JPH06299038A - Antifungal resin composition - Google Patents

Abstract

PURPOSE:To provide an antifungal resin compsn. which is excellent in antifungal properties, molded appearance, and Izod impact strength and is widely usable. CONSTITUTION:The compsn. is produced by compounding 100 pts.wt. resin component comprising 99-10wt.% styrene resin and 1-90wt.% at least one polymer selected from the group consisting of a polyamide, a thermoplastic polyester, and a polyolefin with 0.01-30 pts.wt. silver-based antifungal agent. The styrene resin is obtd. by polymerizing an arom. vinyl compd. alone or together with another copolymerizable vinyl monomer in the presence of 5-80wt.% rubbery polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene resin composition having excellent antibacterial properties, surface appearance of molded articles and Izod impact strength.

[0002]

2. Description of the Related Art Styrenic resins such as ABS resins are resins that have a highly balanced surface appearance, molding processability, Izod impact strength and other physical and mechanical properties. It is used in a wide range of fields such as electronics, OA / home appliances, automobiles, sanitary fields such as toilet seats / kitchen / bathrooms, and miscellaneous goods. In recent years, it has been pointed out that bacteria used in these products propagate and adversely affect the human body. Many styrene-based resins are also used in products that generate bacteria, and it is desired to impart antibacterial properties while maintaining the excellent surface appearance and Izod impact strength of the above styrene-based resins. . As a method of imparting antibacterial properties to a styrelenic resin, there is a method of incorporating a commercially available antibacterial property, but in the case of a stretin resin, there is a drawback that the antibacterial property is difficult to be expressed.

[0003]

The present invention has been made on the basis of the above-mentioned prior art, and is excellent in antibacterial properties, surface appearance of molded articles and Izod impact strength, and can be used in a wide range of applications. The purpose is to provide things.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides (A) an aromatic vinyl compound or another copolymerizable with an aromatic vinyl compound and an aromatic vinyl compound in the presence of 5 to 80% by weight of a rubbery polymer. 99% to 10% by weight of a styrene resin obtained by copolymerizing a vinyl monomer, and at least one selected from (B) polyamide, thermoplastic polyester, and polyolefin.
The present invention provides an antibacterial resin composition containing 0.01 to 30 parts by weight of a silver-based antibacterial agent (C) based on 100 parts by weight of a total of 1 to 90% by weight of a polymer.

Examples of the rubbery polymer used in the component (A) of the present invention include polybutadiene, polyisoprene, and styrene-butadiene copolymer (styrene content of 5 to 5).
60% by weight is preferable), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, acrylic rubber, butadiene- (meth) acrylic. Examples thereof include acid ester copolymers, polyisoprene, styrene-butadiene block copolymers, styrene-isoprene block copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated butadiene-based polymers and ethylene-based ionomers. In addition, styrene-
The butadiene block copolymer and the styrene-isoprene block copolymer include AB type, ABA type, taper type,
Those having a radial teleblock type structure are included. Further, the hydrogenated butadiene-based polymer is a hydride of the block copolymer of the styrene block and the styrene-butadiene random copolymer in addition to the hydride of the block copolymer, and the content of 1,2-vinyl bond in polybutadiene. Of 20% by weight or less and a hydride of a polymer comprising a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight. These rubber polymers are used alone or in combination of two or more.

The amount of the rubbery polymer in the component (A) of the present invention is 5 to 80% by weight, preferably 5 to 70% by weight, more preferably 10 to 60% by weight. If the amount used is less than 5% by weight, the Izod impact strength will be poor, and if it exceeds 80% by weight, the surface appearance of the molded product will be poor.

As the aromatic vinyl compound, styrene,
t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-P-aminoethylstyrene,
N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene and the like are mentioned, and styrene and α-methylstyrene are particularly preferable. . These aromatic vinyl compounds may be used alone or in combination of two or more.

Other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate and hexyl acrylate. Acrylic acid esters such as octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate; methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate,
Methacrylic acid esters such as cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate and benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; Maleimide, N-methylmaleimide,
N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and other α- or β-unsaturated dicarboxylic acid imide compounds; glycidyl methacrylate, allylglycidyl ether and other epoxy compounds; Unsaturated carboxylic acid amides such as acrylamide and methacrylamide;
Amino group-containing unsaturated compounds such as acrylic amine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene; 3-hydroxy-1-propene, 4-hydroxy-1-butene,
Cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-
1-propene, 2-hydroxyethyl acrylate, 2
-Hydroxyl group-containing unsaturated compounds such as hydroxyethyl methacrylate; and oxazoline group-containing unsaturated compounds such as vinylsixazol. Other preferred monomers are acrylonitrile, methacrylic acid, methyl methacrylate, maleic anhydride, N-phenylmaleimide,
Glycidyl methacrylate, 2-hydroxyethyl methacrylate and the like are preferable, and acrylonitrile, N-phenylmaleimide and 2-hydroxyethyl methacrylate are particularly preferable. These other monomers may be used alone or in combination of two or more.

The intrinsic viscosity (measured at 30 ° C. using methylethylketone as a solvent) of the methylethylketone soluble component in the component (A) of the present invention is preferably 0.2 to 2.0 dl / g. If the intrinsic viscosity is less than 0.2 dl / g, the impact resistance is poor, and if it exceeds 2.0 dl / g, the rigidity is poor. This intrinsic viscosity can be controlled by a chain transfer agent, polymerization time, polymerization temperature and the like.

The component (A) of the present invention is obtained by graft copolymerizing the monomer component with the rubber polymer by a known polymerization method such as emulsion polymerization, solution polymerization, bulk polymerization and suspension polymerization. Thus, a graft copolymer resin can be obtained. Further, a thermoplastic resin composed only of the monomer component is obtained and mixed with the above graft copolymer resin,
To obtain the thermoplastic resin used as the component (A) of the present invention, a usual and well-known polymerization method may be used. That is, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization are used.

The graft ratio of the component (A) containing the rubber component is usually 10 to 200% by weight and 10% by weight.
If the amount is less than 200% by weight or more than 200% by weight, the impact resistance tends to be low, which is not preferable. Here, the graft ratio is
It refers to the ratio of the copolymer component directly graft-bonded to the rubber-like polymer to the rubber amount of the graft polymer resin. This graft ratio can be controlled by the amount of polymerization initiator and the polymerization temperature.

The amount of the component (A) used in the present invention is (A) +
In component (B), 99 to 10% by weight, preferably 99 to 20%
%, More preferably 98 to 30% by weight, particularly preferably 95 to 50% by weight. If the amount used exceeds 99% by weight, the fungi is inferior, and if less than 10% by weight, the Izod impact strength is inferior.

The polyamide as the component (B) of the present invention is usually represented by the following formula: H ₂ N- (CH ₂ ) _x -NH _z (where x is an integer of 4 to 12). a linear diamine represented by the following _{formula: HO 2 C- (CH 2)} ( wherein, y is an integer from 2 to 12.) _y -CO ₂ H produced by the condensation of linear carboxylic acids represented by For example, those produced by ring-opening polymerization of lactam can be used.

Preferred examples of these polyamides include nylon 6,6, nylon 6,9 and nylon 6,1.
0, nylon 6,12, nylon 6, nylon 12, nylon 11, nylon 4,6 and the like. Also, nylon 6 / 6,6, nylon 6 / 6,10, nylon 6/1
2, nylon 6/6, 12, nylon 6/6, 6/6,
Copolyamides such as 10, nylon 6/6, 6/12 are also used. Furthermore, nylon 6/6, T (T;
Terephthalic acid component), semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and metaxylene diamine, or alicyclic diamines, polyads obtained from metaxylene diamine and the above linear carboxylic acid It is also possible to use polyester amide, The polyamide may be used alone or in combination with 2
It is also possible to use two or more species together.

Examples of the thermoplastic polyester include those obtained by condensing an aromatic dicarboxylic acid or its ester or ester-forming derivative and a diol by a known method. Examples of the aromatic dicarboxylic acid include naphthalene dicarboxylic acid such as naphthalene-2,6-dicarboxylic acid, terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, adipic acid, sebacic acid, etc. Derivatives can also be used as the thermoplastic polyester. Examples of the above diols include polymethylene glycol having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, or 1,
4-cyclohexanediol, bisphenol A and their ester-forming derivatives are mentioned.

Specific examples of the thermoplastic polyester thus obtained include polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
Examples thereof include bisphenol A isophthalate, and among them, PBT is preferable. The thermoplastic polyester preferably has an intrinsic viscosity at 25 ° C. in an o-chlorophenol solvent ([η] 25 ° C., o-chlorophenol, unit dl / g) of 0.4 to 2, and more preferably Is from 0.6 to 1.5.

Examples of the polyolefin used in the present invention include homopolymers such as polyethylene and polypropylene, ethylene, propylene, and other α-
Examples thereof include copolymers of olefins and functional group-modified polymers thereof. As the functional group used here,
There are a carboxyl group, a hydroxyl group, an epoxy group, an acid anhydride group, an amino group, a maleimide group, and the like, and as a modification method, a method of adding the above-mentioned functional group-containing unsaturated compound to polyolefin, and a method of copolymerizing during the production of polyolefin. and so on. Further, in using the polyolefin of the present invention, a known nucleating agent can be used. Of these, preferred is polypropylene, and particularly preferred is crystalline polypropylene,
The density is usually 0.89 to 0.93 g / cm ³ , and the melt flow rate (ASTM D1238L) is usually 0.1 to 7.
It is 0 g / 10 minutes. Highly crystalline polypropylene having controlled stereoregularity is also preferably used. As the polyolefin, in addition to the propylene homopolymer as described above, propylene and 20% or less of ethylene,
A block or random copolymer with an α-olefin such as 1-butene or 4-methyl-1-pentene, or a composition having polypropylene as a main component and polyethylene mixed therein may be used.

The above-mentioned component (B) of the present invention is one kind or two kinds.
Used in seeds and above. The amount used is 1 to 90% by weight, preferably 1 to 80% by weight, more preferably 2 to 70% by weight, and particularly preferably 5 to 50% by weight of the components (A) + (B).
% By weight. If the amount used is less than 1% by weight, the antibacterial property is poor, and if it exceeds 90% by weight, the Izod impact strength is poor. When the components (A) and (B) of the present invention have poor compatibility, a known compatibilizing agent can be used for enhancing the compatibility during melt kneading.

As the compatibilizer, all known compatibilizers can be used, but examples thereof include the following. Ethylene / glycidyl methacrylate copolymer-graft-styrene / acrylonitrile copolymer Ethylene / glycidyl methacrylate copolymer-graft-polymethyl methacrylate Ethylene / glycidyl methacrylate copolymer-graft-polystyrene Styrene / acrylonitrile copolymer-polymethacryl Methyl acid copolymer Styrene / acrylonitrile copolymer-polypropylene copolymer Polystyrene-polypropylene copolymer

As the silver-based antibacterial agent of the component (C) of the present invention, an organic or inorganic silver compound, a substance having a porous structure (porous structure) carrying a silver compound and / or a silver complex salt And a porous structure in which silver is supported by ion exchange. The silver compound used here is a silver halide such as silver fluoride, silver chloride or silver bromide, silver nitrate, silver sulfate, silver lactate, silver chlorate, silver picrate, protein silver, colloidal silver or carboxylic acid. Silver salt, alkyl ester of phosphoric acid or phosphorous acid,
Examples thereof include silver salts of phenyl ester or alkylphenyl ester.

Of these, colloidal silver is a yellow or reddish brown aqueous colloidal silver, which has a very large antibacterial activity, and has little harm to the human body. Further, silver has excellent heat resistance, good corrosion resistance in the atmosphere, and excellent durability. Such colloidal silver can be easily produced by a method of reducing a metal salt of silver. For example, dilute ammonia water is added to an aqueous solution of silver nitrate to make silver oxide, and then ammonia water is added to form a complex salt, which is diluted with water, and then an aqueous solution of oxalic acid or tannic acid as a reducing agent is added and heated. The method of doing is mentioned. As the reduction method, there are a hydrogen, carbon or carbon monoxide reduction method, a method using an alcal metal, and other known methods. This colloidal silver usually has a silver content of 0.02 to 1% by weight, a particle size of 50 mμ or less, and a pH.
7.0 ± 1.0, preferably the silver component is 0.05 to
It is 0.2% by weight and has a particle size of 10 mμ or less. The antibacterial activity of silver tends to increase as the particles become finer.

Examples of the silver salt of carboxylic acid include the following silver salts of carboxylic acid. Aliphatic saturated monocarboxylic acids having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, such as acetic acid, propion thyroid, butyric acid,
Valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, dosaconic acid, C2-C34, preferably C2-8 aliphatic saturated dicarboxylic acid, for example, oxalic acid, succinic acid, adipic acid, suberic acid, Sebacic acid, aliphatic unsaturated carboxylic acids such as oleic acid, erucic acid, maleic acid, fumaric acid, carbocyclic carboxylic acids such as benzoic acid, phthalic acid, cinnamic acid, hexahydrobenzoic acid, abietic acid,
Hydrogenated abietic acid, hydrocarboxylic acids such as lactic acid, malic acid, tartaric acid, citric acid, salicylic acid, aminocarboxylic acids such as aspartic acid, glutamic acid. In the present invention, preferred silver salts of carboxylic acids are silver salts of saturated aliphatic monocarboxylic acids, especially silver laurate, silver stearate, silver salts of unsaturated unsaturated carboxylic acids, especially silver oleate, and carbocyclic. They are silver salts of carboxylic acids, especially silver benzoate and hydrogenated silver abietic acid.

Further, as the silver salt of an alkyl ester, phenyl ester or alkylphenyl ester of phosphoric acid or phosphorous acid, the following may be mentioned. Mono- or di-silver salt of monoalkyl phosphate (C1-22) ester, Mono- or di-silver salt of monoalkyl phosphite (C1-22) ester, Dialkyl phosphate (carbon 1 to 22) mono-silver salt of esulte, mono- or di-silver salt of phosphoric acid monophenyl ester, mono- or di-silver salt of phosphorous acid monophenyl ester, mono-silver salt of phosphoric acid diphenyl ester, Monosilver salt or disilver salt of phosphoric acid mono [alkyl (C1-22) phenyl] ester, monosilver salt or disilver salt of phosphorous acid mono [alkyl (C1-22) phenyl] ester, phosphorus Acid di [alkyl (C1-C22) phenyl]
One silver salt of ester. Among them, preferred silver salts are mono-silver salts or di-silver salts of molybdic acid phosphate, particularly those having an alkyl group having 6 to 22 carbon atoms, and more preferably di-silver salt of stearyl phosphate and dialkyl phosphate. A monosilver salt of an ester, particularly one having an alkyl group having 6 to 22 carbon atoms, more preferably a monosilver salt of dioctyl phosphate, and a monosilver salt of a phosphoric acid di (alkylphenyl) ester, especially a carbon number of an alkyl group. Of 4 to 22 and more preferably di (4-phosphate)
t-butylphenyl) monosilver salt and di (nonylphenyl) phosphate monosilver salt.

Further, as the porous structure, there are silica gel, activated carbon, zeolite, zirconium phosphate, calcium phosphate, hydrotalcite, calcium-based ceramics, etc., a compound of metallic silver and calcium phosphate, and silver oxide in soluble glass. What is contained (Japanese Patent Application Laid-Open No. Hei 4
No. 178433). Of these, the zeolite can be either a natural product or a synthetic product. For example, as natural zeolite, anarsine (SiO 2
₂ / Al ₂ O ₃ = 3.6 to 5.6), chabazite (S
_{iO 2 / Al 2 O 3 =} 3.2~6.0 and 6.4
7.6), clinoptite (SiO ₂ / Al ₂ O ₃ =
8.5 to 10.5), erionite (SiO ₂ / Al ₂
O ₃ = 5.8-7.4), faujasite (SiO ₂ /
Al ₂ O ₃ = 4.2 to 4.6), mordenite (SiO
₂ / Al ₂ O ₃ = 8.34 to 10.0), Phillipsite (SiO ₂ / Al ₂ O ₃ = 2.6 to 4.4) and the like. These typical natural zeolites are suitable for the present invention.

On the other hand, as a typical synthetic zeolite, A-type zeolite (SiO ₂ / Al ₂ O ₃ = 1.
4 to 2.4), X-type zeolite (SiO ₂ / Al ₂ O ₃
= 2 to 3), Y- type zeolite (SiO ₂ / Al ₂ O ₃
= 3-6), mordenite _{(SiO 2 / Al 2 O 3} = 9
-10) etc., but these synthetic zeolites are suitable as the zeolite used in the present invention.
Particularly preferred are synthetic A-type zeolites, X-type zeolites, Y-type zeolites and synthetic or natural mordenites. There are no particular restrictions on the shape and particle size of the zeolite, but a smaller particle size is preferable, for example, 5 μm or less, particularly 2 μm or less.

Examples of calcium-based ceramics include calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite, with hydroxyapatite being particularly preferred. Hydroxyapatite is C
It has a composition of a ₁₀ (PO ₄ ) ₆ (OH) ₂ , is well adsorbed to proteins and lipids in the main components of bones and teeth, has good affinity with biological components, and has an ion exchange ability. Has been. However, as described above, Ca / P (molar ratio) =
Synthesis of 10/6 hydroxyapatite from calcium and phosphate salts is difficult and uneconomical. On the other hand, it is easy to synthesize a hydroxyapatite analogue having Ca / P (molar ratio) = 1.4 to 1.8 from calcium salt and phosphate, and these analogues are also similar to hydroxyapatite. It can be used in the present invention.

The amount of silver supported on the calcium-based ceramics can be arbitrarily selected within the range of adsorption or ion exchange, but from the viewpoint of the structure retention and antibacterial activity of the calcium-based ceramics, 50% by weight or less based on the ceramics, It is preferably 0.001 to 30% by weight. The antibacterial calcium-based ceramics thus obtained are
Preferably, after firing at 800 ° C. or higher, it is finely pulverized and used as the (C) silver antibacterial agent of the present invention. Since this antibacterial calcium-based ceramic is fired at a high temperature, the bond between the supported silver and the ceramic is strengthened, and the ceramic itself contracts and stabilizes by firing, so the silver supported by the water treatment is It can be mixed with the components (A) and (B) of the present invention in any amount without elution. The above-mentioned (C) silver-based antibacterial agents further include known antibacterial agents such as benzimidazole compounds, organic iodine compounds,
An ether compound, a haloalkyl compound, a nitrile compound, a sulfone compound, etc. can be used together.

The amount of the component (C) used is 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0, relative to 100 parts by weight of the components (A) + (B). .5
To 20 parts by weight, particularly preferably 0.5 to 5 parts by weight. If the amount of the component (C) is less than 0.01 parts by weight, the antibacterial effect is poor, while if it exceeds 30 parts by weight, the Izod impact strength and the appearance of the molded product are poor, which is not preferable. Although the content of silver in the component (C) of the present invention is not particularly specified, it is usually
It is in the range of 0.1 to 20%.

The antibacterial resin composition of the present invention contains glass fiber, carbon fiber, metal fiber, glass beads, wollastonite, rock filler, calcium carbonate, talc,
Fillers such as mica, glass ferry, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers and potassium titanate whiskers can be used alone or in combination. Of these fillers, the shapes of glass fiber and carbon fiber are:
A fiber having a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more is preferable. These fillers correspond to the composition 1 of the present invention.
It is usually used in the range of 5 to 150 parts by weight with respect to 00 parts by weight. Further, known additives such as coupling agents, flame retardants, antioxidants, plasticizers, colorants, lubricants and silicone oils can be added to the composition of the present invention. Further, the composition of the present invention may contain other polymers such as polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, liquid crystal polymer, fluororesin, polyurethane, ethylene-vinyl acetate copolymer depending on the required performance. A coalesce, a silicone polymer, etc. can be appropriately blended.

The antibacterial resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls and the like. A preferred manufacturing method is a method using a twin-screw extruder. Also,
When kneading the respective components, the respective components may be kneaded together or may be kneaded by a multi-stage addition method. The thus obtained antibacterial resin composition of the present invention can be molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile molding, foam molding and the like. When obtained by injection molding, the antibacterial property tends to be better when the injection speed is increased. Various molded products obtained by the above molding method,
Utilizing its excellent properties, it can be used for toilet seats, humidifiers, water purifiers, air conditioners, miscellaneous goods, various other home appliances, parts such as telephones, housings, and the like.

[0031]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. Further, various evaluations in the examples are values measured as follows.

The antibacterial activity test sample (molded product of resin flat plate) was used as a bacterial solution of Staphylococcus aureus (1 m
0.2 ml of about 10 ⁶ ) was inoculated and adhered to a polyethylene film, and stored at 35 ° C., and live cells were cultured on SCDLP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) at the start of storage and 24 hours later. Washed out. The number of viable cells of this washed-out solution was measured by an agar plate culture method (35 ° C., 2 days) using a medium for measuring the number of cells, and converted into the number of viable cells per sample. In this example, the initial number of bacteria tested in the comparative example was 3 × 10 ⁵ .

[0033]Molded product surface appearance  A plate-shaped molded product is formed and the surface appearance of the molded product is evaluated according to the following evaluation criteria.
Was visually evaluated. ○: Good appearance ×: Poor appearance

Izod impact strength Notched according to ASTM D256.

Rubber Polymers (a) -1 to (a) -3 As the component (a) used in the styrene resin (A) of the present invention, the rubber polymers shown in Table 1 were used.

[0036]

[Table 1]

Preparation of Resins (A) -1 to (A) -6 In the presence of the rubbery polymers (a) -1 to (a) -3,
Resins obtained by graft-polymerizing various monomers and resins obtained by polymerizing only monomer components were obtained without the presence of rubbery polymers. The compositions of these resins are shown in Table 2.

[0038]

[Table 2] In addition, resin (A) -1, (A) -2, (A) -3,
(A) -7 is an emulsion polymerization, and resin (A) -4,
(A) -5 and (A) -6 were obtained by solution polymerization.

The following polymers are used as the component (B) of the present invention.
Used . (B) -1; Amylan CM1017 manufactured by Toray Industries, Inc. was used as the polyamide 6. (B) -2; PBT-1 manufactured by Kanebo Co., Ltd. as PBT
24 was used. (B) -3; Mitsubishi Petrochemical Co., Ltd. BC3 was used as polypropylene.

Silver antibacterial agents (C) -1 to (C) 3 (C) -1; Amteclean Z manufactured by Matsushita Amtec Co., Ltd. was used. (C) -2; XAW1 manufactured by Sinanen Zeomic Co., Ltd.
0D was used. (C) -3; Novaron A manufactured by Toagosei Chemical Industry Co., Ltd.
G300 was used.

Other Components (D) Component The following components were used for the purpose of improving the compatibility of the components (A) and (B). (D) -1; Panlite L-1225 manufactured by Teijin Chemicals Ltd. was used as the polycarbonate. (D) -2: A polymer in which acrylonitrile-styrene copolymer was grafted on polypropylene, MODIPER A3400 manufactured by NOF CORPORATION was used.

Preparation of Antibacterial Composition The above components were mixed according to the formulation shown in Table 3, melt-kneaded using a vented twin-screw extruder, and pelletized. The obtained pellets were dried to a water content of 0.1% or less, and injection-molded to form test pieces for measuring antibacterial properties, surface appearance of molded articles and Izod impact strength, and evaluated by the above-mentioned evaluation methods. The evaluation results are shown in Table 3. In Comparative Example 1, the amount of the component (C) used in the present invention was small outside the range of the present invention, and the antibacterial property was poor. In Comparative Example 2, the amount of the component (B) used in the present invention was small outside the range of the present invention, and the antibacterial property was poor. Comparative Example 3
The amount of the component (B) used in the present invention is outside the range of the present invention, and the Izod impact strength is poor. Comparative Example 4
The amount of the component (C) used in the present invention is outside the range of the present invention, and the surface appearance of the molded product and the Izod impact strength are poor.

[0043]

[Table 3]

[0044]

The antibacterial resin composition of the present invention has antibacterial properties,
It has excellent surface appearance and Izod impact strength, and is useful in a wide range of applications, such as toilet seats, humidifiers, air conditioners, miscellaneous goods, various other home appliances, and telephones.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 77/00 LQS 9286-4J (72) Inventor Kenki Furuyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan joint Naru Rubber Co., Ltd.

Claims (1)

[Claims] 1. An aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with an aromatic vinyl compound are copolymerized in the presence of (A) a rubbery polymer in an amount of 5 to 80% by weight. Styrene-based resin 99 to 10% by weight,
(B) 0.01 to 30 parts by weight of the silver-based antibacterial agent (C) based on 100 parts by weight of 1 to 90% by weight of at least one polymer selected from polyamide, thermoplastic polyester and polyolefin. An antibacterial resin composition obtained by