KR20230082393A - Low odor acrylonitrile-butadiene-styrene based resin composition with excellent antibacterial property - Google Patents

Abstract

Provided is a thermoplastic resin composition comprising an acrylate-butadiene-acrylonitrile (ABA)-based graft copolymer, an aromatic vinyl-vinyl cyanide copolymer, a silver-based zeolite, and a metal stearate. The thermoplastic resin composition according to one aspect of the present specification exhibits excellent antibacterial and odor-reducing properties and has excellent mechanical properties, thereby being applied as an antibacterial and odor-reducing material in various fields requiring impact resistance.

Description

Low odor ABS resin composition with excellent antibacterial properties {LOW ODOR ACRYLONITRILE-BUTADIENE-STYRENE BASED RESIN COMPOSITION WITH EXCELLENT ANTIBACTERIAL PROPERTY}

The present specification relates to a low odor ABS-based resin composition having excellent antibacterial properties.

Recently, as interest in personal health and hygiene increases, there is an increasing demand for antibacterial materials used in areas that are directly touched by hands. Accordingly, thermoplastic resin products treated with antibacterial agents capable of removing or inhibiting germs from surfaces of household goods and electronic products are increasing.

In order to prepare an antibacterial thermoplastic resin composition, the addition of an antimicrobial agent is required, and the antimicrobial agent may be divided into an organic antimicrobial agent and an inorganic antimicrobial agent.

Organic antibacterial agents are relatively inexpensive and exhibit high antibacterial effects even in small amounts, but because they have antibacterial properties, they are effective only against specific bacteria, and most of them are toxic substances, so their use is very limited. In addition, there is a risk that the stability at the resin processing temperature is low and the antibacterial effect is lost due to decomposition during high temperature processing, and there are disadvantages in that the residual amount in the molded resin is low.

Inorganic antibacterial agents are widely used in the manufacture of antibacterial resins because metal ions contained in inorganic substances attack the cell membrane of strains to act as antibacterial agents, so they exhibit antibacterial properties against various strains and have excellent thermal stability. However, it is expensive compared to organic antibacterial agents, has disadvantages in that uniform dispersion in the resin is difficult, and antibacterial activity varies depending on the degree of dispersion.

Acrylonitrile-Butadiene-Styrene (ABS) resin is a thermoplastic resin with excellent impact resistance, chemical resistance, and processability, and is widely applied in various fields such as electric and electronic parts, building materials, and automobile parts. When an antibacterial agent is introduced, there is a problem in that mechanical properties are deteriorated.

In addition, existing antibacterial materials are focused only on improving antibacterial properties, but in the field of materials directly experienced by consumers, quality felt through the five senses, so-called emotional quality, belongs to an important factor. Therefore, it is necessary to develop an ABS-based resin composition having excellent antibacterial properties and low odor properties and excellent mechanical properties.

Description of the present specification is to solve the problems of the prior art described above, one object of the present specification is to provide a low odor ABS-based resin composition with excellent antibacterial properties.

Another object of the present specification is to provide a molded article made of an ABS-based resin composition having excellent mechanical properties, antibacterial properties and low odor properties.

According to one aspect, a thermoplastic resin composition including an ABS-based graft copolymer, an aromatic vinyl-vinyl cyanide copolymer, a silver-based zeolite, and a metal stearate is provided.

In one embodiment, the ABS-based graft copolymer is 55 to 65 parts by weight of a diene-based rubbery polymer; and 35 to 45 parts by weight of a monomer mixture in which an aromatic vinyl monomer and a vinyl cyanide monomer are mixed at a weight ratio of 60 to 80: 20 to 40; may be a graft polymerized copolymer.

In one embodiment, the diene-based rubbery polymer is polybutadiene; butadiene-aromatic vinyl compound copolymers including butadiene-styrene copolymers and butadiene-vinyltoluene copolymers; butadiene-vinyl cyanide compound copolymers including butadiene-acrylonitrile copolymers and butadiene-methacrylonitrile copolymers; polyisoprene; And it may be one selected from the group consisting of a combination of two or more of them.

In one embodiment, the content of the ABS-based graft copolymer may be 10 to 35% by weight based on the total weight of the thermoplastic resin composition.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be a copolymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are polymerized in a weight ratio of 60 to 80:20 to 40.

In one embodiment, the aromatic vinyl monomer may be one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinyl toluene, and combinations of two or more thereof.

In one embodiment, the vinyl cyanide monomer may be one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations of two or more thereof.

In one embodiment, the content of the aromatic vinyl-vinyl cyanide copolymer may be 55 to 80% by weight based on the total weight of the thermoplastic resin composition.

In one embodiment, the silver-based zeolite may include 0.1 to 5 parts by weight of silver ions based on 100 parts by weight of the zeolite.

In one embodiment, the silver-based zeolite may be silver-zinc zeolite.

In one embodiment, the BET specific surface area of the silver-based zeolite may be 10 to 150 m ² /g.

In one embodiment, the content of the silver-based zeolite may be 0.1 to 3.0% by weight based on the total weight of the thermoplastic resin composition.

In one embodiment, the metal stearate is selected from the group consisting of magnesium stearate, zinc stearate, calcium stearate, barium stearate, aluminum stearate, potassium stearate, sodium stearate, and a combination of two or more thereof can be one

In one embodiment, the content of the metal stearate may be 0.01 to 1% by weight based on the total weight of the thermoplastic resin composition.

In one embodiment, the thermoplastic resin composition may further include a heat-resistant SAN resin.

In one embodiment, the heat-resistant SAN resin is one selected from the group consisting of alpha methyl styrene, phenyl maleimide, and mixtures thereof; vinyl cyanide monomer; And it may be a copolymer of a monomer mixture containing a styrenic monomer.

According to another aspect, a molded article made of the thermoplastic resin composition described above is provided.

The thermoplastic resin composition according to one aspect of the present specification has excellent mechanical properties while exhibiting excellent antibacterial and odor-lowering properties, and can be applied as an antibacterial low-odor material in various fields requiring impact resistance.

Effects of one aspect of the present specification are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration described in the detailed description or claims of this specification.

Hereinafter, one aspect of the present specification will be described with reference to the accompanying drawings. However, the descriptions in this specification may be implemented in many different forms, and thus are not limited to the embodiments described herein. And in order to clearly explain one aspect of the present specification in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected" to another part, this includes not only the case where it is "directly connected" but also the case where it is "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

When ranges of numerical values are set forth herein, unless the specific range is stated otherwise, the values have the precision of significant digits provided in accordance with the standard rules in chemistry for significant digits. For example, 10 includes the range 5.0 to 14.9, and the number 10.0 includes the range 9.50 to 10.49.

As used herein, the term "ABS" means Acrylonitrile-Butadiene-Styrene.

As used herein, the term “SAN copolymer” refers to a copolymer of styrene and acrylonitrile.

As used herein, the term "zeolite" is a crystalline aluminosilicate having a three-dimensional structure, an inorganic polymer in which silicon (Si) and aluminum (Al) are linked through four cross-linking oxygens, respectively. means

thermoplastic resin composition

The thermoplastic resin composition according to one aspect of the present specification may include an ABS-based graft copolymer, an aromatic vinyl-vinyl cyanide copolymer, a silver-based zeolite, and a metal stearate.

The ABS-based graft copolymer is a diene-based rubbery polymer; and a monomer mixture in which an aromatic vinyl monomer and a vinyl cyanide monomer are mixed; this may be a graft polymerized copolymer.

As the polymerization method of the ABS-based graft copolymer, conventional methods known in the art such as emulsion polymerization and suspension polymerization may be used, and for example, emulsion polymerization may be used, but is not limited thereto.

The ABS-based graft copolymer is 55 to 65 parts by weight of a diene-based rubbery polymer; and 35 to 45 parts by weight of a monomer mixture in which an aromatic vinyl monomer and a vinyl cyanide monomer are mixed at a weight ratio of 60 to 80: 20 to 40; may be a graft polymerized copolymer. If the content of the diene-based rubbery polymer is less than 55 parts by weight, the content of the rubber component in the thermoplastic resin composition may decrease and mechanical properties including impact strength may be lowered. Formability may deteriorate. When the input amount or content of the vinyl cyanide monomer relative to 60 to 80 parts by weight of the aromatic vinyl monomer is less than 20 parts by weight or greater than 40 parts by weight, compatibility and kneadability with the aromatic vinyl-vinyl cyanide copolymer are lowered, Impact strength of the thermoplastic resin composition may decrease or unnecessary discoloration may occur.

The diene-based rubbery polymer may be polybutadiene; butadiene-aromatic vinyl compound copolymers including butadiene-styrene copolymers and butadiene-vinyltoluene copolymers; butadiene-vinyl cyanide compound copolymers including butadiene-acrylonitrile copolymers and butadiene-methacrylonitrile copolymers; polyisoprene; And it may be one selected from the group consisting of a combination of two or more of them, but is not limited thereto.

The content of the ABS-based graft copolymer may be 10 to 35% by weight based on the total weight of the thermoplastic resin composition. For example, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt% %, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, It may be 34% by weight, 35% by weight or a value between two of these values. When the content of the ABS-based graft copolymer is out of the above range, the impact resistance, low light characteristics and fluidity of the thermoplastic resin composition may be deteriorated.

The aromatic vinyl-vinyl cyanide copolymer may be a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer in a weight ratio of 60 to 80:20 to 40.

The aromatic vinyl monomer may be one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinyl toluene, and a combination of two or more of these, but is not limited thereto.

The vinyl cyanide monomer may be one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and a combination of two or more of these, but is not limited thereto.

The aromatic vinyl-vinyl cyanide copolymer may have a weight average molecular weight of 110,000 to 200,000 g/mol. For example, 110,000 g/moL, 120,000 g/moL, 130,000 g/moL, 140,000 g/moL, 150,000 g/moL, 160,000 g/moL, 170,000 g/moL, 180,000 g/moL, 190,000 g/moL, 200,000 It can be g/moL or a value between two of these values.

The content of the aromatic vinyl-vinyl cyanide copolymer may be 55 to 80% by weight based on the total weight of the thermoplastic resin composition. For example, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66% %, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight, 76% by weight, 77% by weight, 78% by weight, It may be 79% by weight, 80% by weight or a value between two of these values. When the content of the aromatic vinyl-vinyl cyanide copolymer is out of the above range, mechanical properties of the thermoplastic resin composition and quality of a molded article may be deteriorated.

The silver-based zeolite is an inorganic antibacterial agent in which silver ions are impregnated into zeolite, which is a porous inorganic support, and suppresses the outflow of volatile organic compounds (VOCs, Volatile Organic Compounds) in the thermoplastic resin composition. there is. When zeolite is used as a carrier of silver ions, compared to the case of using a porous inorganic material other than zeolite, the efficiency of improving antibacterial and odor-reducing properties can be increased compared to the silver ion content.

Silver nanoparticles or silver-based compounds may be toxic to the human body when they are added in excess and used as antibacterial agents. On the other hand, when a silver-based zeolite in which silver ions are supported inside the zeolite is dispersed and used in a thermoplastic resin composition, the aforementioned problems can be suppressed even when the amount of silver ions is relatively increased. In addition, since silver ions inside the zeolite are slowly released, the antibacterial activity can be maintained for a relatively long time.

The silver-based zeolite may be discontinuously dispersed in a continuous phase rubber-modified styrenic copolymer matrix. The silver-based zeolite can implement low odor characteristics by trapping volatile organic compounds generated from the copolymer matrix of the peripheral portion.

The silver-based zeolite may include 0.1 to 5 parts by weight of silver ions based on 100 parts by weight of the zeolite. For example, the content of the silver ion is 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3 parts by weight, 3.1 parts by weight, 3.2 parts by weight, 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight, 4 parts by weight, 4.1 parts by weight, 4.2 parts by weight, 4.3 parts by weight, 4.4 parts by weight, 4.5 parts by weight, 4.6 parts by weight, 4.7 parts by weight, 4.8 parts by weight part, 4.9 parts by weight, 5 parts by weight, or a value between two of these values. If the content of the silver ion is less than the above range, the antibacterial properties of the resin may deteriorate, and if the content exceeds the above range, the effect of improving antibacterial properties is insignificant, and expensive silver ions may be excessively used, resulting in a decrease in economic feasibility.

The silver-based zeolite may further include metal ions exhibiting antibacterial properties together with silver ions, and may include, for example, zinc ions and copper ions, but is not limited thereto.

The silver-based zeolite may be silver-zinc zeolite, but is not limited thereto. The silver-zinc zeolite is an inorganic complex containing silver ions and zinc ions in which the cations of the zeolite are exchanged for silver ions (Ag ⁺ ) and zinc ions (Zn ²⁺ ). The antibacterial effect of the inorganic antibacterial agent can be maximized.

The zinc ion content may be 0.1 to 5 parts by weight based on 100 parts by weight of zeolite. For example, the zinc ion content is 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3 parts by weight, 3.1 parts by weight, 3.2 parts by weight, 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight, 4 parts by weight, 4.1 parts by weight, 4.2 parts by weight, 4.3 parts by weight, 4.4 parts by weight, 4.5 parts by weight, 4.6 parts by weight, 4.7 parts by weight, 4.8 parts by weight part, 4.9 parts by weight, 5 parts by weight, or a value between two of these values. If the zinc ion content is less than the above range, the antibacterial properties of the resin may be reduced, and if it exceeds the above range, the antimicrobial property improvement effect may be insignificant.

The BET specific surface area of the silver-based zeolite may be 10 to 150 m ² /g. For example, 10 m ² /g, 15 m ² /g, 20 m ² /g, 25 m 2 /g, 30 m ² /g, 35 m ² /g, 40 m ² /g, 45 m ² / ^g g, 50 m ² /g, 55 m ² /g, 60 m ² /g, 65 m ² /g, 70 m ² /g, 75 m ² /g, 80 m ² /g, 85 m ² /g, 90 m ² /g, 95 m ² /g, 100 m ² /g, 105 m ² /g, 110 m ² /g, 115 m ² /g, 120 m ² /g, 125 m ² /g, 130 m ² /g, 135 m ² /g, 140 m ² /g, 145 m ² /g, 150 m ² /g, or a value between these two values. If the BET specific surface area of the silver-based zeolite is out of the above range, antibacterial and odor reducing properties of the resin may be deteriorated.

The content of the silver-based zeolite may be 0.1 to 3.0% by weight based on the total weight of the thermoplastic resin composition. For example, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight. %, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight, 1.9% by weight, 2.0% by weight, 2.1% by weight, 2.2% by weight, 2.3% by weight, 2.4% by weight, It may be 2.5% by weight, 2.6% by weight, 2.7% by weight, 2.8% by weight, 2.9% by weight, 3.0% by weight or a value between two of these values. If the content of the silver-based zeolite is less than the above range, antibacterial and odor-reducing properties of the resin may be deteriorated, and if it exceeds the above range, impact resistance may be deteriorated, making it difficult to express the impact strength required for the ABS-based resin.

The metal stearate may act as a dispersant in the resin composition to improve the dispersibility of the silver-based zeolite in the resin. Accordingly, deterioration of mechanical properties of the thermoplastic resin composition can be prevented, antibacterial and anti-odor properties can be improved, and the amount of antibacterial agent used can be reduced.

The metal stearate may be one selected from the group consisting of magnesium stearate, zinc stearate, calcium stearate, barium stearate, aluminum stearate, potassium stearate, sodium stearate, and a combination of two or more thereof. For example, it may be magnesium stearate, but is not limited thereto.

The content of the metal stearate may be 0.01 to 1% by weight based on the total weight of the thermoplastic resin composition. For example, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt% % or a value between two of these values. If the content of the metal stearate is less than the above range, the dispersibility of the silver-based zeolite in the resin may deteriorate, and thus mechanical properties, antibacterial properties, and odor-reducing properties may deteriorate.

The thermoplastic resin composition may further include a heat-resistant SAN resin. The heat-resistant SAN resin may be used to provide heat resistance required for molded articles in various fields.

The heat-resistant SAN resin is one selected from the group consisting of alpha-methylstyrene, phenyl maleimide, and mixtures thereof; vinyl cyanide monomer; And it may be a copolymer of a monomer mixture containing a styrenic monomer. For example, a tertiary copolymer obtained by copolymerizing alpha methyl styrene or phenyl maleimide with a vinyl cyanide monomer and a styrenic monomer, or alpha-menyl styrene; phenylmaleimide; vinyl cyanide monomer; And it may be a quaternary copolymer copolymerized with a styrenic monomer.

The styrene-based monomer may be one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and a combination of two or more of these, but is not limited thereto.

In one example, the heat-resistant SAN resin is a quaternary copolymerized copolymer of 30 to 50% by weight of alphamethylstyrene, 15 to 25% by weight of phenylmaleimide, 15 to 25% by weight of vinyl cyanide monomer, and 5 to 25% by weight of a styrenic monomer. It may be a combination, but is not limited thereto.

The heat-resistant SAN resin may have a weight average molecular weight of 80,000 to 100,000 g/mol, but is not limited thereto.

The content of the heat-resistant SAN resin may be 5 to 20% by weight based on the total weight of the thermoplastic resin composition. For example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt% %, 17% by weight, 18% by weight, 19% by weight, 20% by weight or may be a value between two of these values. If the content of the heat-resistant SAN resin is less than the above range, the heat resistance of the thermoplastic resin may decrease, and if the content exceeds the above range, impact resistance and flowability may decrease.

The thermoplastic resin composition may further include additives included in conventional thermoplastic resin compositions. The additive may be one selected from the group consisting of a flame retardant, a filler, an antioxidant, an anti-drip agent, a lubricant, a release agent, a nucleating agent, an antistatic agent, a stabilizer, a pigment, a dye, and combinations of two or more thereof, but is not limited thereto.

The thermoplastic resin composition maintains the mechanical properties of the ABS-based resin, has excellent antibacterial properties, low odor characteristics and heat resistance, and can be applied as an antibacterial low odor material in various fields such as electric and electronic parts, building materials, and automobile parts.

The thermoplastic resin composition may exhibit an antibacterial effect against various bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Salmonella, and Pneumococcus, and may exhibit, for example, 99.99% strain removal ability against Staphylococcus aureus. It is not limited.

molding

A molded article according to another aspect of the present specification may be made of the thermoplastic resin composition described above. The thermoplastic resin composition may be manufactured into various molded articles through molding methods such as extrusion molding, injection molding, vacuum molding, and casting molding.

Hereinafter, the embodiments of the present specification will be described in more detail. However, the following experimental results are only representative experimental results among the above examples, and cannot be interpreted as the scope and contents of the present specification are reduced or limited by the examples. Each effect of the various embodiments of the present specification that is not explicitly presented below is to be described in detail in the corresponding section.

Examples and Comparative Examples

ABS graft copolymer, SAN copolymer, antibacterial agent, heat-resistant reinforcing agent, dispersant, and antioxidant were mixed according to the composition ratio shown in Table 1 below, and then the resin composition in which each component was mixed was extruded with a twin-screw extruder at a processing temperature of 230 ° C.

Ingredients (% by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 ABS graft copolymer 29.0 29.0 29.0 29.0 29.0 29.0 29.0 29.0 29.0 SAN copolymer 69.9 69.4 68.9 55.4 70.4 69.4 69.4 69.7 65.4 Heat Resistant Reinforcement - - - 14.0 - - - - - silver-zinc zeolite 0.5 1.0 1.5 1.0 - - - 1.0 5.0 Silver Supported Zirconium Phosphate - - - - - 1.0 - - - organic antibacterial - - - - - - 1.0 - - dispersant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 - 0.3 antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

The ABS graft copolymer used ABS having a rubber content of 59% by weight.

A SAN copolymer having a vinyl cyan monomer content of 28% and a weight average molecular weight of 180,000 g/mol was used.

The heat-resistant reinforcing agent is a quaternary copolymer obtained by copolymerizing 40% by weight of alpha-methylstyrene, 20% by weight of phenylmaleimide, 22% by weight of vinyl cyanide monomer, and 18% by weight of styrene monomer, and has a weight average molecular weight of 80,000 to 100,000 g/moL. A heat-resistant SAN resin was used.

As the antibacterial agent, an inorganic antibacterial agent, silver zinc zeolite, was used, and in Comparative Examples 2 and 3, silver-supported zirconium phosphate or an organic antimicrobial agent was used. A silver-zinc zeolite having a BET specific surface area of 84 m ² /g, a pore size of 106 Å, and a silver ion content of 0.97 parts by weight was used. The silver-supported zirconium phosphate had a BET specific surface area of 3.8 m ² /g, a pore size of 103 Å, and a silver ion content of 7.3 parts by weight. Thiabendazole was used as the organic antibacterial agent.

Magnesium stearate was used as the dispersant, and 1076 compound, a phenolic primary antioxidant, was used as the antioxidant.

Experimental example

Mechanical properties, antibacterial properties, low odor properties and heat resistance of the resin compositions according to the Examples and Comparative Examples were evaluated, and the results are shown in Table 2 below.

Experimental Example 1: Evaluation of mechanical properties

Specimens of the resin compositions according to the above Examples and Comparative Examples were prepared in accordance with ASTM D 256, and the impact strength of each specimen was measured according to the Izod impact test.

Experimental Example 2: Antimicrobial evaluation

Specimens of the resin compositions according to the above Examples and Comparative Examples were prepared in accordance with the JIS Z 2801 antibacterial evaluation method. The specimen was inoculated with Staphylococcus aureus, and the antibacterial activity value was measured after 24 hours.

Experimental Example 3: Evaluation of Low Odor Characteristics

A specimen of the resin composition according to Examples and Comparative Examples was prepared in a size of 3X3 cm, placed in a 1L glass bottle, heated at 80 ° C. for 2 hours, and then left at room temperature (23 ° C.) for 60 minutes. did At least two or more personnel evaluated the odor intensity of the pretreated specimen and gave a grade (rank 1: no odor, grade 2: I can't tell what the smell is, but I feel the smell, grade 3: the smell is weakly detected and what kind of smell Detectable, Grade 4: Easily perceptible strong odor, Grade 5: Very strong odor, Grade 6: Unbearable intense odor causing breathing difficulties).

Experimental Example 4: Evaluation of heat resistance

Specimens of the resin compositions according to Examples and Comparative Examples were prepared according to ASTM D 648, and the heat deflection temperature of each specimen was measured.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Impact strength (J/m) 19 17 16 15 21 17 16 14 5 Antibacterial activity (log) 3.2 4 or more 4 or more 4 or more 0 2 One 4 or more 4 or more Odor Intensity (Rating) 2 2 One 2 5 4 5 2 One Heat deflection temperature (℃) 86 86 86 93 85 86 86 86 86

Referring to Table 2, the impact strength of the specimens prepared with the resin compositions of Examples 1 to 4 was as high as 15 J/m or more, and it was confirmed that the mechanical properties were excellent. However, in the case of Comparative Example 5 in which 5.0% by weight of silver-zinc zeolite was added, the impact strength was rapidly decreased, and it was confirmed that the impact strength of Comparative Example 4, which did not use a dispersant, was also insufficient.

Examples 1 to 4 and Comparative Examples 4 and 5 using the silver-zinc zeolite antibacterial agent exhibited a high antibacterial activity value of 3 log or more, and in particular, the antibacterial activity value of Examples 2 to 4 and Comparative Examples 4 and 5 was 4 log or more, It was confirmed that the strain removal ability was 99.99%. On the other hand, Comparative Examples 2 and 3 using silver-supported zirconium phosphate or an organic antimicrobial agent showed a low antibacterial activity value of 2 log or less, confirming that the antibacterial activity was insufficient.

Comparing Example 2 and Comparative Example 2 including the inorganic antimicrobial agent in the same weight, the silver-zinc zeolite of Example 2 has a lower content of impregnated silver ions than the silver-supported zirconium phosphate of Comparative Example 2, showed higher antibacterial activity.

Examples 1 to 4 and Comparative Examples 4 and 5 using the silver-zinc zeolite antibacterial agent also had excellent odor control properties, so that no odor or only a very weak odor was detected, whereas Comparative Examples 1 to 3 could easily detect a strong odor. there was.

Example 4 using the heat-resistant SAN resin as a heat-resistant reinforcing agent was measured to have a higher heat deflection temperature than Example 2 that did not include the heat-resistant reinforcing agent, confirming that the heat resistance was excellent.

When the silver-zinc zeolite antibacterial agent and the dispersant are used together, it was confirmed that it is possible to prepare an antibacterial ABS resin that has high antibacterial activity and excellent odor control properties while maintaining the mechanical properties of the ABS resin, and thus has little odor. In addition, it was confirmed that the heat resistance of the low odor ABS resin having excellent antibacterial properties can also be improved by using a heat resistance reinforcing agent.

The above description of the present specification is for illustrative purposes, and those skilled in the art to which one aspect of the present specification pertains can easily be modified into other specific forms without changing the technical spirit or essential features described in the present specification. you will be able to understand Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present specification is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted as being included in the scope of the present specification.

Claims (17)

A thermoplastic resin composition comprising an ABS-based graft copolymer, an aromatic vinyl-vinyl cyanide copolymer, a silver-based zeolite, and a metal stearate. According to claim 1,
The ABS-based graft copolymer is 55 to 65 parts by weight of a diene-based rubbery polymer; and 35 to 45 parts by weight of a monomer mixture in which an aromatic vinyl monomer and a vinyl cyanide monomer are mixed at a weight ratio of 60 to 80: 20 to 40; is a graft-polymerized copolymer, a thermoplastic resin composition. According to claim 2,
The diene-based rubbery polymer may be polybutadiene; butadiene-aromatic vinyl compound copolymers including butadiene-styrene copolymers and butadiene-vinyltoluene copolymers; butadiene-vinyl cyanide compound copolymers including butadiene-acrylonitrile copolymers and butadiene-methacrylonitrile copolymers; polyisoprene; And one selected from the group consisting of a combination of two or more of them, a thermoplastic resin composition. According to claim 1,
The content of the ABS-based graft copolymer is 10 to 35% by weight based on the total weight of the thermoplastic resin composition, the thermoplastic resin composition. According to claim 1,
The aromatic vinyl-vinyl cyanide copolymer is a copolymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are polymerized in a weight ratio of 60 to 80: 20 to 40, the thermoplastic resin composition. According to claim 5,
The aromatic vinyl monomer is one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinyl toluene, and a combination of two or more thereof, the thermoplastic resin composition. According to claim 5,
The vinyl cyanide monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and a combination of two or more of them, the thermoplastic resin composition. According to claim 1,
The content of the aromatic vinyl-vinyl cyanide copolymer is 55 to 80% by weight based on the total weight of the thermoplastic resin composition, the thermoplastic resin composition. According to claim 1,
The silver-based zeolite comprises 0.1 to 5 parts by weight of silver ions based on 100 parts by weight of zeolite, a thermoplastic resin composition. According to claim 1,
The silver-based zeolite is a silver-zinc zeolite, a thermoplastic resin composition. According to claim 1,
The BET specific surface area of the silver-based zeolite is 10 to 150 m ² /g, the thermoplastic resin composition. According to claim 1,
The content of the silver-based zeolite is 0.1 to 3.0% by weight based on the total weight of the thermoplastic resin composition, the thermoplastic resin composition. According to claim 1,
The metal stearate is one selected from the group consisting of magnesium stearate, zinc stearate, calcium stearate, barium stearate, aluminum stearate, potassium stearate, sodium stearate, and a combination of two or more thereof, a thermoplastic resin composition. . According to claim 1,
The content of the metal stearate is 0.01 to 1% by weight based on the total weight of the thermoplastic resin composition, the thermoplastic resin composition. According to claim 1,
The thermoplastic resin composition further comprises a heat-resistant SAN resin, the thermoplastic resin composition. According to claim 15,
The heat-resistant SAN resin is one selected from the group consisting of alpha methyl styrene, phenyl maleimide, and mixtures thereof; vinyl cyanide monomer; And a copolymer of a monomer mixture containing a styrenic monomer, a thermoplastic resin composition. A molded article made of the thermoplastic resin composition of claim 1.