% by weight of a vinyl cyanide-based monomer can

3. In the above 1 or 2 embodiment, the aliphatic polyamide resin is polyamide 6, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,10, polyamide 6, 12, polyamide 10,10, and polyamide 10,12.

4. In the above 1 to 3 embodiments, the polyetheresteramide block copolymer is an amino carboxylic acid having 6 or more carbon atoms, a lactam or a diamine-dicarboxylic acid salt; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms; it may be a block copolymer of a reaction mixture containing.

5. In the embodiments 1 to 4, the silver-based compound may include at least one of metal silver, silver oxide, silver halide, and a carrier containing silver ions.

6. In embodiments 1 to 5, the weight ratio of the aliphatic polyamide resin and the polyetheresteramide block copolymer may be about 1:0.5 to about 1:2.

7. In embodiments 1 to 6, the weight ratio of the silver-based compound and the zinc oxide may be about 1:2 to about 1:25.

8. In the embodiments 1 to 7, the thermoplastic resin composition is prepared by adding a corona virus S-type (BetaCoV / KCDC03) virus solution dropwise to a 5 cm × 5 cm specimen according to the ISO 21702 evaluation method, 25 ° C, RH Under the 50% condition, the time for the virus concentration reduction rate measured for each time period to reach 99% may be about 1 to about 10 hours.

9. In the embodiments 1 to 8, the thermoplastic resin composition is based on ASTM D2290, 85 ° C., 98 N under the condition of a submerged creep tester (creep tester) ASTM D638 standard tensile strength measurement specimen is deformed It may be about 0.05 to about 0.25 mm in length.

10. In the embodiments 1 to 9, the thermoplastic resin composition has a flexural strength of about 73,000 to about 100,000 kgf/cm ² days, measured at a rate of 2.8 mm/min using a 3.2 mm thick specimen according to ASTM D790. can

11. In embodiments 1 to 10, the thermoplastic resin composition has a heat deflection temperature (HDT) of about 98 to about 120 measured under conditions of a load of 18.56 kgf/cm ² and a heating rate of 120° C./hr in accordance with ASTM D648. may be °C.

12. In the embodiments 1 to 11, the thermoplastic resin composition has a melt-flow index (MI) of about 9 to about 30 g/10 measured under the condition of a load of 10 kg and 220 ° C according to ASTM D1238 can be minutes

13. Another aspect of the 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 1 to 12 above.

The present invention has the effect of providing a thermoplastic resin composition having excellent antiviral properties, creep properties, stiffness, thermal stability, fluidity, etc., and molded articles formed therefrom.

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

The thermoplastic resin composition according to the present invention includes (A) an aromatic vinyl-vinyl cyanide-based copolymer resin; (B) an aliphatic polyamide resin; (C) glass fibers; (D) a polyetheresteramide block copolymer; (E) silver (Ag)-based compounds; and (F) zinc oxide.

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

(A) Aromatic vinyl-vinyl cyanide copolymer resin

Aromatic vinyl-vinyl cyanide-based copolymer resin according to one embodiment of the present invention can improve mechanical properties such as impact resistance and rigidity, fluidity, etc. of a thermoplastic resin composition, and is used in conventional thermoplastic resin compositions. - It may be a vinyl cyanide-based copolymer resin.

In embodiments, the aromatic vinyl-vinyl cyanide-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer and then polymerizing them, and the polymerization may be performed by emulsion polymerization, suspension polymerization, bulk polymerization, and the like. It can be carried out by the polymerization method of.

In embodiments, the aromatic vinyl-vinyl cyanide-based copolymer resin may be a polymer of a monomer mixture including about 50 to about 80% by weight of an aromatic vinyl-based monomer and about 20 to about 50% by weight of a vinyl cyanide-based monomer.

In embodiments, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinyl naphthalene, etc. can be used. These may be applied alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be about 50 to about 80% by weight, for example, about 60 to about 70% by weight, based on 100% by weight of the entire aromatic vinyl-vinyl cyanide-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance and fluidity.

In specific embodiments, examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and fumaronitrile, but are not limited thereto. don't These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be about 20 to about 50% by weight, for example, about 30 to about 40% by weight, based on 100% by weight of the total weight of the aromatic vinyl-vinyl cyanide-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance and fluidity.

In embodiments, the aromatic vinyl-vinyl cyanide copolymer resin has a weight average molecular weight (Mw) of about 10,000 to about 300,000 g/mol, for example, about 50,000 to about 200,000 g, as measured by gel permeation chromatography (GPC). /mol. Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

(B) aliphatic polyamide resin

An aliphatic polyamide resin according to one embodiment of the present invention is applied to the aromatic vinyl-vinyl cyanide copolymer resin together with glass fiber, a polyether esteramide block copolymer, a silver compound, and zinc oxide to form a thermoplastic resin composition (molded article) ), which can improve antiviral properties, creep properties, stiffness, thermal stability, fluidity, etc., and aliphatic polyamide resins used in conventional thermoplastic resin compositions can be used.

In embodiments, the aliphatic polyamide resin is polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, and polyamide 6,10, polyamide 6,12, polyamide 10,10, and polyamide 10,12, combinations thereof, and the like.

In an embodiment, the aliphatic polyamide resin has a relative viscosity [η _rel ] of about 2 to 20 as measured by an Ubbelohde viscometer at 25 ° C after dissolving the aliphatic polyamide resin in concentrated sulfuric acid solution (96%) at a concentration of 0.5 g / dL. about 3, such as about 2.3 to about 2.8. Within the above range, the processability and impact resistance of the thermoplastic resin composition may be excellent.

In embodiments, the aliphatic polyamide resin may be included in an amount of about 4 to about 20 parts by weight, for example, about 5 to about 16 parts by weight, based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin. When the content of the aliphatic polyamide resin is less than about 4 parts by weight based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide copolymer resin, antiviral properties of the thermoplastic resin composition (molded article) may deteriorate, etc. When it exceeds about 20 parts by weight, there is a concern that creep characteristics, rigidity, etc. of the thermoplastic resin composition (molded article) may decrease.

(C) glass fiber

The glass fiber according to one embodiment of the present invention is applied together with an aliphatic polyamide resin, a polyetheresteramide block copolymer, a silver compound and zinc oxide to the aromatic vinyl-vinyl cyanide copolymer resin to form a thermoplastic resin composition (molded article) ), which can improve antiviral properties, creep properties, stiffness, thermal stability, fluidity, etc., glass fibers used in conventional thermoplastic resin compositions can be used.

In embodiments, the glass fiber may be in the form of a fiber and may have cross sections of various shapes such as circular, elliptical, and rectangular. For example, it may be preferable in terms of mechanical properties to use fibrous glass fibers of circular and/or rectangular cross-section.

In embodiments, the circular cross-section of the glass fiber may have a cross-sectional diameter of about 5 to about 20 μm and a length of about 2 to about 20 mm before processing, and the rectangular cross-section of the glass fiber may have a cross-sectional aspect ratio (long diameter of the cross section / The short diameter of the cross section may be about 1.5 to about 10, the short diameter may be about 2 to about 10 μm, and the length before processing may be about 2 to about 20 mm. Stiffness, processability, etc. of the thermoplastic resin composition may be improved within the above range.

In a specific embodiment, the glass fiber may be treated with a conventional surface treatment agent. A silane-based compound, a urethane-based compound, an epoxy-based compound, etc. may be used as the surface treatment agent, but is not limited thereto.

In embodiments, the glass fiber may be included in an amount of about 20 to about 60 parts by weight, for example, about 30 to about 50 parts by weight, based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin. When the content of the glass fiber is less than about 20 parts by weight based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin, there is a concern that creep characteristics, stiffness, etc. of the thermoplastic resin composition (molded article) may be lowered, and about When it exceeds 60 parts by weight, there is a fear that the fluidity and the like of the thermoplastic resin composition (molded article) may decrease.

(D) polyetheresteramide block copolymer

The polyether esteramide block copolymer according to one embodiment of the present invention is applied to the aromatic vinyl-vinyl cyanide-based copolymer resin together with an aliphatic polyamide resin, glass fiber, a silver compound, and zinc oxide to form a thermoplastic resin composition (molded article). ), which can improve antiviral properties, creep properties, stiffness, heat stability, fluidity, etc., of amino carboxylic acids having 6 or more carbon atoms, lactams or diamine-dicarboxylic acid salts; polyalkylene glycol; And a block copolymer of a reaction mixture comprising; and a dicarboxylic acid having 4 to 20 carbon atoms.

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

In embodiments, 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. , copolymers of ethylene glycol and tetrahydrofuran, and the like can be exemplified. For example, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, and the like can be used.

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

In embodiments, 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 diamine having 6 or more carbon atoms may form an ester bond. 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 embodiment, the polyether esteramide block copolymer may be prepared by a known synthesis method, for example, prepared according to the synthesis method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Publication No. 55-133424 It can be.

In embodiments, the polyetheresteramide block copolymer may include about 10 to about 95% by weight of the polyether-ester block. Within the above range, the impact resistance of the thermoplastic resin composition (molded article) may be excellent.

In embodiments, the polyether esteramide block copolymer may be included in about 4 to about 20 parts by weight, for example, about 5 to about 16 parts by weight, based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin. there is. When the content of the polyether esteramide block copolymer is less than about 4 parts by weight based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin, antiviral properties and fluidity of the thermoplastic resin composition (molded article) are deteriorated. If it exceeds about 20 parts by weight, there is a fear that the stiffness, creep characteristics, etc. of the thermoplastic resin composition (molded article) may decrease.

In embodiments, the weight ratio of the aliphatic polyamide resin and the polyetheresteramide block copolymer (aliphatic polyamide resin:polyetheresteramide block copolymer) is about 1:0.5 to about 1:2, for example about 1 : 0.52 to about 1:1.9. Within the above range, antiviral properties, creep properties, and stiffness of the thermoplastic resin composition (molded article) may be further improved.

(E) silver (Ag) compound

The silver-based compound according to one embodiment of the present invention is applied to the aromatic vinyl-vinyl cyanide-based copolymer resin together with an aliphatic polyamide resin, glass fiber, a polyether esteramide block copolymer, and zinc oxide to form a thermoplastic resin composition (molded article). ) It is possible to improve antiviral properties, creep properties, stiffness, thermal stability, fluidity, and the like. 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, metal silver, silver oxide, silver halide, a carrier containing silver ions, a combination thereof, and the like. Among these, a carrier containing silver ions can be used. Examples of the carrier include zeolite, silica gel, calcium phosphate, zirconium phosphate, sodium phosphate-zirconium, phosphate-sodium-hydrogen-zirconium, and the like. It is preferable that the said carrier has a porous structure. Since the carrier having a porous structure can retain the silver component even therein, not only the content of the silver component can be increased, but also the retention performance (retention performance) of the silver component is improved. Specifically, as the silver-based compound, silver sodium hydrogen zirconium phosphate or the like may be used.

In embodiments, the silver-based compound has an average particle size (D50) of about 15 μm or less, for example, about 0.1 to about may be 12 μm.

In embodiments, the silver-based compound may be included in an amount of about 0.1 to about 2 parts by weight, for example, about 0.5 to about 1.5 parts by weight, based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin. When the content of the silver-based compound is less than about 0.1 part by weight based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide copolymer resin, antiviral properties of the thermoplastic resin composition (molded article) may deteriorate, and about 2 When it exceeds parts by weight, there is a fear that the stiffness, creep characteristics, etc. of the thermoplastic resin composition (molded article) may decrease.

(F) zinc oxide

Zinc oxide of the present invention is applied together with an aliphatic polyamide resin, glass fiber, polyether esteramide block copolymer and zinc oxide to the aromatic vinyl-vinyl cyanide copolymer resin, resulting in antiviral properties of the thermoplastic resin composition (molded article). , Creep characteristics, stiffness, thermal stability, fluidity, etc. can be improved, and zinc oxide applied to conventional thermoplastic resin compositions can be used.

In a specific embodiment, the zinc oxide is composed of primary particles (single particles) and secondary particles formed by aggregation of the primary particles, and a particle size analyzer (Beckman Coulter Co., Laser Diffraction Particle Size Analyzer, LS 13 320 equipment) The measured average particle size (D50) of the primary particles may be about 1 to about 50 nm, for example about 1 to about 30 nm, and the average particle size (D50) of the secondary particles is about 0.1 to about 10 μm , for example about 0.5 to about 5 μm. Within the above range, antiviral properties and impact resistance of the thermoplastic resin composition (molded article) may be excellent.

In embodiments, the zinc oxide may be included in an amount of about 1 to about 20 parts by weight, for example, about 2 to about 18 parts by weight, based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin. When the content of the zinc oxide is less than about 1 part by weight based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide copolymer resin, antiviral properties of the thermoplastic resin composition (molded article) may deteriorate, and about 20 When it exceeds parts by weight, there is a fear that the stiffness, creep characteristics, etc. of the thermoplastic resin composition (molded article) may decrease.

In embodiments, the weight ratio of the polyetheresteramide block copolymer and the sum of the silver-based compound and the zinc oxide (polyetheresteramide block copolymer: silver-based compound + zinc oxide) is about 1: 0.2 to about 1: 3, eg For example, it may be about 1:0.25 to about 1:2.5. When the weight ratio is less than about 1:0.2, creep properties and stiffness of the thermoplastic resin composition (molded article) may deteriorate, and when the weight ratio exceeds about 1:3, the antiviral property of the thermoplastic resin composition (molded article) may deteriorate. There is a risk of deterioration.

In embodiments, the weight ratio (silver-based compound:zinc oxide) of the silver-based compound and the zinc oxide may be about 1:2 to about 1:25, for example, about 1:2.2 to about 1:23. Within the above range, antiviral properties, creep properties, and stiffness of the thermoplastic resin composition (molded article) may be further improved.

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 additive include flame retardants, fillers, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, and the like, but are not limited thereto. When using the additive, the content thereof may be about 0.001 to about 40 parts by weight, for example about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the aromatic vinyl-vinyl cyanide-based copolymer resin.

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

In an embodiment, the thermoplastic resin composition is prepared by dropping a coronavirus S-type (BetaCoV/KCDC03) virus solution on a 5 cm × 5 cm specimen according to the ISO 21702 evaluation method, and at 25 ° C. and RH 50% for each time period. The time for the measured virus concentration reduction rate to reach 99% may be about 1 to about 10 hours, for example about 2 to about 9 hours.

In embodiments, the thermoplastic resin composition has a length at which the tensile strength measurement specimen of the ASTM D638 standard is deformed, measured by a creep tester in liquid at 85 ° C. and 98 N, in accordance with ASTM D2290. 0.25 mm, for example about 0.12 to about 0.24 mm.

In one embodiment, the thermoplastic resin composition has a flexural strength of about 73,000 to about 100,000 kgf/cm ² , for example about 75,000 to about 75,000 kgf/cm 2 according to ASTM D790, measured at a speed of 2.8 mm/min using a 3.2 mm thick specimen. It may be about 95,000 kgf/cm ² .

In embodiments, the thermoplastic resin composition has a heat deflection temperature (HDT) of about 98 to about 120 ° C., measured under conditions of a load of 18.56 kgf / cm ² and a heating rate of 120 ° C / hr, in accordance with ASTM D648, for example, about 102 to about 110 °C.

In embodiments, the thermoplastic resin composition has a melt-flow index (MI) of about 9 to about 30 g/10 min, for example, about 10 to about 18 g/10 min.

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

In a specific embodiment, the molded article is useful as an antiviral interior/exterior material for products that are in frequent physical contact because it has excellent antiviral properties, creep properties, stiffness, thermal stability, fluidity, and balance of physical properties thereof. For example, it is useful as a cross fan material for air conditioners.

Hereinafter, the present invention will be described in more detail through examples, but these examples are only for the purpose of explanation 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) Aromatic vinyl-vinyl cyanide copolymer resin

A SAN resin (weight average molecular weight: 150,000 g/mol) prepared by polymerizing 66% by weight of styrene and 34% by weight of acrylonitrile was used.

(B) aliphatic polyamide resin

Polyamide 6 (manufacturer: KP Chem tech, product name: EN300) was used.

(C) glass fiber

Circular cross-section glass fibers (manufacturer: NEG, product name: T-351) were used.

(D) block copolymer

(D1) Polyamide 6-polyethylene oxide block copolymer (PA6-b-PEO, manufacturer: Sanyo chemical, product name: PELECTRON AS) was used.

(D2) A polypropylene-polyethylene oxide block copolymer (PP-b-PEO, manufacturer: Sanyo chemical, product name: PELECTRON PVL, refractive index: 1.50) was used.

(E) silver (Ag) compound

Silver phosphate glass (manufacturer: Fuji Chemical Industries, LTD. product name: BM-102SD) was used.

(F) zinc oxide

Zinc oxide (manufacturer: SH energy & chemical, product name: ANYZON) was used.

Examples 1 to 11 and Comparative Examples 1 to 13

After adding each of the components in an amount as described in Tables 1, 2, 3 and 4 below, pellets were prepared by extrusion at 230 ° C. For extrusion, a twin-screw extruder with L/D = 36 and a diameter of 45 mm was used, and the pellets produced were dried at 80 ° C for more than 2 hours and then injected in a 6 oz injection machine (molding temperature: 230 ° C, mold temperature: 60 ° C). A specimen was prepared. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1, 2, 3 and 4 below.

How to measure physical properties

(1) Antiviral evaluation: Based on the ISO 21702 evaluation method, coronavirus S-type (BetaCoV/KCDC03) virus solution was dropped on a 5 cm × 5 cm size specimen, and the virus concentration reduction rate at 25 ° C and RH 50% conditions The time (unit: hour) to reach this 99% was measured for each time period.

(2) Creep property evaluation: Tensile strength measurement specimen of ASTM D638 standard with a creep tester (manufacturer: YONEKURA MFG. Co., Ltd) under conditions of 85 ° C and 98 N in accordance with ASTM D2290 The deformed length (unit: mm) was measured.

(3) Rigidity evaluation: According to ASTM D790, flexural strength (unit: kgf/cm ² ) was measured at a speed of 2.8 mm/min using a 3.2 mm thick specimen.

(4) Thermal stability evaluation: The heat distortion temperature (HDT, unit: °C) was measured under the conditions of a load of 18.56 kgf/cm ² and a heating rate of 120 °C/hr in accordance with ASTM D648.

(5) Evaluation of fluidity: Melt-flow index (MI, unit: g/10 min) was measured under the condition of a load of 10 kg and 220 ° C in accordance with ASTM D1238.

	Example
	One	2	3	4	5
(A) (parts by weight)	100	100	100	100	100
(B) (parts by weight)	5.7	10.7	15.7	10.7	10.7
(C) (parts by weight)	43	43	43	30	50
(D1) (parts by weight)	10.7	10.7	10.7	10.7	10.7
(D2) (parts by weight)	-	-	-	-	-
(E) (parts by weight)	0.9	0.9	0.9	0.9	0.9
(F) (parts by weight)	11.4	11.4	11.4	11.4	11.4
Corona virus (S-type) concentration 99% reduction time (hr)	9	6	6	7	6
Creep deformation length (mm)	0.16	0.18	0.18	0.24	0.15
Flexural strength (kgf/cm 2 )	80,000	80,000	76,000	75,000	88,000
Heat deflection temperature (℃)	105	105	106	104	109
Melt flow rate (g/10 min)	12	13	14	16	10

	Example
	6	7	8	9	10	11
(A) (parts by weight)	100	100	100	100	100	100
(B) (parts by weight)	10.7	10.7	10.7	10.7	10.7	10.7
(C) (parts by weight)	43	43	43	43	43	43
(D1) (parts by weight)	5.7	15.7	10.7	10.7	10.7	10.7
(D2) (parts by weight)	-	-	-	-	-	-
(E) (parts by weight)	0.9	0.9	0.5	1.5	0.9	0.9
(F) (parts by weight)	11.4	11.4	11.4	11.4	2	18
Corona virus (S-type) concentration 99% reduction time (hr)	9	6	8	6	9	5
Creep deformation length (mm)	0.15	0.18	0.17	0.2	0.16	0.22
Flexural strength (kgf/cm 2 )	85,000	80,000	81,000	77,000	82,000	75,000
Heat deflection temperature (℃)	107	104	105	105	105	105
Melt flow rate (g/10 min)	10	16	12	13	11	15

	comparative example
	One	2	3	4	5	6
(A) (parts by weight)	100	100	100	100	100	100
(B) (parts by weight)	One	25	10.7	10.7	10.7	10.7
(C) (parts by weight)	43	43	15	65	43	43
(D1) (parts by weight)	10.7	10.7	10.7	10.7	One	25
(D2) (parts by weight)	-	-	-	-	-	-
(E) (parts by weight)	0.9	0.9	0.9	0.9	0.9	0.9
(F) (parts by weight)	11.4	11.4	11.4	11.4	11.4	11.4
Corona virus (S-type) concentration 99% reduction time (hr)	18	6	8	6	24	6
Creep deformation length (mm)	0.18	0.31	0.28	0.12	0.13	0.32
Flexural strength (kgf/cm 2 )	80,000	71,000	61,000	91,000	88,000	66,000
Heat deflection temperature (℃)	104	106	104	108	108	102
Melt flow rate (g/10 min)	11	15	18	6	8	21

	comparative example
	7	8	9	10	11	12	13
(A) (parts by weight)	100	100	100	100	100	100	100
(B) (parts by weight)	10.7	10.7	10.7	10.7	10.7	10.7	10.7
(C) (parts by weight)	43	43	43	43	43	43	43
(D1) (parts by weight)	-	10.7	10.7	10.7	10.7	4	20
(D2) (parts by weight)	10.7	-	-	-	-	-	-
(E) (parts by weight)	0.9	0.05	2.5	0.9	0.9	2	0.1
(F) (parts by weight)	11.4	11.4	11.4	0.5	25	22	One
Corona virus (S-type) concentration 99% reduction time (hr)	18	15	6	16	6	22	9
Creep deformation length (mm)	0.18	0.18	0.29	0.16	0.3	0.2	0.31
Flexural strength (kgf/cm 2 )	80,000	80,000	68,000	83,000	71,000	78,000	67,000
Heat deflection temperature (℃)	105	105	105	105	105	107	103
Melt flow rate (g/10 min)	13	13	14	10	17	13	17

From the above results, the thermoplastic resin composition of the present invention has antiviral properties (virus death time), creep properties (creep deformation length), stiffness (flexural strength), thermal stability (heat deformation temperature), fluidity (melt flow index) ), etc. are all excellent.

On the other hand, in the case of Comparative Example 1 in which the content of the aliphatic polyamide resin is less than the range of the present invention, it can be seen that the antiviral property is lowered, and in the case of Comparative Example 2 in which the content of the aliphatic polyamide resin exceeds the range of the present invention , It can be seen that creep characteristics, stiffness, etc. are reduced, and in the case of Comparative Example 3, in which the content of glass fibers is less than the scope of the present invention, it can be seen that creep characteristics, stiffness, etc. are reduced, and the content of glass fibers is within the scope of the present invention. In the case of Comparative Example 4 exceeding , it can be seen that fluidity and the like are lowered. In the case of Comparative Example 5, in which the content of the polyetheresteramide block copolymer is less than the scope of the present invention, it can be seen that antiviral properties, fluidity, etc. are reduced, and the content of the polyetheresteramide block copolymer exceeds the scope of the present invention In the case of Comparative Example 6, it can be seen that creep characteristics, stiffness, etc. are reduced, and in Comparative Example 7 in which the polypropylene-polyethylene oxide block copolymer (C2) is applied instead of the polyether esteramide block copolymer of the present invention, It can be seen that the antiviral activity and the like are lowered. In the case of Comparative Example 8 in which the content of the silver-based compound is less than the range of the present invention, it can be seen that antiviral properties, etc. are reduced, and in the case of Comparative Example 9 in which the content of the silver-based compound exceeds the range of the present invention, creep properties, stiffness, etc. It can be seen that this decrease, and in the case of Comparative Example 10, in which the content of zinc oxide is less than the range of the present invention, it can be seen that antiviral properties, etc. are reduced, and the content of zinc oxide exceeds the scope of the present invention. In this case, it can be seen that creep characteristics, stiffness, etc. are reduced. In addition, even if the contents of the polyetheresteramide block copolymer (D1), the silver-based compound (E), and the zinc oxide (F) are included in the scope of the present invention, the polyetheresteramide block copolymer (D1) and In the case of Comparative Example 12 in which the weight ratio (D1:E+F) of the sum of the silver-based compound (E) and the zinc oxide (F) exceeds the scope of the present invention (1:6), antiviral properties, etc. are reduced. In the case of Comparative Example 13, which is less than the range of the present invention (1: 0.06), it can be seen that creep characteristics, stiffness, etc. are reduced.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a limiting sense. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

Claims (13)

1. About 100 parts by weight of an aromatic vinyl-vinyl cyanide copolymer resin;

   about 4 to about 20 parts by weight of an aliphatic polyamide resin;

   about 20 to about 60 parts by weight of glass fibers;

   about 4 to about 20 parts by weight of a polyetheresteramide block copolymer;

   about 0.1 to about 2 parts by weight of a silver (Ag) compound; and

   About 1 to about 20 parts by weight of zinc oxide,

   The polyether ester amide block copolymer and the weight ratio of the sum of the silver-based compound and the zinc oxide (polyether ester amide block copolymer: silver-based compound + zinc oxide) is about 1: 0.2 to about 1: 3, characterized in that the thermoplastic resin composition.
2. The method of claim 1, wherein the aromatic vinyl-vinyl cyanide-based copolymer resin is a polymer of a monomer mixture comprising about 50 to about 80% by weight of an aromatic vinyl-based monomer and about 20 to about 50% by weight of a vinyl cyanide-based monomer. A thermoplastic resin composition to be.
3. The method of claim 1 or 2, wherein the aliphatic polyamide resin is polyamide 6, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,10, polyamide 6, A thermoplastic resin composition comprising at least one of 12, polyamide 10,10, and polyamide 10,12.
4. The polyetheresteramide block copolymer according to any one of claims 1 to 3, wherein the polyetheresteramide block copolymer is selected from an amino carboxylic acid having 6 or more carbon atoms, a lactam or a diamine-dicarboxylic acid salt; polyalkylene glycol; And a dicarboxylic acid having 4 to 20 carbon atoms; a block copolymer of a reaction mixture comprising a thermoplastic resin composition.
5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the silver-based compound includes at least one of metal silver, silver oxide, silver halide, and a carrier containing silver ions.
6. 6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the weight ratio of the aliphatic polyamide resin and the polyetheresteramide block copolymer is from about 1:0.5 to about 1:2.
7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein a weight ratio of the silver-based compound and the zinc oxide is from about 1:2 to about 1:25.
8. The method according to any one of claims 1 to 7, wherein the thermoplastic resin composition is prepared by adding a coronavirus S-type (BetaCoV/KCDC03) virus solution to a 5 cm × 5 cm specimen according to the ISO 21702 evaluation method, The thermoplastic resin composition, characterized in that the time for the virus concentration reduction rate to reach 99% measured at 25 ° C. and 50% RH conditions for each time period is about 1 to about 10 hours.
9. The method according to any one of claims 1 to 8, wherein the thermoplastic resin composition is based on ASTM D2290, tensile strength of ASTM D638 standard measured by a submerged creep tester under conditions of 85 ° C. and 98 N A thermoplastic resin composition, characterized in that the length to which the specimen is deformed is from about 0.05 to about 0.25 mm.
10. The method according to any one of claims 1 to 9, wherein the thermoplastic resin composition has a flexural strength of about 73,000 to about 100,000 kgf measured at a speed of 2.8 mm/min using a 3.2 mm thick specimen according to ASTM D790. / cm ² Thermoplastic resin composition, characterized in that.
11. The method according to any one of claims 1 ^to 10, wherein the thermoplastic resin composition has a heat distortion temperature (HDT) of about A thermoplastic resin composition, characterized in that 98 to about 120 ℃.
12. The method according to any one of claims 1 to 11, wherein the thermoplastic resin composition has a melt-flow index (MI) of about 9 to about 10 kg and a melt-flow index measured at 220° C. according to ASTM D1238. A thermoplastic resin composition, characterized in that 30 g / 10 minutes.
13. A molded article characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 12.