Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition comprising a base resin containing recycled resin, a new acrylic graft polymer, a new diene graft polymer, and a new vinyl non-graft polymer, and additives including a polyamide elastomer, an olefin non-graft polymer, a metal stearate, a first antibacterial agent containing zinc ions carried on a silicate glass support, and a second antibacterial agent containing silver ions carried on a phosphate glass support, wherein the thermoplastic resin composition contains 0.20 to 2.00 parts by weight of the first antibacterial agent and 0.02 to 0.50 parts by weight of the second antibacterial agent per 100 parts by weight of the base resin.

Description

[Technical Field]

[0001] The present invention claims the benefit of priority based on Korean Patent Application No. 10-2022-0147651, filed November 8, 2022, and all contents disclosed in the documents of this Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a thermoplastic resin composition. [Background technology]

[0003] Recently, as people have become more concerned about personal health and hygiene and income levels have risen, the demand for thermoplastic resin molded products with antibacterial and hygienic functions has increased. As a result, the number of thermoplastic resin molded products that can remove or inhibit bacteria from the surfaces of household goods and home appliances has increased, and the development of stable and reliable functional antibacterial materials has been required.

[0004] To produce an antibacterial thermoplastic resin composition, an antibacterial agent must be added, and such antibacterial agents can be divided into organic and inorganic antibacterial agents. Organic antibacterial agents can be harmful to the human body, can decompose during processing at high temperatures, resulting in the loss or reduction of antibacterial efficacy, and have poor antibacterial durability, making them unsuitable for various applications. Inorganic antibacterial agents have excellent thermal stability, but can be difficult to disperse or discolor during processing at high temperatures, and have poor antibacterial durability due to the continued elution of metal ions supported on the support, making them unsuitable for various applications.

[0005] Therefore, research is being conducted on antibacterial thermoplastic resin compositions that are harmless to the human body, maintain antibacterial activity even when processed at high temperatures, have good antibacterial durability, and can be used in various fields. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP1997-241475A Summary of the Invention [Problem to be solved by the invention]

[0007] The problem to be solved by the present invention is to provide a thermoplastic resin composition that is excellent in all of antibacterial properties, antibacterial durability, chemical resistance, appearance properties, and impact resistance. [Means for solving the problem]

[0008] In order to solve the above-mentioned problems, 1) the present invention provides a thermoplastic resin composition comprising a base resin containing recycled resin, a new acrylic graft polymer, a new diene graft polymer, and a new vinyl non-graft polymer, and additives including a polyamide elastomer, an olefin non-graft polymer, a metal stearate, a first antibacterial agent containing zinc ions carried on a silicate glass support, and a second antibacterial agent containing silver ions carried on a phosphate glass support, wherein the thermoplastic resin composition contains 0.20 to 2.00 parts by weight of the first antibacterial agent and 0.02 to 0.50 parts by weight of the second antibacterial agent per 100 parts by weight of the base resin.

[0009] 2) The present invention provides the thermoplastic resin composition according to 1) above, wherein the weight ratio of the first antibacterial agent to the second antibacterial agent is 1:0.10 to 0.50.

[0010] 3) The present invention provides the thermoplastic resin composition according to 1) or 2), wherein the polyamide elastomer has a weight average molecular weight of 1,000 to 350,000 g / mol.

[0011] 4) The present invention provides a thermoplastic resin composition according to any one of 1) to 3) above, wherein the polyamide elastomer includes at least one of polyetheramide and polyetheresteramide.

[0012] 5) The present invention provides a thermoplastic resin composition according to any one of 1) to 4) above, which comprises 0.10 to 10.00 parts by weight of the polyamide elastomer per 100 parts by weight of the base resin.

[0013] 6) The present invention provides a thermoplastic resin composition according to any one of 1) to 5), wherein the non-grafted olefin polymer contains an olefin monomer unit and at least one of a vinyl acetate monomer unit and an alkyl (meth)acrylate monomer unit.

[0014] 7) The present invention provides a thermoplastic resin composition according to 6), wherein the non-grafted olefin polymer contains 68.0 to 80.0% by weight of the olefin monomer unit and 20.0 to 32.0% by weight of one or more of the vinyl acetate monomer unit and the alkyl (meth)acrylate monomer unit.

[0015] 8) The present invention provides a thermoplastic resin composition according to any one of 1) to 7) above, which comprises 0.50 to 5.00 parts by weight of the non-grafted olefin polymer per 100 parts by weight of the base resin.

[0016] 9) The present invention provides a thermoplastic resin composition according to any one of 1) to 8), wherein the metal stearate includes one or more of potassium stearate, calcium stearate, sodium stearate, magnesium stearate, and aluminum stearate.

[0017] 10) The present invention provides a thermoplastic resin composition according to any one of 1) to 9) above, which comprises 0.05 to 3.00 parts by weight of the metal stearate per 100 parts by weight of the base resin.

[0018] 11) The present invention provides a thermoplastic resin composition in any one of 1) to 10) above, wherein the recycled resin contains a diene rubber polymer, a vinyl cyanide monomer unit, and a vinyl aromatic monomer unit.

[0019] 12) The present invention provides a thermoplastic resin composition in any one of 1) to 11) above, wherein the recycled resin contains 10 to 30% by weight of a diene rubber polymer, 15 to 30% by weight of vinyl cyanide monomer units, and the remainder of vinyl aromatic monomer units.

[0020] 13) The present invention provides a thermoplastic resin composition according to any one of 1) to 12) above, which comprises 15.00 to 70.00 parts by weight of the recycled resin per 100 parts by weight of the base resin.

[0021] 14) The present invention provides a thermoplastic resin composition according to any one of 1) to 13), wherein the new acrylic graft polymer comprises an acrylic rubber polymer and a shell containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted to the acrylic rubber polymer.

[0022] 15) The present invention provides a thermoplastic resin composition according to any one of 1) to 14) above, which comprises 1.00 to 10.00 parts by weight of the new acrylic graft polymer per 100 parts by weight of the base resin.

[0023] 16) The present invention provides a thermoplastic resin composition according to any one of 1) to 15), wherein the nascent diene graft polymer comprises a diene rubbery polymer and a shell containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted to the diene rubbery polymer.

[0024] 17) The present invention provides a thermoplastic resin composition according to any one of 1) to 16) above, which comprises 5.00 to 30.00 parts by weight of the new diene graft polymer per 100 parts by weight of the base resin.

[0025] 18) The present invention provides a thermoplastic resin composition according to any one of 1) to 17), wherein the new vinyl-based non-graft polymer contains vinyl aromatic monomer units and vinyl cyanide monomer units. [Effects of the Invention]

[0026] The thermoplastic resin composition of the present invention maintains basic physical properties such as chemical resistance, appearance characteristics, and impact resistance, and also has excellent antibacterial properties and antibacterial durability, and therefore can be used as a raw material for various antibacterial products. DETAILED DESCRIPTION OF THE INVENTION

[0027] The present invention will now be described in more detail to aid in understanding the present invention.

[0028] The terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted as having meanings and concepts that are consistent with the technical idea of ​​the present invention, based on the principle that inventors can appropriately define the concepts of terms in order to best explain their inventions.

[0029] In the present invention, the average particle size can be measured using a dynamic light scattering method, and more specifically, it can mean the arithmetic average particle size in the particle size distribution measured by the dynamic light scattering method, i.e., the intensity distribution average particle size.

[0030] In the present invention, the average particle size can be measured using a Nicomp 380 device manufactured by Particle Sizing Systems.

[0031] In the present invention, the weight average molecular weight of the non-grafted vinyl polymer can be measured as a relative value to that of a standard polystyrene sample by gel permeation chromatography using tetrahydrofuran as an eluent.

[0032] In the present invention, the weight average molecular weight of the polyamide elastomer can be measured by dissolving the polyamide elastomer in tetrahydrofuran at a concentration of 1 mg / ml, filtering the solution through a 450 nm syringe filter, and then subjecting the solution to gel permeation chromatography.

[0033] In the present invention, the diene monomer may be one or more of 1,3-butadiene, isoprene, chloroprene and piperylene, among which 1,3-butadiene is preferred.

[0034] In the present invention, the alkyl (meth)acrylate monomer may be a general term for alkyl acrylate monomers and alkyl methacrylate monomers. The alkyl (meth)acrylate monomer is a C1 to C 10 The alkyl (meth)acrylate monomer may be one or more of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and decyl (meth)acrylate, and among these, butyl acrylate is preferred.

[0035] In the present invention, the vinyl aromatic monomer may be one or more of styrene, α-methylstyrene, α-ethylstyrene and p-methylstyrene, among which styrene is preferred.

[0036] In the present invention, the vinyl cyanide monomer may be one or more of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, among which acrylonitrile is preferred.

[0037] In the present invention, the olefinic monomer may be one or more of ethylene, propylene and butylene, of which ethylene is preferred.

[0038] thermoplastic resin composition A thermoplastic resin composition according to one embodiment of the present invention comprises: 1. a base resin including recycled resin, a new acrylic graft polymer, a new diene graft polymer, and a new vinyl non-graft polymer; and additives including a polyamide elastomer, an olefin non-graft polymer, a metal stearate, a first antibacterial agent including zinc ions carried on a silicate glass support, and a second antibacterial agent including silver ions carried on a phosphate glass support, wherein the first antibacterial agent is contained in an amount of 0.20 to 2.00 parts by weight, and the second antibacterial agent is contained in an amount of 0.02 to 0.50 parts by weight per 100 parts by weight of the base resin.

[0039] The components of the thermoplastic resin composition according to one embodiment of the present invention will be described in detail below.

[0040] 1. Base resin 1) Recycled resin Recycled resin is a component included in a thermoplastic resin composition to be certified as an eco-friendly product. It is a recycled product made by processing and reusing used resin or resin waste. Specifically, the recycled resin may refer to a resin that is collected, crushed, washed, separated, and sorted from resin waste, and then processed and reused according to its intended use. The form of the recycled resin is not particularly limited.

[0041] The recycled resin may include one or more of recycled polyethylene, recycled polypropylene, recycled polyester, recycled polystyrene, recycled polyamide, recycled polycarbonate, recycled diene-based graft polymers, and recycled vinyl-based non-graft polymers.

[0042] The recycled resin may include a diene rubber polymer, a vinyl cyanide monomer unit, and a vinyl aromatic monomer unit. The diene rubber polymer may improve the impact resistance of the recycled resin. The vinyl cyanide monomer unit may improve the chemical resistance of the recycled resin. Furthermore, the vinyl aromatic monomer unit may improve the processability of the recycled resin.

[0043] On the other hand, the recycled resin may contain 10.0 to 30.0 wt %, preferably 10.0 to 25.0 wt %, more preferably 10.0 to 20.0 wt % of a diene rubber polymer. When the above conditions are satisfied, the impact resistance of the recycled resin can be further improved.

[0044] The recycled resin may contain 15.0 to 30.0 wt %, preferably 16.0 to 27.0 wt %, and more preferably 18.0 to 24.0 wt % of vinyl cyanide monomer units. When the above conditions are met, the chemical resistance of the recycled resin can be further improved.

[0045] The recycled resin may contain a residual amount of vinyl aromatic monomer units to bring the total weight to 100% by weight.

[0046] The thermoplastic resin composition may contain 15.00 to 70.00 parts by weight, preferably 15.00 to 65.00 parts by weight, and more preferably 20.00 to 60.00 parts by weight of the recycled resin per 100 parts by weight of the base resin. When the above conditions are met, a carbon reduction effect can be obtained and good physical properties can be achieved.

[0047] 2) New acrylic graft polymers The new acrylic graft polymer is a never-before-used acrylic graft polymer, which is a component that improves the weather resistance and impact resistance of thermoplastic resin compositions.

[0048] The nascent acrylic graft polymer may include an acrylic rubber polymer and a shell including vinyl aromatic monomer units and vinyl cyanide monomer units grafted to the acrylic rubber polymer. The shell may include vinyl aromatic monomer units and vinyl cyanide monomer units that are not grafted to the acrylic rubber polymer.

[0049] The acrylic rubber polymer can be produced by polymerizing, specifically, crosslinking, alkyl (meth)acrylate monomers. The acrylic rubber polymer may have an average particle size of 50 to 600 nm, preferably 100 to 550 nm, and more preferably 120 to 500 nm. When the above conditions are met, both impact resistance and weather resistance can be improved.

[0050] The new acrylic graft polymer may contain the acrylic rubber polymer in an amount of 30.0 to 70.0 wt %, preferably 35.0 to 65.0 wt %, more preferably 40.0 to 60.0 wt %. When the above conditions are satisfied, the impact resistance and weather resistance of the acrylic graft polymer can be further improved.

[0051] The nascent acrylic graft polymer may contain the vinyl aromatic monomer units in an amount of 20.0 to 60.0 wt %, preferably 25.0 to 55.0 wt %, more preferably 30.0 to 50.0 wt %. When the above conditions are satisfied, the processability of the acrylic graft polymer can be further improved.

[0052] The nascent acrylic graft polymer may contain the vinyl cyanide monomer unit in an amount of 1.0 to 30.0 wt %, preferably 3.0 to 25.0 wt %, and more preferably 5.0 to 20.0 wt %. When the above conditions are satisfied, the chemical resistance of the acrylic graft polymer can be further improved.

[0053] The thermoplastic resin composition may contain 1.00 to 10.00 parts by weight, preferably 1.50 to 8.50 parts by weight, and more preferably 2.00 to 7.00 parts by weight of the new acrylic graft polymer per 100 parts by weight of the base resin. When the above conditions are met, the weather resistance and impact resistance of the thermoplastic resin composition can be further improved.

[0054] 3) New diene-based graft polymers The nascent diene graft polymer is a diene graft polymer that has never been used before and is a component that improves the impact resistance of thermoplastic resin compositions.

[0055] The nascent diene graft polymer may include a diene rubbery polymer and a shell containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted to the diene rubbery polymer. The shell may include vinyl aromatic monomer units and vinyl cyanide monomer units that are not grafted to the diene rubbery polymer.

[0056] The diene rubber polymer may be prepared by crosslinking a diene monomer or a monomer mixture containing a diene monomer as a main component.

[0057] The diene rubbery polymer may have an average particle size of 50 to 600 nm, preferably 150 to 450 nm, and more preferably 200 to 400 nm. When the above conditions are satisfied, the impact resistance of the newly produced diene graft polymer can be improved.

[0058] The nascent diene graft polymer may contain the diene rubber polymer in an amount of 40.0 to 80.0 wt %, preferably 45.0 to 75.0 wt %, more preferably 50.0 to 70.0 wt %. When the above conditions are satisfied, the impact resistance of the nascent diene graft polymer can be further improved.

[0059] The nascent diene graft polymer may contain the vinyl aromatic monomer units in an amount of 10.0 to 50.0 wt %, preferably 15.0 to 45.0 wt %, more preferably 20.0 to 40.0 wt %. When the above conditions are satisfied, the processability of the nascent diene graft polymer can be further improved.

[0060] The nascent diene graft polymer may contain the vinyl cyanide monomer unit in an amount of 1.0 to 30.0 wt %, preferably 3.0 to 27.0 wt %, and more preferably 5.0 to 25.0 wt %. When the above conditions are satisfied, the chemical resistance of the nascent diene graft polymer can be further improved.

[0061] The thermoplastic resin composition may contain 5.00 to 30.00 parts by weight, preferably 7.00 to 27.00 parts by weight, and more preferably 10.00 to 25.00 parts by weight of the new diene graft polymer per 100 parts by weight of the base resin. When the above conditions are satisfied, the impact resistance of the thermoplastic resin composition can be further improved.

[0062] 4) New vinyl non-graft polymers The nascent vinyl non-grafted polymer is a component that improves the processability of the thermoplastic resin composition.

[0063] The nascent vinyl-based non-grafted polymer may include a vinyl aromatic monomer unit and a vinyl cyanide monomer unit. Specifically, the nascent vinyl-based non-grafted polymer may include a vinyl aromatic monomer unit to improve processability, and a vinyl cyanide monomer to improve chemical resistance.

[0064] The nascent vinyl-based non-graft polymer may contain vinyl aromatic monomer units and vinyl cyanide monomer units in a weight ratio of 90.0:10.0 to 60.0:40.0, preferably 85.0:15.0 to 65.0:35.0, and more preferably 80.0:20.0 to 70.0:30.0. By satisfying the above conditions, a nascent vinyl-based non-graft polymer with well-balanced improved processability and chemical resistance can be produced.

[0065] The thermoplastic resin composition may contain the nascent non-grafted vinyl polymer as the balance so that the sum of the components of the base resin is 100 parts by weight.

[0066] 2. Additives 1) Polyamide elastomer The polyamide elastomer is a component that improves the antibacterial durability of the thermoplastic resin composition. Specifically, the unshared electron pairs of the polyamide elastomer allow the elution rate of the metal ions of the inorganic antibacterial agent to be controlled to be constant and slow, thereby significantly improving the antibacterial durability of the thermoplastic resin composition.

[0067] The polyamide elastomer may include one or more of polyetheramide and polyetheresteramide. The polyamide elastomer may include a hard segment including one or more of PA6, PA66, PA6 / 66, PA610, PA612, PA614, and PA616, and an OH group. - or NH2 - The soft segments may be in the form of polyether segments functionalized to a polymer.

[0068] The weight-average molecular weight of the polyamide elastomer may be 1,000 to 350,000 g / mol, preferably 10,000 to 340,000 g / mol, more preferably 50,000 to 335,000 g / mol, and most preferably 150,000 to 300,000 g / mol. When the above conditions are satisfied, a thermoplastic resin composition having improved antibacterial durability, impact resistance, appearance quality, and chemical resistance can be produced.

[0069] The thermoplastic resin composition may contain 0.10 to 10.00 parts by weight, preferably 0.10 to 7.00 parts by weight, and more preferably 0.10 to 5.00 parts by weight of the polyamide elastomer per 100 parts by weight of the base resin. When the above conditions are satisfied, a thermoplastic resin composition can be produced that has improved antibacterial durability, as well as improved impact resistance, appearance quality, and chemical resistance.

[0070] 2) Olefin-based non-graft polymers The olefin-based non-grafted polymer is a component that improves the antimicrobial durability and chemical resistance of the thermoplastic resin composition.

[0071] The olefin-based non-grafted polymer may include an olefin-based monomer unit and one or more of a vinyl acetate monomer unit and an alkyl (meth)acrylate-based monomer unit in order to improve the antibacterial durability, chemical resistance, and appearance properties of the thermoplastic resin composition.

[0072] The non-grafted olefin polymer may contain 68.0 to 80.0 wt%, preferably 70.0 to 78.0 wt%, and more preferably 71.0 to 76.0 wt% of the olefin monomer units. The non-grafted olefin polymer may contain 20.0 to 32.0 wt%, preferably 22.0 to 30.0 wt%, and more preferably 24.0 to 29.0 wt% of one or more of the vinyl acetate monomer units and the alkyl (meth)acrylate monomer units. When the above conditions are satisfied, the antibacterial durability, chemical resistance, and appearance properties of the thermoplastic resin composition can be further improved.

[0073] The non-grafted olefin polymer may be one or more of an ethylene-vinyl acetate polymer, an ethylene-methyl acrylate polymer, and an ethylene-butyl acrylate polymer.

[0074] The thermoplastic resin composition may contain 0.50 to 5.00 parts by weight, preferably 0.70 to 4.00 parts by weight, and more preferably 1.00 to 3.00 parts by weight of the non-grafted olefin polymer relative to 100 parts by weight of the base resin. When the above conditions are met, the non-grafted olefin polymer can be uniformly dispersed in the thermoplastic resin composition, and the appearance characteristics, antibacterial durability, and chemical resistance of the thermoplastic resin composition can be improved.

[0075] 3) Metal stearates Metal stearates are components that improve the antimicrobial persistence of thermoplastic resin compositions containing recycled resins.

[0076] The recycled resin may contain a halogen element, but to prevent the halogen element from reacting with the zinc ions and silver ions contained in the first and second antibacterial agents, the metal stearate preferably contains a metal that is more reactive than the zinc ions and silver ions contained in the first and second antibacterial agents described below. Therefore, the metal stearate may include one or more of potassium stearate, calcium stearate, sodium stearate, magnesium stearate, and aluminum stearate, and among these, it is preferable to include one or more of calcium stearate and magnesium stearate.

[0077] The thermoplastic resin composition may contain 0.05 to 3.00 parts by weight, preferably 0.05 to 2.50 parts by weight, and more preferably 0.05 to 2.00 parts by weight of the metal stearate relative to 100 parts by weight of the base resin. When the above conditions are satisfied, the antibacterial durability of the thermoplastic resin composition can be further improved.

[0078] 4) First antibacterial agent The first antibacterial agent comprises zinc ions supported on a silicate glass support, and is a component that reduces the manufacturing cost of the thermoplastic resin composition and improves antibacterial activity and antibacterial persistence.

[0079] The thermoplastic resin composition may contain 0.20 to 2.00 parts by weight, preferably 0.20 to 1.70 parts by weight, and more preferably 0.20 to 1.50 parts by weight of the first antibacterial agent per 100 parts by weight of the base resin. If the content of the first antibacterial agent is less than the above-mentioned condition, the antibacterial activity and antibacterial durability of the thermoplastic resin composition will be significantly reduced. Furthermore, if the content of the first antibacterial agent is greater than the above-mentioned condition, the impact resistance of the thermoplastic resin composition will be significantly reduced.

[0080] 5) Second antibacterial agent The second antibacterial agent includes silver ions supported on a phosphate glass support. The second antibacterial agent is a component that improves the antibacterial properties and antibacterial durability of the thermoplastic resin composition. The phosphate glass support maintains a slow elution rate of the silver ions from the second antibacterial agent, resulting in excellent antibacterial durability.

[0081] On the other hand, the second antibacterial agent has excellent compatibility with the nascent diene graft polymer and the nascent acrylic graft polymer and does not deteriorate their physical properties. However, if the thermoplastic resin composition contains an antibacterial agent containing silver ions supported on a zirconium phosphate support instead of the second antibacterial agent, the antibacterial activity and antibacterial durability can be improved, but the compatibility between the nascent diene graft polymer and the nascent acrylic graft polymer may be reduced, resulting in a decrease in the impact resistance of the thermoplastic resin composition.

[0082] The thermoplastic resin composition may contain 0.02 to 0.50 parts by weight, preferably 0.02 to 0.40 parts by weight, and more preferably 0.02 to 0.30 parts by weight, of the second antibacterial agent relative to 100 parts by weight of the base resin. If the second antibacterial agent is contained in an amount less than the above-mentioned range, the antibacterial activity and antibacterial durability of the thermoplastic resin composition will be significantly reduced. Furthermore, if the second antibacterial agent is contained in an amount greater than the above-mentioned range, the antibacterial activity and antibacterial durability of the thermoplastic resin composition will be reduced and production costs will increase, which is undesirable.

[0083] Meanwhile, the weight ratio of the first antibacterial agent to the second antibacterial agent may be 1:0.01-0.50, preferably 1:0.01-0.40, and more preferably 1:0.01-0.20. When the above conditions are satisfied, the overall physical properties of the thermoplastic resin composition are well balanced, and excellent antibacterial durability can be achieved.

[0084] While the present invention may be embodied in various different forms, it is to be understood that the invention is not limited to the specific embodiments set forth herein, and that the invention may be embodied in various different forms without departing from the spirit or scope of the present invention.

[0085] Examples and Comparative Examples Information regarding the ingredients used in the following examples and comparative examples is as follows:

[0086] 1. Base resin 1) Recycled resin: Recycled resin containing 15% by weight of butadiene rubber polymer, 21% by weight of acrylonitrile units, and 64% by weight of styrene units

[0087] 2) New acrylic graft polymer: ASA graft polymer containing 50.0 wt% of butyl acrylate rubbery polymer having an average particle size of 140 nm and a shell containing 36.5 wt% of styrene monomer units and 13.5 wt% of acrylonitrile monomer units grafted onto the butyl acrylate rubbery polymer.

[0088] 3) New diene-based graft polymer: ABS graft polymer containing 60.0% by weight of a butadiene rubber-like polymer having an average particle size of 300 nm and a shell containing 30.0% by weight of styrene monomer units and 10.0% by weight of acrylonitrile monomer units grafted onto the butadiene rubber-like polymer.

[0089] 4) New vinyl non-grafted polymer: styrene / acrylonitrile polymer containing 76.0% by weight of styrene monomer units and 24.0% by weight of acrylonitrile monomer units.

[0090] 2. Additives 1) Polyamide elastomer (1): Polyetheramide 1: MH2030 (weight average molecular weight: 150,000 g / mol) manufactured by AKEMA

[0091] (2) Polyetheramide 2: Pelestat 6500 manufactured by Sanyo (weight average molecular weight: 300,000 g / mol)

[0092] 2) Olefin-based non-graft polymers (1) Random ethylene-methyl acrylate polymer 1: LOTRYL 24MA02T manufactured by SK Geocentric Co., Ltd. (ethylene monomer unit: 76.0 wt %, methyl acrylate monomer unit: 24.0 wt %, flow index (ASTM D1238, 190°C, 2.16 kg): 2.0 g / 10 min, melting point (ISO 11357-3): 95°C)

[0093] (2) Random ethylene-methyl acrylate polymer 2: LOTRYL 29MA03T manufactured by SK Geocentric Co., Ltd. (ethylene monomer unit: 71.0 wt %, methyl acrylate monomer unit: 29.0 wt %, flow index (ASTM D1238, 190°C, 2.16 kg): 3.0 g / 10 min), melting point (ISO 11357-3): 92°C)

[0094] 3) Metal stearates (1) Calcium stearate (2) Magnesium stearate

[0095] 4) First antibacterial agent: VZ600 manufactured by TOAGOSEI (zinc ions supported on a silicate glass support)

[0096] 5) Second antibacterial agent: IONPURE WPA (silver ions supported on a phosphate glass support) manufactured by ISHIZUKA Co., Ltd.

[0097] The above-mentioned components were mixed and stirred in the amounts shown in Tables 1 to 6 below to produce thermoplastic resin compositions.

[0098] Experimental Example 1 The thermoplastic resin compositions of the Examples and Comparative Examples were fed into a twin-screw extruder set at 230°C and extruded to produce pellets. These pellets were extruded to produce test pieces, and the physical properties were measured by the following methods. The results are shown in Tables 1 to 6 below.

[0099] (1) Antibacterial activity value: In accordance with the ISO 22196 antibacterial evaluation method, Escherichia coli and Staphylococcus aureus were inoculated onto test pieces measuring 5 cm x 5 cm x 0.3 cm, and after culturing for 24 hours at 35°C and a relative humidity of 90%, the antibacterial activity value was measured.

[0100] (2) Antibacterial durability (after pretreatment): In accordance with the ISO 22196 antibacterial evaluation method, a 5cm x 5cm x 0.3cm test piece was immersed in water at 50°C for 32 hours, and then inoculated with Escherichia coli and Staphylococcus aureus. After culturing for 24 hours at 35°C and 90% relative humidity, the antibacterial activity value was measured.

[0101] (3) Appearance quality: An injection test piece having a curved surface was scored with a blade, folded, and then the condition of the folded surface was visually evaluated. ○: No peeling occurred △: When the injection test piece is scored with a knife and folded, and then another force is applied, peeling occurs on the folded surface. ×: After making a crease in the injection test piece with a knife and folding it, peeling occurred on the folded surface without applying any additional force.

[0102] (4) Chemical resistance: A test piece fixed to a jig with a strain of 1.1% was immersed in cyclopentane for 3 minutes, and then subjected to a 180° bending test. ○: No change △: Fine cracks occurred ×: cracks occur and then break

[0103] (5) Impact strength (kg·cm / cm, 1 / 4 In): Izod impact strength was measured at 25°C in accordance with ASTM D265. An Izod impact strength of 20 kg·cm / cm or more was considered to have excellent impact resistance.

[0104] [Table 1]

[0105] [Table 2]

[0106] [Table 3]

[0107] [Table 4]

[0108] [Table 5]

[0109] [Table 6]

[0110] Referring to Tables 1 to 6, Examples 1 to 13 achieved excellent antibacterial properties, appearance quality, chemical resistance, and impact strength. However, Comparative Examples 1 and 2, which contained a small amount of zinc ions supported on a silicate glass support, showed significantly reduced antibacterial properties and antibacterial durability compared to Examples 1 to 13.

[0111] Furthermore, Comparative Examples 3 and 4, which contained an excessive amount of zinc ions supported on the silicate glass support, had significantly lower impact strength than Examples 1-13.

[0112] Furthermore, Comparative Example 5, which contained a small amount of silver ions supported on the phosphate glass support, showed a marked decrease in antibacterial durability compared to Examples 1-13.

[0113] Furthermore, Comparative Example 6, which contained an excessive amount of silver ions carried on the phosphate glass carrier, exhibited significantly lower antibacterial properties, antibacterial durability, and impact strength than Examples 1-13.

[0114] Furthermore, Comparative Example 7, which did not contain the new acrylic graft polymer, had a lower impact strength than Examples 1-13.

[0115] Furthermore, in Comparative Example 8, which did not contain a polyamide elastomer, the antibacterial durability was significantly reduced compared to Examples 1-13.

[0116] Furthermore, in Comparative Example 9, which did not contain a non-grafted olefin polymer, the antibacterial activity, antibacterial durability and impact strength were significantly reduced compared to Examples 1-13.

[0117] Furthermore, in Comparative Example 10, which did not contain the olefin-based non-graft polymer and the metal stearate, the antibacterial activity, antibacterial durability and impact strength were significantly lower than those in Examples 1-13.

[0118] Furthermore, in Comparative Example 11, which did not contain zinc ions supported on a silicate glass support, the antibacterial activity, antibacterial durability and impact strength were significantly reduced compared to Examples 1-13.

[0119] Furthermore, in Comparative Example 12, which did not contain silver ions supported on a phosphate glass support, the antibacterial activity, antibacterial durability and impact strength were significantly reduced compared to Examples 1-13.

[0120] Furthermore, in Comparative Example 13, which contained silver ions carried on a zirconium phosphate carrier instead of silver ions carried on a phosphate glass carrier, the impact strength was significantly reduced compared to Examples 1-13.

Claims

1. a base resin including recycled resin, a new acrylic graft polymer, a new diene graft polymer, and a new vinyl non-graft polymer; an additive comprising a polyamide-based elastomer, an olefin-based non-graft polymer, a metal stearate, a first antibacterial agent comprising zinc ions carried on a silicate glass support, and a second antibacterial agent comprising silver ions carried on a phosphate glass support; For 100 parts by weight of the base resin, 0.20 to 2.00 parts by weight of the first antibacterial agent; and 0.02 to 0.50 parts by weight of the second antibacterial agent.

2. The thermoplastic resin composition according to claim 1, wherein the weight ratio of the first antibacterial agent to the second antibacterial agent is 1:0.10-0.

50.

3. 2. The thermoplastic resin composition according to claim 1, wherein the polyamide elastomer has a weight average molecular weight of 1,000 to 350,000 g / mol.

4. The thermoplastic resin composition according to claim 1 , wherein the polyamide-based elastomer comprises at least one of polyetheramide and polyetheresteramide.

5. For 100 parts by weight of the base resin, The thermoplastic resin composition according to claim 1, comprising 0.10 to 10.00 parts by weight of the polyamide elastomer.

6. The thermoplastic resin composition according to claim 1, wherein the non-grafted olefin polymer comprises an olefin monomer unit and at least one of a vinyl acetate monomer unit and an alkyl (meth)acrylate monomer unit.

7. The thermoplastic resin composition according to claim 6, wherein the non-grafted olefin polymer comprises 68.0 to 80.0% by weight of the olefin monomer unit and 20.0 to 32.0% by weight of one or more of the vinyl acetate monomer unit and the alkyl (meth)acrylate monomer unit.

8. For 100 parts by weight of the base resin, The thermoplastic resin composition according to claim 1, comprising 0.50 to 5.00 parts by weight of the non-grafted olefin polymer.

9. 2. The thermoplastic resin composition of claim 1, wherein the metal stearate comprises one or more of potassium stearate, calcium stearate, sodium stearate, magnesium stearate, and aluminum stearate.

10. For 100 parts by weight of the base resin, The thermoplastic resin composition according to claim 1, comprising 0.05 to 3.00 parts by weight of said metal stearate.

11. 2. The thermoplastic resin composition according to claim 1, wherein the recycled resin comprises a diene-based rubber polymer, vinyl cyanide-based monomer units, and vinyl aromatic-based monomer units.

12. 2. The thermoplastic resin composition according to claim 1, wherein the recycled resin comprises 10.0 to 30.0 wt. % of a diene-based rubber polymer, 15.0 to 30.0 wt. % of a vinyl cyanide-based monomer unit, and the remaining amount of a vinyl aromatic-based monomer unit.

13. For 100 parts by weight of the base resin, The thermoplastic resin composition according to claim 1, comprising 15.00 to 70.00 parts by weight of the recycled resin.

14. The nascent acrylic graft polymer is an acrylic rubber polymer; 2. The thermoplastic resin composition according to claim 1, comprising a shell containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted onto the acrylic rubbery polymer.

15. For 100 parts by weight of the base resin, The thermoplastic resin composition of claim 1, comprising 1.00 to 10.00 parts by weight of the nascent acrylic graft polymer.

16. The nascent diene graft polymer is a diene rubbery polymer; 2. The thermoplastic resin composition according to claim 1, comprising a shell containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted onto said diene rubbery polymer.

17. For 100 parts by weight of the base resin, The thermoplastic resin composition according to claim 1, comprising 5.00 to 30.00 parts by weight of the nascent diene graft polymer.

18. 2. The thermoplastic resin composition of claim 1, wherein the nascent vinyl-based non-grafted polymer comprises vinyl aromatic-based monomer units and vinyl cyanide-based monomer units.

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