Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition comprising: a base resin comprising a recycled resin, a pristine acrylic graft polymer, a pristine diene graft polymer, and a pristine vinyl non-graft polymer; and an additive comprising a first antibacterial agent and a second antibacterial agent, the first antibacterial agent comprising a polyamide-based elastomer, an olefin-based non-graft polymer, a metal stearate, and zinc ions supported on a silica glass support, and the second antibacterial agent comprising silver ions supported on a phosphate glass support, and 0.20 parts by weight to 2.00 parts by weight of the first antibacterial agent and 0.02 parts by weight to 0.50 parts by weight of the second antibacterial agent are contained based on 100 parts by weight of the base resin.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0147651, filed on November 8, 2022, the entire contents of which are incorporated into this specification by reference. Technical Field

[0003] The present invention relates to a thermoplastic resin composition. Background Art

[0004] With the increasing concern for personal health and hygiene and rising income levels, there is a growing demand for thermoplastic resin molded products with antimicrobial hygiene functions. As the production of thermoplastic resin molded products that can remove or reduce bacteria from the surfaces of household goods and home appliances increases, there is a need to develop functional antimicrobial materials with stability and reliability.

[0005] In order to produce an antibacterial thermoplastic resin composition, an antibacterial agent needs to be added, which can be divided into organic antibacterial agents and inorganic antibacterial agents. Organic antibacterial agents may be harmful to the human body and decompose when processed at high temperatures, so their antibacterial effect may be lost or reduced, and they cannot be used in various fields due to their poor antibacterial durability. On the other hand, inorganic antibacterial agents have excellent thermal stability, but when processed at high temperatures, it is challenging to disperse inorganic antibacterial agents or discoloration may occur, and due to the continuous elution of metal ions loaded on the carrier, their antibacterial durability is reduced, so they cannot be used in various fields.

[0006] Therefore, research has been conducted on antimicrobial thermoplastic resin compositions which are harmless to the human body, maintain antimicrobial ability even when processed at high temperatures, and can be used in various fields due to their excellent antimicrobial durability.

[0007] [Related technical literature]

[0008] [Patent Document]

[0009] (Patent Document 1) JP1997-241475A Summary of the invention

[0010] Technical issues

[0011] The present invention aims to provide a thermoplastic resin composition having excellent antibacterial performance, antibacterial durability, chemical resistance, appearance characteristics and impact resistance.

[0012] Technical Solution

[0013] In order to solve the above problems, 1) the present invention provides a thermoplastic resin composition, comprising: a base resin comprising a recycled resin, an original acrylic graft polymer, an original diene graft polymer and an original vinyl non-graft polymer; and an additive comprising a first antibacterial agent and a second antibacterial agent, wherein the first antibacterial agent comprises a polyamide elastomer, an olefin non-graft polymer, a metal stearate and zinc ions supported on a silica glass carrier, and the second antibacterial agent comprises silver ions supported on a phosphate glass carrier, wherein, based on 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 are included.

[0014] 2) According to 1), the present invention provides a thermoplastic resin composition, wherein the weight ratio of the first antibacterial agent to the second antibacterial agent is 1:0.10 to 0.50.

[0015] 3) According to 1) or 2), the present invention provides a thermoplastic resin composition, wherein the polyamide-based elastomer has a weight average molecular weight of 1,000 to 350,000 g / mol.

[0016] 4) According to any one of 1) to 3), the present invention provides a thermoplastic resin composition, wherein the polyamide-based elastomer comprises one or more of polyether amide and polyether ester amide.

[0017] 5) According to any one of 1) to 4), the present invention provides a thermoplastic resin composition comprising 0.10 parts by weight to 10.00 parts by weight of the polyamide-based elastomer based on 100 parts by weight of the base resin.

[0018] 6) According to any one of 1) to 5), the present invention provides a thermoplastic resin composition, wherein the olefinic non-grafted polymer comprises: an olefinic monomer unit; and one or more of a vinyl acetate monomer unit and an alkyl (meth)acrylate monomer unit.

[0019] 7) According to 6), the present invention provides a thermoplastic resin composition, wherein the olefin non-grafted polymer comprises: 68.0 wt% to 80.0 wt% of the olefin monomer unit; and 20.0 wt% to 32.0 wt% of one or more of the vinyl acetate monomer unit and the (meth) alkyl acrylate monomer unit.

[0020] 8) According to any one of 1) to 7), the present invention provides a thermoplastic resin composition comprising 0.50 to 5.00 parts by weight of the olefin-based non-grafted polymer based on 100 parts by weight of the base resin.

[0021] 9) According to any one of 1) to 8), the present invention provides a thermoplastic resin composition, wherein the metal stearate comprises one or more of potassium stearate, calcium stearate, sodium stearate, magnesium stearate and aluminum stearate.

[0022] 10) According to any one of 1) to 9), the present invention provides a thermoplastic resin composition comprising 0.05 to 3.00 parts by weight of the metal stearate based on 100 parts by weight of the base resin.

[0023] 11) According to any one of 1) to 10), the present invention provides a thermoplastic resin composition, wherein the recycled resin comprises a diene rubber polymer, a vinyl cyanide monomer unit and an aromatic vinyl monomer unit.

[0024] 12) According to any one of 1) to 11), the present invention provides a thermoplastic resin composition, wherein the recycled resin comprises 10 wt % to 30 wt % of a diene rubber polymer, 15 wt % to 30 wt % of a vinyl cyanide monomer unit and the remainder of an aromatic vinyl monomer unit.

[0025] 13) According to any one of 1) to 12), the present invention provides a thermoplastic resin composition comprising 15.00 to 70.00 parts by weight of the recycled resin based on 100 parts by weight of the base resin.

[0026] 14) According to any one of 1) to 13), the present invention provides a thermoplastic resin composition, wherein the original acrylic graft polymer comprises: an acrylic rubber polymer; and a shell comprising aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the acrylic rubber polymer.

[0027] 15) According to any one of 1) to 14), the present invention provides a thermoplastic resin composition comprising 1.00 to 10.00 parts by weight of the original acrylic graft polymer based on 100 parts by weight of the base resin.

[0028] 16) According to any one of 1) to 15), the present invention provides a thermoplastic resin composition, wherein the original diene graft polymer comprises: a diene rubber polymer; and a shell comprising aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer.

[0029] 17) According to any one of 1) to 16), the present invention provides a thermoplastic resin composition comprising 5.00 to 30.00 parts by weight of the original diene-based graft polymer based on 100 parts by weight of the base resin.

[0030] 18) According to any one of 1) to 17), the present invention provides a thermoplastic resin composition, wherein the original vinyl-based non-grafted polymer comprises an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit.

[0031] Beneficial Effects

[0032] The thermoplastic resin composition of the present invention has excellent antibacterial performance and antibacterial durability while maintaining its basic physical properties such as chemical resistance, appearance characteristics and impact resistance. Therefore, the thermoplastic resin composition can be used as a raw material for various antibacterial products. DETAILED DESCRIPTION

[0033] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0034] The terms and words in this specification and claims should not be construed as limited to their ordinary meanings or dictionary meanings, but based on the principle that inventors can appropriately define the concepts of the terms in order to interpret their inventions in the best manner, the terms or words should be construed as meanings and concepts consistent with the technical concept of the present invention.

[0035] In the present invention, the average particle size may be measured by a dynamic light scattering method, and specifically, the average particle size may refer to an arithmetic average particle size in a particle size distribution measured by a dynamic light scattering method, that is, an average particle size based on a scattering intensity distribution.

[0036] In the present invention, the average particle size can be measured using a Nicomp 380 instrument commercially available from Particle Sizing Systems.

[0037] In the present invention, the weight average molecular weight of the vinyl-based non-grafted polymer can be measured as a relative value with respect to a standard polystyrene sample by gel permeation chromatography using tetrahydrofuran as an eluent.

[0038] In the present invention, the weight average molecular weight of the polyamide-based elastomer may be measured by gel permeation chromatography after dissolving the polyamide-based elastomer in a tetrahydrofuran (THF) solution at a concentration of 1 mg / ml and filtering the solution through a 450 nm syringe filter.

[0039] In the present invention, the diene monomer may be one or more of 1,3-butadiene, isoprene, chloroprene and piperylene, preferably 1,3-butadiene.

[0040] In the present invention, the (meth)acrylic acid alkyl ester monomer may be a term covering both acrylic acid alkyl ester monomers and methacrylic acid alkyl ester monomers. The (meth)acrylic acid alkyl ester monomer may be (meth)acrylic acid C 1 -C 10 The alkyl ester 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, preferably butyl acrylate.

[0041] In the present invention, the aromatic vinyl monomer may be one or more of styrene, α-methylstyrene, α-ethylstyrene and p-methylstyrene, preferably styrene.

[0042] In the present invention, the vinyl cyanide monomer may be one or more of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, preferably acrylonitrile.

[0043] In the present invention, the olefin monomer may be one or more of ethylene, propylene and butene, preferably ethylene.

[0044] Thermoplastic resin composition

[0045] The thermoplastic resin composition according to one embodiment of the present invention comprises: 1. a base resin comprising a recycled resin, an original acrylic graft polymer, an original diene graft polymer and an original vinyl non-graft polymer; and an additive comprising a first antibacterial agent and a second antibacterial agent, wherein the first antibacterial agent comprises a polyamide elastomer, an olefin non-graft polymer, a metal stearate and zinc ions supported on a silica glass carrier, and the second antibacterial agent comprises silver ions supported on a phosphate glass carrier, wherein, based on 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 are included.

[0046] Hereinafter, components of a thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

[0047] 1. Base resin

[0048] 1) Recycled resin

[0049] The recycled resin is a component contained in a thermoplastic resin composition certified as an environmentally friendly product, and is a recycled product that is reused by processing used resin or resin waste. Specifically, the recycled resin may be resin waste that can be reused after being collected, crushed, washed, separated and classified, and processed for various purposes. There is no particular limitation on the form of the recycled resin.

[0050] The recycled resin may include one or more of recycled polyethylene, recycled polypropylene, recycled polyester, recycled polystyrene, recycled polyamide, recycled polycarbonate, recycled diene-based grafted polymers, and recycled vinyl-based non-grafted polymers.

[0051] The recycled resin may contain a diene rubber polymer, a vinyl cyanide monomer unit and an aromatic vinyl 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. In addition, the aromatic vinyl monomer unit may improve the processing properties of the recycled resin.

[0052] 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 the diene rubber polymer. When this condition is met, the impact resistance of the recycled resin can be further improved.

[0053] The recycled resin may contain 15.0 wt % to 30.0 wt %, preferably 16.0 wt % to 27.0 wt %, more preferably 18.0 wt % to 24.0 wt % of vinyl cyanide monomer units. When this condition is met, the chemical resistance of the recycled resin may be further improved.

[0054] The recycled resin may contain the remaining amount of the aromatic vinyl-based monomer unit such that the total weight of the recycled resin becomes 100 weight %.

[0055] The thermoplastic resin composition may contain the recycled resin in an amount of 15.00 to 70.00 parts by weight, preferably 15.00 to 65.00 parts by weight, more preferably 20.00 to 60.00 parts by weight, based on 100 parts by weight of the base resin. When this condition is met, a carbon reduction effect and an appropriate level of physical properties can be achieved.

[0056] 2) Original acrylic graft polymer

[0057] The original acrylic graft polymer is an acrylic graft polymer that has never been used, which is a component for improving weather resistance and impact resistance of a thermoplastic resin composition.

[0058] The original acrylic graft polymer may include: an acrylic rubber polymer; and a shell including aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the acrylic rubber polymer. The shell may include aromatic vinyl monomer units and vinyl cyanide monomer units not grafted to the acrylic rubber polymer.

[0059] The acrylic rubber polymer can be prepared by polymerization, specifically cross-linking (meth) alkyl acrylate monomers. The acrylic rubber polymer can have an average particle size of 50 nm to 600 nm, preferably 100 nm to 550 nm, more preferably 120 nm to 500 nm. When this condition is met, impact resistance and weather resistance can be improved.

[0060] The original acrylic graft polymer may contain 30.0 wt % to 70.0 wt %, preferably 35.0 wt % to 65.0 wt %, more preferably 40.0 wt % to 60.0 wt % of the acrylic rubber polymer. When this condition is met, the impact resistance and weather resistance of the acrylic graft polymer can be further improved.

[0061] The original acrylic graft polymer may contain 20.0 wt % to 60.0 wt %, preferably 25.0 wt % to 55.0 wt %, more preferably 30.0 wt % to 50.0 wt % of aromatic vinyl monomer units. When this condition is met, the processing properties of the acrylic graft polymer can be further improved.

[0062] The original 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 %, more preferably 5.0 to 20.0 wt %. When this condition is met, the chemical resistance of the acrylic graft polymer can be further improved.

[0063] The thermoplastic resin composition may include 1.00 to 10.00 parts by weight, preferably 1.50 to 8.50 parts by weight, more preferably 2.00 to 7.00 parts by weight of the original acrylic graft polymer based on 100 parts by weight of the base resin. When this condition is met, the weather resistance and impact resistance of the thermoplastic resin composition can be further improved.

[0064] 3) Original diene grafted polymer

[0065] The original diene-based graft polymer is a diene-based graft polymer that has never been used, and is a component for improving the impact resistance of the thermoplastic resin composition.

[0066] The original diene graft polymer may include a diene rubber polymer; and a shell including aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer. The shell may include aromatic vinyl monomer units and vinyl cyanide monomer units not grafted to the diene rubber polymer.

[0067] The diene-based rubber polymer may be prepared by crosslinking a diene-based monomer or a monomer composition containing a diene-based monomer as a main component.

[0068] The diene rubber polymer may have an average particle size of 50 nm to 600 nm, preferably 150 nm to 450 nm, more preferably 200 nm to 400 nm. When this condition is satisfied, the impact resistance of the original diene graft polymer may be improved.

[0069] The original diene graft polymer may contain 40.0 to 80.0 wt %, preferably 45.0 to 75.0 wt %, more preferably 50.0 to 70.0 wt % of the diene rubber polymer. When this condition is met, the impact resistance of the original diene graft polymer can be further improved.

[0070] The original diene graft polymer may contain 10.0 wt % to 50.0 wt %, preferably 15.0 wt % to 45.0 wt %, more preferably 20.0 wt % to 40.0 wt % of aromatic vinyl monomer units. When this condition is met, the processing properties of the original diene graft polymer can be further improved.

[0071] The original 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%, more preferably 5.0 to 25.0 wt%. When this condition is met, the chemical resistance of the original diene graft polymer can be further improved.

[0072] Based on 100 parts by weight of the base resin, the thermoplastic resin composition may include 5.00 to 30.00 parts by weight, preferably 7.00 to 27.00 parts by weight, more preferably 10.00 to 25.00 parts by weight of the original diene-based graft polymer. When this condition is met, the impact resistance of the thermoplastic resin composition can be further improved.

[0073] 4) Original vinyl non-grafted polymer

[0074] The original vinyl-based non-grafted polymer is a component for improving the processability of the thermoplastic resin composition.

[0075] The original vinyl-based non-grafted polymer may include an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit. Specifically, the original vinyl-based non-grafted polymer may include an aromatic vinyl-based monomer unit to improve processability and a vinyl cyanide-based monomer to improve chemical resistance.

[0076] The original vinyl-based non-grafted polymer may contain an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit in a weight ratio of 90.0:10.0 to 60.0:40.0, preferably 85.0:15.0 to 65.0:35.0, more preferably 80.0:20.0 to 70.0:30.0. When this condition is met, an original vinyl-based non-grafted polymer having coordinated improved processing properties and chemical resistance can be prepared.

[0077] The thermoplastic resin composition may contain the original vinyl-based non-grafted polymer as a balance such that the total amount of components of the base resin becomes 100 parts by weight.

[0078] 2. Additives

[0079] 1) Polyamide elastomer

[0080] The polyamide elastomer is a component that improves the antibacterial durability of the thermoplastic resin composition. Specifically, due to the lone pair electrons of the polyamide elastomer, the elution rate of the metal ions of the inorganic antibacterial agent is controlled to be constant but slow, thus significantly improving the antibacterial durability of the thermoplastic resin composition.

[0081] The polyamide elastomer may include one or more of polyetheramide and polyetheresteramide. In addition, the polyamide elastomer may include a hard segment and a soft segment, wherein the hard segment includes one or more of PA6, PA66, PA6 / 66, PA610, PA612, PA614 and PA616, and the soft segment is OH- or NH 2 - The form of functionalized polyether segments.

[0082] The weight average molecular weight of the polyamide-based elastomer may be 1,000 g / mol to 350,000 g / mol, preferably 10,000 g / mol to 340,000 g / mol, more preferably 50,000 g / mol to 335,000 g / mol, and most preferably 150,000 g / mol to 300,000 g / mol. When this condition is met, a thermoplastic resin composition having improved antibacterial durability, impact resistance, appearance quality, and chemical resistance can be prepared.

[0083] Based on 100 parts by weight of the base resin, the thermoplastic resin composition may include 0.10 to 10.00 parts by weight, preferably 0.10 to 7.00 parts by weight, more preferably 0.10 to 5.00 parts by weight of the polyamide-based elastomer. When this condition is met, a thermoplastic resin composition having improved antibacterial durability and further improved impact resistance, appearance quality, and chemical resistance can be prepared.

[0084] 2) Olefin non-grafted polymers

[0085] The olefinic non-grafted polymer is a component for improving the antimicrobial durability and chemical resistance of the thermoplastic resin composition.

[0086] The olefinic non-grafted polymer may include: an olefinic monomer unit; and one or more of a vinyl acetate monomer unit and an alkyl (meth)acrylate monomer unit to improve the antimicrobial durability, chemical resistance and appearance characteristics of the thermoplastic resin composition.

[0087] The olefinic non-grafted polymer may contain olefinic monomer units in an amount of 68.0 wt % to 80.0 wt %, preferably 70.0 wt % to 78.0 wt %, more preferably 71.0 wt % to 76.0 wt %. The olefinic non-grafted polymer may contain one or more of vinyl acetate monomer units and (meth) alkyl acrylate monomer units in an amount of 20.0 wt % to 32.0 wt %, preferably 22.0 wt % to 30.0 wt %, more preferably 24.0 wt % to 29.0 wt %. When this condition is met, the antimicrobial durability, chemical resistance and appearance characteristics of the thermoplastic resin composition can be further improved.

[0088] The olefin-based non-grafted polymer may be one or more of ethylene-vinyl acetate polymer, ethylene-methyl acrylate polymer, and ethylene-butyl acrylate polymer.

[0089] Based on 100 parts by weight of the base resin, the thermoplastic resin composition may include 0.50 to 5.00 parts by weight, preferably 0.70 to 4.00 parts by weight, more preferably 1.00 to 3.00 parts by weight of the olefinic non-grafted polymer. When this condition is met, the olefinic non-grafted 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.

[0090] 3) Metal stearates

[0091] The metal stearate is a component that improves the antimicrobial durability of a thermoplastic resin composition containing the recycled resin.

[0092] The recycled resin may contain a halogen element, and in order to prevent the halogen element from reacting with the zinc ions and silver ions respectively contained in the first antibacterial agent and the second antibacterial agent, it is preferred that the metal stearate contains a metal that is more reactive than the zinc ions and silver ions respectively contained in the first antibacterial agent and the second antibacterial agent. Therefore, the metal stearate may include one or more of potassium stearate, calcium stearate, sodium stearate, magnesium stearate, and aluminum stearate, wherein one or more of calcium stearate and magnesium stearate are preferred.

[0093] Based on 100 parts by weight of the base resin, the thermoplastic resin composition may include 0.05 to 3.00 parts by weight, preferably 0.05 to 2.50 parts by weight, more preferably 0.05 to 2.00 parts by weight of the metal stearate. When this condition is met, the antibacterial durability of the thermoplastic resin composition can be further improved.

[0094] 4) The first antimicrobial agent

[0095] The first antimicrobial agent is a component comprising zinc ions supported on a silica glass carrier, reducing the manufacturing cost of the thermoplastic resin composition, and improving the antimicrobial performance and antimicrobial durability.

[0096] Based on 100 parts by weight of the base resin, the thermoplastic resin composition may include 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. When the first antibacterial agent is included in an amount smaller than the above conditions, the antibacterial performance and antibacterial durability of the thermoplastic resin composition are significantly reduced. When the first antibacterial agent is included in an amount larger than the above conditions, the impact resistance of the thermoplastic resin composition is significantly reduced.

[0097] 5) Second antimicrobial agent

[0098] The second antimicrobial agent comprises silver ions supported on a phosphate glass carrier. The second antimicrobial agent is a component that improves the antimicrobial properties and antimicrobial persistence of the thermoplastic resin composition. Due to the phosphate glass carrier, the elution rate of the silver ions of the second antimicrobial agent remains slow, so the second antimicrobial agent has excellent antimicrobial persistence.

[0099] The second antimicrobial agent does not reduce the physical properties of the original diene graft polymer and the original acrylic graft polymer due to its excellent compatibility with the original diene graft polymer and the original acrylic graft polymer. However, when the thermoplastic resin composition contains an antimicrobial agent containing silver ions supported on a zirconium phosphate carrier instead of the second antimicrobial agent, the antimicrobial performance and antimicrobial durability can be improved, but the compatibility with the original diene graft polymer and the original acrylic graft polymer is reduced, and therefore, the impact resistance of the thermoplastic resin composition may be reduced.

[0100] Based on 100 parts by weight of the base resin, the thermoplastic resin composition may include 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. When the second antibacterial agent is included in an amount smaller than the above conditions, the antibacterial performance and antibacterial persistence of the thermoplastic resin composition are significantly reduced. When the second antibacterial agent is included in an amount larger than the above conditions, the antibacterial performance and antibacterial persistence of the thermoplastic resin composition are reduced, and the manufacturing cost is undesirably increased.

[0101] The weight ratio of the first antibacterial agent to the second antibacterial agent may be 1: 0.01 to 0.50, preferably 1: 0.01 to 0.40, more preferably 1: 0.01 to 0.20. When this condition is met, the overall physical properties of the thermoplastic resin composition are harmonious and the antibacterial durability is improved.

[0102] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in many different forms and is not limited to the embodiments described in this specification.

[0103] Examples and Comparative Examples

[0104] Descriptions of components used in the following Examples and Comparative Examples are as follows.

[0105] 1. Base resin

[0106] 1) Recycled resin: containing 15 wt% butadiene rubber polymer, 21 wt% acrylonitrile units and 64 wt% styrene units

[0107] 2) Original acrylic graft polymer: ASA graft polymer comprising 50.0 wt% of butyl acrylate rubber polymer having an average particle size of 140 nm; and a shell comprising 36.5 wt% of styrene monomer units and 13.5 wt% of acrylonitrile monomer units grafted to the butyl acrylate rubber polymer

[0108] 3) Original diene-based graft polymer: ABS graft polymer comprising 60.0 wt% of a butadiene rubber polymer having an average particle size of 300 nm; and a shell comprising 30.0 wt% of styrene monomer units and 10.0 wt% of acrylonitrile monomer units grafted to the butadiene rubber polymer

[0109] 4) Original vinyl non-grafted polymer: styrene / acrylonitrile polymer, comprising 76.0 wt% styrene monomer units and 24.0 wt% acrylonitrile monomer units

[0110] 2. Additives

[0111] 1) Polyamide elastomer

[0112] (1): Polyetheramide 1: MH 2030 commercially available from AKEMA (weight average molecular weight: 150,000 g / mol)

[0113] (2) Polyetheramide 2: Pelestat 6500 commercially available from Sanyo Chemical (weight average molecular weight: 300,000 g / mol)

[0114] 2) Olefin non-grafted polymers

[0115] (1) Random ethylene-methyl acrylate polymer 1 commercially available from SK Geo Centric Co., Ltd: LOTRYL24MA02T (ethylene monomer unit: 76.0 wt%, methyl acrylate monomer unit: 24.0 wt%, melt flow index (ASTM D1238, 190° C., 2.16 kg): 2.0 g / 10 min, melting point (ISO 11357-3): 95° C.)

[0116] (2) Random ethylene-methyl acrylate polymer 2 commercially available from SK Geo Centric Co., Ltd: LOTRYL29MA03T (ethylene monomer unit: 71.0 wt%, methyl acrylate monomer unit: 29.0 wt%, melt flow index (ASTM D1238, 190°C, 2.16 kg): 3.0 g / 10 min), melting point (ISO 11357-3): 92°C)

[0117] 3) Metal stearates

[0118] (1) Calcium stearate

[0119] (2) Magnesium stearate

[0120] 4) First antimicrobial agent: VZ600 (zinc ions supported on a silica glass carrier) commercially available from Toagosei Co., Ltd.

[0121] 5) Second antimicrobial agent: IONPURE WPA (silver ions supported on a phosphate glass carrier) commercially available from Ishizuka Glass Co., Ltd.

[0122] The above components were mixed in the amounts shown in Table 1 to Table 6 below and stirred to prepare a thermoplastic resin composition.

[0123] Experimental Example 1

[0124] Each thermoplastic resin composition of Examples and Comparative Examples was put into a twin-screw extruder set at 230° C. and extruded to prepare pellets. The pellets were injection molded to prepare samples, and physical properties were evaluated using the following methods and the results are shown in Tables 1 to 6 below.

[0125] (1) Antimicrobial activity: According to the ISO 22196 antimicrobial evaluation method, 5 cm×5 cm×0.3 cm samples were inoculated with Escherichia coli and Staphylococcus aureus, respectively, and cultured at 35° C. and 90% relative humidity for 24 hours to measure the antimicrobial activity.

[0126] (2) Antimicrobial persistence (after pretreatment) According to the ISO 22196 antimicrobial evaluation method, 5 cm × 5 cm × 0.3 cm samples were immersed in 50 °C water for 32 h, inoculated with Escherichia coli and Staphylococcus aureus, respectively, and cultured at 35 °C and 90% relative humidity for 24 h to measure the antimicrobial activity.

[0127] (3) Appearance quality: Each injection-molded sample having a curved surface was scratched with a knife and folded, and the state of the folded surface was evaluated with naked eyes.

[0128] ○: No peeling occurred

[0129] △: After the injection molded sample was scratched and folded with a knife, peeling occurred on the folded surface when additional force was applied

[0130] ×: After the injection molded sample was scratched with a knife and folded, peeling occurred on the folded surface even without applying force

[0131] (4) Chemical resistance: A sample fixed on a fixture at a strain rate of 1.1% was immersed in cyclopentane for 3 minutes and subjected to a 180° bending test.

[0132] ○: No change

[0133] △: Small cracks appear

[0134] ×: Fracture after cracking

[0135] (5) Impact strength (kgf·cm / cm, 1 / 4 inch): Izod impact strength was measured according to ASTM D265 at 25° C. When the Izod impact strength was 20 kg·cm / cm or more, the impact resistance was judged to be excellent.

[0136] [Table 1]

[0137]

[0138]

[0139] [Table 2]

[0140]

[0141]

[0142] [Table 3]

[0143]

[0144]

[0145] [Table 4]

[0146]

[0147]

[0148] [Table 5]

[0149]

[0150]

[0151] [Table 6]

[0152]

[0153]

[0154] Referring to Tables 1 to 6, Examples 1 to 13 exhibited excellent antibacterial properties, appearance quality, chemical resistance, and impact strength. However, Comparative Examples 1 and 2, which included a small amount of zinc ions supported on a silica glass carrier, had significantly reduced antibacterial properties and antibacterial persistence compared to Examples 1 to 13.

[0155] Comparative Examples 3 and 4, which include excessive amounts of zinc ions supported on a silica glass carrier, have significantly reduced impact strength compared to Examples 1 to 13.

[0156] Comparative Example 5, which includes a small amount of silver ions supported on a phosphate glass carrier, has significantly reduced antimicrobial persistence compared to Examples 1 to 13.

[0157] Comparative Example 6, which includes an excessive amount of silver ions supported on a phosphate glass carrier, has significantly reduced antimicrobial performance, antimicrobial durability, and impact strength compared to Examples 1 to 13.

[0158] Comparative Example 7, which does not include the original acrylic graft polymer, has reduced impact strength compared to Examples 1 to 13.

[0159] Comparative Example 8, which does not include a polyamide-based elastomer, has significantly lower antimicrobial persistence than Examples 1 to 13.

[0160] Comparative Example 9, which does not include an olefin-based non-grafted polymer, has significantly reduced antimicrobial performance, antimicrobial durability, and impact strength compared to Examples 1 to 13.

[0161] Comparative Example 10, which does not include the olefinic non-grafted polymer and the metal stearate, has significantly reduced antibacterial performance, antibacterial durability, and impact strength compared to Examples 1 to 13.

[0162] Comparative Example 11, which does not include zinc ions supported on a silica glass carrier, has significantly reduced antimicrobial performance, antimicrobial durability, and impact strength compared to Examples 1 to 13.

[0163] Comparative Example 12, which does not include silver ions supported on a phosphate glass carrier, has significantly reduced antimicrobial performance, antimicrobial durability, and impact strength compared to Examples 1 to 13.

[0164] Comparative Example 13, which includes silver ions supported on a zirconium phosphate support instead of silver ions supported on a phosphate glass support, has significantly reduced impact strength compared to Examples 1 to 13.

Claims

1. A thermoplastic resin composition comprising: a base resin comprising recycled resin, virgin acrylic graft polymer, virgin diene graft polymer, and virgin vinyl non-graft polymer; and The additive comprises a first antibacterial agent and a second antibacterial agent, wherein the first antibacterial agent comprises a polyamide elastomer, an olefin non-grafted polymer, a metal stearate and zinc ions supported on a silica glass carrier, and the second antibacterial agent comprises silver ions supported on a phosphate glass carrier, in, Based on 100 parts by weight of the base resin, 0.20 parts by weight to 2.00 parts by weight of the first antibacterial agent and 0.02 parts by weight to 0.50 parts by weight of the second antibacterial agent are included.

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 to 0.

50.

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

4. The thermoplastic resin composition according to claim 1, wherein The polyamide elastomer includes one or more of polyether amide and polyether ester amide. 5 . The thermoplastic resin composition according to claim 1 , comprising 0.10 parts by weight to 10.00 parts by weight of the polyamide-based elastomer based on 100 parts by weight of the base resin.

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

7. The thermoplastic resin composition according to claim 6, wherein The olefin-based non-grafted polymer comprises: 68.0 wt % to 80.0 wt % of the olefin-based monomer units; and 20.0 wt % to 32.0 wt % of one or more of the vinyl acetate-based monomer units and the (meth)acrylic acid alkyl ester-based monomer units. 8 . The thermoplastic resin composition according to claim 1 , comprising 0.50 parts by weight to 5.00 parts by weight of the olefin-based non-graft polymer based on 100 parts by weight of the base resin.

9. The thermoplastic resin composition according to claim 1, wherein The metal stearate includes one or more of potassium stearate, calcium stearate, sodium stearate, magnesium stearate and aluminum stearate. 10 . The thermoplastic resin composition according to claim 1 , comprising 0.05 parts by weight to 3.00 parts by weight of the metal stearate based on 100 parts by weight of the base resin.

11. The thermoplastic resin composition according to claim 1, wherein The recycled resin comprises a diene rubber polymer, a vinyl cyanide monomer unit and an aromatic vinyl monomer unit.

12. The thermoplastic resin composition according to claim 1, wherein The recycled resin includes 10.0 wt % to 30.0 wt % of the diene-based rubber polymer, 15.0 wt % to 30.0 wt % of the vinyl cyanide-based monomer unit, and the balance of the aromatic vinyl-based monomer unit. 13 . The thermoplastic resin composition according to claim 1 , comprising 15.00 parts by weight to 70.00 parts by weight of the recycled resin based on 100 parts by weight of the base resin.

14. The thermoplastic resin composition according to claim 1, wherein The original acrylic graft polymer includes: an acrylic rubber polymer; and a shell including an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit grafted to the acrylic rubber polymer. 15 . The thermoplastic resin composition according to claim 1 , comprising 1.00 to 10.00 parts by weight of the original acrylic graft polymer based on 100 parts by weight of the base resin.

16. The thermoplastic resin composition according to claim 1, wherein The original diene-based graft polymer includes: a diene-based rubber polymer; and a shell including aromatic vinyl-based monomer units and vinyl cyanide-based monomer units grafted to the diene-based rubber polymer. 17 . The thermoplastic resin composition according to claim 1 , comprising 5.00 parts by weight to 30.00 parts by weight of the original diene-based graft polymer based on 100 parts by weight of the base resin.

18. The thermoplastic resin composition according to claim 1, wherein The original vinyl-based non-grafted polymer comprises aromatic vinyl-based monomer units and vinyl cyanide-based monomer units.

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