JPH1135787A - Antibacterial thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial thermoplastic resin composition excellent in antibacterial action, impact resistance and molded article surface external appearance and further excellent in flame retardance as well. SOLUTION: This antibacterial thermoplastic resin composition comprises (A) 100 pts.wt. rubber-reinforced thermoplastic resin, (B) 0.1-1 pt.wt. silver-based antibacterial agent and (C) 0.1-2 pts.wt. zinc oxide having a specific surface area of 2-12 m<2> /g. An antibacterial and flame retardant thermoplastic resin composition comprises 100 pts.wt. antibacterial thermoplastic resin composition and 3-60 pts.wt. flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent antibacterial properties, impact resistance, surface appearance of a molded article, and flame retardancy.

[0002]

2. Description of the Related Art Rubber-reinforced thermoplastic resin such as ABS resin and flame-retardant ABS resin are used for molding surface appearance, impact resistance, and the like.
Due to its excellent rigidity and moldability, it is used in a wide range of fields such as OA / home appliances, electric / electronics, and vehicles. In recent years, bacteria may be generated in these products, and there is a concern about the effects on the human body.
For this bacterium, a rubber-reinforced thermoplastic resin containing a silver-based inorganic antibacterial agent has been generally developed. However, in order to increase the antibacterial activity of silver-based inorganic antibacterial agents, it is necessary to increase the amount of the antibacterial agents, and deterioration of physical properties, especially impact resistance, deterioration of molded product surface appearance, and the like are inevitable. . On the other hand, from the viewpoint of fire safety, there is an increasing demand for materials having flame retardancy. However, rubber-reinforced thermoplastic resins such as ABS resins have the drawback of being easily flammable. In fields where flame retardancy is required, a halogen compound is used as a flame retardant, and antimony trioxide is used as a flame retardant aid. The flame-retardant resin composition described above is generally used. However, when a flame retardant and a flame retardant auxiliary are blended with the rubber-reinforced thermoplastic resin, there is a disadvantage that the impact resistance and the surface appearance of the molded product are inferior.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has antibacterial properties, impact resistance,
It is an object of the present invention to provide a thermoplastic resin composition having excellent surface appearance of a molded article and further excellent flame retardancy.

[0004]

According to the present invention, (A) 0.1 to 1 part by weight of a silver-based antibacterial agent and (C) a specific surface area of 2 parts by weight per 100 parts by weight of a rubber-reinforced thermoplastic resin. ~ 12m
^The present invention provides an antibacterial thermoplastic resin composition (hereinafter, also referred to as "antibacterial thermoplastic resin composition") containing 0.1 to ² parts by weight of zinc oxide of ² / g. Further, the present invention provides an antibacterial / flame retardant thermoplastic resin composition (hereinafter referred to as "antibacterial") comprising 3 to 60 parts by weight of a flame retardant (D) with respect to 100 parts by weight of the above antibacterial thermoplastic resin composition. Also provided is "composition of the present invention" by combining the above-mentioned antibacterial thermoplastic resin composition with the above-mentioned antibacterial thermoplastic resin composition. Things.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The rubber-reinforced thermoplastic resin (A) used in the composition of the present invention may be an aromatic vinyl compound, a vinyl cyanide compound and, if necessary, a rubber-based polymer in the presence of a rubbery polymer. It is obtained by graft polymerization of a monomer component composed of another copolymerizable vinyl monomer, but is separately obtained by (co) polymerizing only the above monomer component (A ′) (co) A polymer may be blended.

Examples of the rubbery polymer used in the rubber-reinforced thermoplastic resin (A) of the present invention include polybutadiene, polyisoprene, butyl rubber, and styrene-butadiene copolymer (styrene content is preferably 5 to 60% by weight). Styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, silicone rubber, polyurethane rubber, acrylic rubber, butadiene- (meth) Acrylic ester copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene-based polymer,
Ethylene ionomers and the like can be mentioned.

The styrene-butadiene block copolymer and the styrene-isoprene block copolymer include those having an AB type, an ABA type, a taper type, and a radial teleblock type structure. The hydrogenated butadiene-based polymer includes, in addition to the hydride of the block copolymer, a styrene block and a hydride of a styrene-butadiene random copolymer block, and a 1,2-vinyl bond in polybutadiene. 20% by weight
It includes the following blocks and hydrides of polymers composed of polybutadiene blocks having a 1,2-vinyl bond content of more than 20% by weight. Among these, hydrogenated diene polymers (homo, block and random) such as polybutadiene, styrene-butadiene copolymer, ethylene-α-olefin copolymer, hydrogenated butadiene polymer, and silicone rubber are preferred. . These rubbery polymers can be used alone or in combination of two or more.

(A) Among the monomer components used in the rubber-reinforced thermoplastic resin, aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methylstyrene and p-methylstyrene. -Hydroxystyrene, α-ethylstyrene, methyl-α-methylstyrene, dimethylstyrene, bromostyrene, tribromostyrene, divinylstyrene, vinylpyridine, vinylxylene, 1,1-diphenylstyrene, fluorostyrene, chlorostyrene, dichlorostyrene , Trichlorostyrene, sodium styrenesulfonate and the like. Of these, styrene, α-methylstyrene and p-methylstyrene are preferred. These aromatic vinyl compounds are used alone or in combination of two or more. The amount of the aromatic vinyl compound to be used is preferably 50 to 90% by weight in the monomer component, more preferably 60 to 90% by weight.
If it is 80% by weight, if less than 50% by weight, sufficient moldability cannot be obtained, while if it exceeds 90% by weight, impact resistance cannot be obtained, which is not preferable.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. The vinyl cyanide compounds can be used alone or in combination of two or more. The amount of the vinyl cyanide compound used is preferably 50 to 10% by weight, more preferably 40 to 20% by weight in the monomer component. If it is less than 10% by weight, the impact resistance is poor. On the other hand, if it exceeds 50% by weight, the color tone of the obtained rubber-reinforced thermoplastic resin becomes brown, and the molding processability and the thermal stability at the time of molding are unfavorable. .

[0010] As the above-mentioned monomer component, other copolymer-functional vinyl monomers can be used, if necessary, and the preferred amount thereof is 40% by weight or less. The other copolymerizable vinyl monomers include (meth)
Alkyl acrylate, maleimide compound, unsaturated acid, unsaturated compound containing acid anhydride group, unsaturated compound containing epoxy group, unsaturated compound containing amino group, unsaturated compound containing hydroxyl group, unsaturated compound containing oxazoline group, etc. These can be used alone or in combination of two or more.

Among them, alkyl (meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate Alkyl acrylates such as phenyl acrylate, benzyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate DOO, phenyl methacrylate, include alkyl methacrylate such as benzyl methacrylate, Among these, butyl acrylate,
Methyl methacrylate is preferred.

The maleimide compounds include maleimide, N-methylmaleimide, N-ethylmaleimide,
-Propylmaleimide, N-isopropylmaleimide,
N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-carboxylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-bromophenyl) maleimide, tribromophenylmaleimide, N- (chlorophenyl) maleimide and the like.
-Phenylmaleimide and N-cyclohexylmaleimide are preferred. Examples of the unsaturated acid include acrylic acid, methacrylic acid, and maleic acid. Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. As the epoxy group-containing unsaturated compound, glycidyl methacrylate,
Allyl glycidyl ether and the like can be mentioned. Examples of the amino group-containing unsaturated compound include acrylamine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, acrylic styrene, acrylamide, methacrylamide and the like.

Examples of the unsaturated compound having a hydroxyl group include hydroxylstyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, and trans-4-hydroxy-2-butene. , 3-hydroxy-2-methyl-1-propene, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and the like. Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.

The amount of the rubbery polymer in the rubber-reinforced thermoplastic resin (A) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. If the content is less than 5% by weight, the impact strength is reduced, while if it exceeds 50% by weight, the impact strength is reduced.
Molding processability, elastic modulus and heat deformation temperature are lowered, which is not preferable.

The graft ratio of the rubber-reinforced thermoplastic resin (A) is preferably 5 to 150% by weight, more preferably 10 to 150% by weight. Graft rate is 5% by weight
If it is less than 3, the effect of adding the rubber component is not sufficiently exhibited, and sufficient impact resistance cannot be obtained. On the other hand, when the content exceeds 150% by weight, the moldability decreases. Here, the graft ratio (% by weight) is a value obtained by the following equation, where x is the weight of the rubber component in 1 g of the rubber-reinforced thermoplastic resin, and y is the weight of the insoluble matter in methyl ethyl ketone. Graft ratio (% by weight) = [(y−x) / x] × 100 The average molecular weight of the rubber-reinforced thermoplastic resin (A) of the present invention is determined by the intrinsic viscosity [η] of the methyl ethyl ketone-soluble component as a matrix component. (Measured in methyl ethyl ketone at 30 ° C.) is preferably 0.2 to 1.0 dl / g, more preferably 0.3 to 0.9 dl / g, particularly preferably 0.35 to 0.8 dl / g. . This intrinsic viscosity [η]
Is less than 0.2 dl / g, a balance between rigidity and impact resistance cannot be obtained, while if it exceeds 1.0 dl / g, moldability deteriorates. Above intrinsic viscosity [η]
Can be easily controlled by changing the type and amount of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent, and the like, and further, a polymerization time, a polymerization temperature, and the like.

The (A ') (co) polymer which can be separately compounded with (A) the rubber-reinforced thermoplastic resin is an aromatic vinyl compound, a vinyl cyanide compound and, if necessary, a copolymer thereof. A (co) polymer obtained by (co) polymerizing a monomer component comprising another possible vinyl monomer, and an aromatic vinyl compound and a vinyl cyanide compound used in the (co) polymer. , Other copolymerizable vinyl monomers,
(A) The same as the monomer component used for the rubber-reinforced thermoplastic resin.

The (A ′) (co) polymer may be polymerized separately, or (A) the method of adding the monomer component may be appropriately adjusted during the production of the rubber-reinforced thermoplastic resin. Thus, a method of producing (A) a rubber-reinforced thermoplastic resin containing this (A ′) (co) polymer may be used. Preferably, the former method is used. That is, the component (A ') is produced by, for example, solution polymerization, suspension polymerization, or emulsion polymerization, but is preferably produced by solution polymerization. Here, a preferable polymerization method in solution polymerization depends on the monomer composition ratio and the monomer reactivity ratio in the reaction system, and when the copolymerization reaction proceeds from the reaction system having a certain monomer composition ratio, Except when the monomer composition ratio is an azeotropic composition, the composition ratio of the unreacted monomer and the composition of the copolymer formed therefrom change with the copolymerization reaction. Therefore, in order to produce a (A ′) (co) polymer having a uniform composition and excellent quality, the initial charge is carried out at a monomer composition ratio suitable for the monomer composition ratio. Start the polymerization reaction, thereafter, by additionally supplying to the reaction system of the copolymerization reaction, until the copolymerization reaction is terminated, the monomer composition ratio of the copolymerization reaction system,
It is preferable to keep it substantially constant.

Further, as a medium in the solution polymerization, toluene, acetonitrile, dimethylformamide, etc. can be used, and as a polymerization initiator, such as paramenthane hydroperoxide, lauroyl peroxide or the like, or chain transfer by thermal polymerization. As the agent, mercaptans, hydrocarbons and the like are used, and the polymerization temperature is about 60 to 150 ° C.

On the other hand, the rubber-reinforced thermoplastic resin (A) undergoes radical graft polymerization of the above monomer component by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like in the presence of a rubbery polymer. , Can be manufactured. Preferably,
It is emulsion polymerization. At this time, a polymerization initiator,
Chain transfer agents (molecular weight regulators), emulsifiers, water and the like are used. Incidentally, the rubbery polymer and the monomer component used for producing the rubber-reinforced thermoplastic resin (A) may be prepared by adding the monomer component in a lump and polymerizing in the presence of the total amount of the rubbery polymer. The polymerization may be carried out in a divided or continuous manner. Moreover, you may superpose | polymerize by the method which combined these. Further, the whole or a part of the rubbery polymer may be added during the polymerization to carry out the polymerization.

Examples of the polymerization initiator include organic hydroperoxides represented by cumene hydroxyperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphoric acid formulations, sulfoxylate formulations and the like. A redox system in combination with a reducing agent, or a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide or the like is used. Preferably, it is an oil-soluble initiator, and is a redox system obtained by combining a cumene hydroperoxide, a diisopropylbenzene hydroperoxide, a paramenthane hydroperoxide with a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, and the like. Is good. Moreover, you may combine the said oil-soluble initiator and a water-soluble initiator. When combined, the addition ratio of the water-soluble initiator is preferably 50% by weight or less, more preferably 25% by weight or less of the total amount. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator to be used is generally 0.1 to 1.5% by weight, preferably 0.2 to 0.7% by weight, based on the monomer component.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, and the like. Examples include hydrocarbons such as carbon tetrachloride, ethylene bromide and pentaphenylethane, or dimers of acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, and α-methylstyrene. These chain transfer agents can be used alone or in combination of two or more. The method of using the chain transfer agent may be any of batch addition, divisional addition, and continuous addition. The amount of the chain transfer agent is usually about 0.05 to 2.0% by weight based on the monomer component.

As the emulsifier, an anionic surfactant,
Nonionic surfactants, and amphoteric surfactants are included. Among them, examples of the anionic surfactant include a higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, a phosphoric acid, and a fatty acid salt. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenyl ether type or the like of ordinary polyethylene glycol is used. Further, as an amphoteric surfactant,
Examples thereof include those having a carboxylate, sulfate, sulfonate, or phosphate as an anion portion, and amine salts, quaternary ammonium salts, or the like as a cation portion. The amount of emulsifier used is usually
It is about 0.3 to 5.0% by weight.

The rubber-reinforced thermoplastic resin (A) is preferably subjected to emulsion polymerization at a polymerization temperature of 10 to 120 ° C., preferably 30 to 110 ° C. When the rubber-reinforced thermoplastic resin (A) of the present invention is obtained by emulsion polymerization,
The average rubber particle diameter of the rubbery polymer latex is preferably 0.2 to 0.8 μm, more preferably 0.25 to
0.5 μm. When a latex having an average particle size in this range is used, a high balance of physical properties can be realized.

The rubber-reinforced thermoplastic resin (A) of the present invention is subjected to a graft copolymerization process by emulsion polymerization, followed by a recovery process such as coagulation-washing, dehydration-desolubilization, etc., followed by drying to obtain a powder or granules. At the time of blending the rubber-reinforced thermoplastic resin (A), a heat stabilizer, a lubricant and the like can be added to form a pellet. When the rubber-reinforced thermoplastic resin (A) is mixed with the (A ') (co) polymer, it can be produced by any mixing means capable of uniformly kneading. In this mixing, a single screw extruder, a twin screw extruder,
A common one in melt kneading of a resin such as a Banbury mixer or a kneader can be used. At this time, additives such as a heat stabilizer, an ultraviolet absorber, a lubricant, and an antistatic agent, and a coloring agent may be added.

Next, (B) used in the composition of the present invention
The silver-based antibacterial agent has an effect of imparting antibacterial activity to bacteria such as Escherichia coli and Staphylococcus aureus in the composition of the present invention. Here, (B) the silver-based antibacterial agent is an organic antibacterial agent.
An inorganic silver compound, an inorganic substance having a silver compound and / or a silver complex salt supported thereon, an inorganic substance having an ion exchange ability having been ion-exchanged with silver ions, and a boric acid-based glass containing a silver compound. And the like.
Silver compounds used here include silver oxide, silver chloride,
Silver nitrate, silver sulfate, silver acetate, silver chlorate, silver bromide, silver fluoride, silver picrate, protein silver, colloidal silver, silver salt of carboxylic acid, alkyl ester of phosphoric acid or phosphorous acid, phenyl ester or alkyl And silver salts of phenyl esters.

Examples of the silver salt of a carboxylic acid include the following silver salts of a carboxylic acid. Aliphatic saturated monocarboxylic acids having 1 to 30, preferably 2 to 22 carbon atoms, such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, docosanoic acid; Preferably 2 to 8 aliphatic saturated dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, aliphatic unsaturated carboxylic acids such as oleic acid, erucic acid, maleic acid, fumaric acid, carbon Cyclic 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 aliphatic saturated monocarboxylic acids, especially silver laurate, silver stearate, silver salts of aliphatic unsaturated carboxylic acids, especially silver oleate, and Silver salts of carbocyclic carboxylic acids, especially silver benzoate and hydrogenated silver abietic acid.
The silver-based antibacterial agents of the present invention also include those in which the carboxylic acid portion of a copolymer of methacrylic acid or acrylic acid alone or with another copolymerizable monomer is a silver salt.

Examples of the inorganic substance carrying the silver compound and / or silver complex salt include silica gel, activated carbon, hydrotalcite, and calcium-based ceramics such as calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite. Examples of the inorganic substance having an ion exchange ability include zeolite and zirconium phosphate. As the zeolite, both natural products and synthetic products can be used.

The amount of the silver-based antibacterial agent (B) is 0.1 to 1 part by weight, preferably 0.1 to 0.8 part by weight, based on 100 parts by weight of the rubber-reinforced thermoplastic resin (A). Preferably it is 0.1 to 0.6 parts by weight. If the amount is less than 0.1 part by weight, the effect of adding the component (B) is low, and sufficient antibacterial properties cannot be obtained. On the other hand, if it exceeds 1 part by weight, the impact strength of the molded product and the surface appearance of the molded product are reduced. When the amount of the component (B) is within the above range, a composition of the present invention having high antibacterial activity can be obtained in the presence of zinc oxide (C).

Next, (C) used in the composition of the present invention
The component is zinc oxide (zinc white) having a specific specific surface area. (C) The specific surface area of zinc oxide is ^{2 to} 12 m ² /
g, preferably 3 to 11 m ² / g. Those having a large particle size of less than 2 m ² / g do not exhibit high antibacterial activity in the presence of the component (B) of the present invention, and also reduce the surface appearance of molded articles. On the other hand, those having a small particle size of more than 12 m ² / g, when incorporated into the composition of the present invention, cause aggregation in the resin and exhibit high antibacterial activity against bacteria in the presence of the component (B) of the present invention. Absent. (C) The amount of zinc oxide used is
(A) With respect to 100 parts by weight of the rubber-reinforced thermoplastic resin, 0.1 parts by weight.
The amount is 1 to 2 parts by weight, preferably 0.2 to 2 parts by weight, more preferably 0.3 to 1 part by weight. If the amount is less than 0.1 part by weight, the antibacterial activity against bacteria is not improved, while if it exceeds 2 parts by weight, the impact strength and the surface appearance of the molded article are reduced. In the composition of the present invention, when (C) the amount of zinc oxide used is within the above range and (B) the amount of silver-based antibacterial agent is within the above range, the composition has an even higher antibacterial activity and high impact. A composition having high moldability and high surface appearance of a molded article can be obtained.

The antibacterial thermoplastic resin composition of the present invention comprises
By blending (D) a flame retardant, it is possible to obtain an antibacterial / flame retardant thermoplastic resin composition further imparted with flame retardancy. As the flame retardant (D), those used as general polymer flame retardants such as rubber and resin can be used. Examples include halogen-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds, silicon-containing compounds, and the like. Specific examples of the halogen-containing compound include tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), and tetrabromobisphenol A-bis (2,3
-Dibromopropyl ether), hexabromodiphenyl ether, decabromodiphenyl ether, bis (tribromophenoxy) ethane, hexabromocyclododecane, and the like.

Further, monobromophenol, tribromophenol, pentabromophenol, tribromocresol, tetrabromobisphenol S, cyanuric chloride and the like are polymerized, or at least one selected from the group consisting of these and the above-mentioned halogen-containing compounds. Obtained by copolymerizing with one kind of halogen-containing compound,
Oligomer-type halogen-containing compounds are exemplified. Furthermore, a polycarbonate oligomer of tetrabromobisphenol A, a polycarbonate oligomer of tetrabromobisphenol A and bisphenol A, a polycarbonate oligomer of tetrabromobisphenol S, a polycarbonate oligomer of tetrabromobisphenol S and bisphenol A, and the like are also included. further,
Halogenated epoxy oligomers are also included.

Examples of the phosphorus-containing compound include organic phosphorus-containing compounds, red phosphorus, phosphazene-based compounds, and ammonium polyphosphate. Among them, examples of the organic phosphorus-containing compound include phosphates represented by triphenyl phosphate and phosphites represented by triphenyl phosphite. here,
As the organic phosphorus-containing compound, triphenyl phosphate, triphenyl thiophosphate, trixylenyl phosphate, trixylenyl thiophosphate, hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) and the like are preferable.

As the nitrogen-containing compound, trizine,
Examples include triazolysine, urea, guanidine, amino acids, melamine and derivatives thereof. Examples of the silicon-containing compound include general organosiloxanes. Specific examples include silicone oil, silicone resin, organic silane compound, polysilane, and the like.
Also, aluminum silicate, sodium silicate, silicon dioxide and the like can be mentioned. The above (D) flame retardants can be used alone or in combination of two or more.

(D) As the flame retardant, a bromine-containing compound,
Preference is given to chlorine-containing compounds, phosphorus and / or nitrogen-containing compounds. From the viewpoints of environmental protection and hygiene, phosphorus and / or nitrogen-containing compounds are preferable, and phosphates represented by triphenyl phosphate and triphenyl thiophosphate, hydroquinone bis (diphenyl phosphate), and hydroquinone bis (dicresyl phosphate) are particularly preferable. And the like. Phosphate oligomers represented by), aluminum polyphosphate, red phosphorus, melamine and the like are preferred.

The amount of the flame retardant (D) used in the antibacterial / flame retardant thermoplastic resin composition of the present invention is as described in the above (A) to (A).
(C) Antibacterial thermoplastic resin composition 1 containing component as a main component
3 to 60 parts by weight, preferably 5 to 5 parts by weight, per 100 parts by weight
0 parts by weight, more preferably 5 to 40 parts by weight. 3
If the amount is less than 10 parts by weight, the flame retardancy becomes insufficient, while if it exceeds 60 parts by weight, the rigidity and the impact resistance become insufficient.

In order to improve the flame retardant effect of the flame retardant (D), an antimony-containing compound can be used as a flame retardant auxiliary. The amount of the flame retardant aid used is (A)
Usually, 0.1 parts by weight per 100 parts by weight of the rubber-reinforced thermoplastic resin.
It is 1 to 20 parts by weight, preferably 0.5 to 15 parts by weight. Antimony-containing compounds are used in particular as auxiliaries for improving the flame retardancy of halogen-containing compounds. Examples of the antimony-containing compound include antimony trioxide, sodium antimonate, antimony tetroxide, (colloidal) antimony pentoxide, and antimony phosphate. Among them, antimony trioxide is preferable.

[0038] The composition of the present invention contains glass fiber, carbon fiber, metal fiber,
Metal flake, glass beads, wollastonite, milled fiber of glass, rock filler, glass flake, calcium carbonate, talc, mica, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide, zinc oxide whisker, titanium Fillers such as potassium acid whiskers, glass balloons and ceramic balloons can be used alone or in combination of two or more. Among these fillers, the shape of glass fiber or carbon fiber is 6 to 60.
Those having a fiber diameter of μm and a fiber length of 30 μm or more are preferred. These fillers may be used as component (A) 100 of the present invention.
It is usually used in the range of 1 to 150 parts by weight with respect to 100 parts by weight of parts by weight.

The composition of the present invention may contain a known coupling agent, antioxidant, weather (light) resistant agent, plasticizer, coloring agent (pigment, dye, etc.), lubricant, antistatic agent, foaming agent, etc. Additives can be blended. Further, according to the required performance, the composition of the present invention may contain other thermoplastic polymers such as polyethylene, polypropylene, polymethyl methacrylate, polyamide resin, polyamide elastomer, polybutylene terephthalate, and polyethylene terephthalate. Polyester, polyester elastomer, LCP, PPS, polysulfone, polyphenylene ether and the like can be appropriately blended.

The composition of the present invention can be obtained by mixing using a usual mixing method. For example, it is obtained by mixing the components with a mixer and kneading the components using various extruders, Banbury mixers, kneaders, rolls, feeder ruders and the like. A preferred production method is a method using an extruder and a Banbury mixer. The kneading temperature is preferably 180 to 260.
° C, more preferably 190-230 ° C. Also,
When kneading the respective components, the respective components may be kneaded all at once, or may be added and kneaded several times. The kneading may be carried out in an extruder with a multi-stage addition type,
Alternatively, the mixture can be kneaded with a Banbury mixer, a kneader, or the like, and then pelletized with an extruder. Furthermore, each component can be simply melt-kneaded in a molding machine and molded.

The composition of the present invention thus obtained can be molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile extrusion molding, foam molding, injection press, press molding, blow molding, or the like. Can be. Various molded products obtained by the above molding method are used for various parts, housings, chassis, trays, etc. in OA / home appliances, electric / electronics, sundries, automobile, etc. Can be used.

[0042]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and% are by weight unless otherwise specified. The various evaluations in the examples were measured as follows.

Antibacterial activity test An antibacterial activity test against bacteria was performed using the material of the present invention. Antibacterial activity test piece; produced by injection molding. 1/8 thickness
Inch Izod impact specimens were used. The test piece was left at room temperature for one day or more and used for bonding. Bacterial species; Escherichia coli = Escherichia coli IFO
3972 Staphylococcus aureus = Staphylococcus au
reus 12732

Antibacterial activity test content: Test medium NA medium = normal agar medium (manufactured by Eiken Chemical Co., Ltd.) 1 / 500NB medium = normal broth containing 0.2% meat extract [manufactured by Eiken Chemical Co., Ltd.] Was diluted 500 times with purified water to adjust the pH to 7.0 ± 0.2. SCDLP medium = SCDLP medium [manufactured by Nippon Pharmaceutical Co., Ltd.] SA medium = standard agar medium [manufactured by Eiken Chemical Co., Ltd.] Preparation of bacterial solution Test bacteria pre-cultured in NA medium at 37 ± 1 ° C for 16 to 24 hours The seed strain was re-inoculated into the NA medium, and then 37 ± 1 ° C., 16-
The cells cultured for 20 hours are uniformly dispersed in a 1/500 NB medium, and the number of cells per ml is 2.5 × 10 ⁵ -1.
It was adjusted to be 2 × 10 ⁶ .

Preparation of Sample A sample (5 cm × 4 cm) was lightly wiped with absorbent cotton impregnated with 99.5% (V / V) ethanol, and air-dried to obtain a sample. Test operation Bacterial solution was dropped on each of two samples at a rate of 0.5 ml per 25 cm ² , and a polyethylene film was covered thereon and adhered tightly.
%. The same test was performed using a plastic petri dish as a control sample. Measurement of viable cell count After 24 hours of storage, surviving bacteria were washed out of the sample with an SCDLP medium, and the viable cell count of the washed liquid was measured by an agar plate culture method (cultured at 35 ° C. for 2 days) using an SA medium.
It was converted per sample. Also, immediately after inoculation,
Performed on control samples.

The specific surface area of zinc oxide was measured by a BET method. The measuring device used was a micromeritics specific surface area automatic measuring device manufactured by Shimadzu Corporation. Impact resistance Measured according to Izod impact strength (ASTM D256). The test piece was molded at a cylinder temperature of 200 ° C. set. A thin-walled product was formed at a cylinder temperature of 200 ° C., and the surface appearance was visually determined. ；: The surface gloss of the molded product is high. X: The surface gloss of the molded product is low. A vertical combustion test with a thickness of 1/16 ″ was performed based on the flame-retardant UL94 V-0 standard.

The components used in the examples and comparative examples of the present invention are as follows. Preparation of Rubbery Polymers a-1 to a-3 Table 1 was used as the rubbery polymer used for the rubber-reinforced thermoplastic resin (A) of the present invention. (A) Preparation of Rubber-Reinforced Thermoplastic Resins A-1 to A-4 Various monomer components are graft-polymerized in the presence of the rubbery polymers a -1 to a-3 to prepare a rubber-reinforced thermoplastic resin. Obtained. A-1 to A-2 are emulsion polymerizations, and A-3 to A-
No. 4 was obtained by solution polymerization. Table 2 shows these rubber-reinforced thermoplastic resins. Preparation of (A ') Copolymers A'-1 to A'-3 Table 3 shows the composition and intrinsic viscosity of the component (A').

(B) Preparation of silver-based antibacterial agent Zeomic XAW-10D manufactured by Kawabunshi Co., Ltd., Novalon AG-300 manufactured by Toa Gosei Co., Ltd., and Amtec Clean-Z manufactured by Matsushita Electric Industrial Co., Ltd. did. It is shown in Table 4. (C) Preparation of zinc oxide Zinc oxide (zinc white) manufactured by Sakai Chemical Co., Ltd. was used. Table 5
Shown in (D) Preparation of Flame Retardant Platherm EP-16 (hereinafter also referred to as "D-1") manufactured by Dainippon Ink and Chemicals, Inc. was used.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

Examples 1 to 9 and Comparative Examples 1 to 7 The components were mixed according to the formulation shown in Tables 6 to 7, melt-kneaded at a barrel setting temperature of 220 ° C. by a single screw extruder, and pelletized. After sufficiently drying the pellets, using an injection molding machine,
Test pieces were prepared at a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C., and evaluated by the above evaluation method. The evaluation results are shown in Tables 6 and 7.
Shown in As is clear from Table 6, Examples 1 to 9 are compositions of the present invention, which have a high antibacterial activity which is the object of the present invention, and have high impact resistance, molded article surface appearance (glossiness) and the like. Are better. On the other hand, as is clear from Table 7, Comparative Examples 1 and 2 contain the component (B),
This is the case where no component is contained, and the antibacterial activity is inferior. Comparative Example 3 is a case where the component (B) is out of the range of the present invention and the compounding amount is large, and the impact resistance and the surface appearance of the molded product are inferior. In Comparative Examples 4 and 5, the specific surface area of the component (C) is out of the range of the present invention, the antibacterial activity is inferior, and the impact strength and the surface appearance of the molded product are also reduced. Comparative Example 6 is a case where the component (C) is out of the range of the present invention and the compounding amount is large, and although the antibacterial activity is high, the impact resistance and the surface appearance of the molded product are inferior. Comparative Example 7 is a case where the component (B) is out of the range of the present invention and its compounding amount is small, and the antibacterial activity is inferior.

[0055]

[Table 6]

[0056]

[Table 7]

[0057]

The composition of the present invention is excellent in antibacterial properties against bacteria, impact resistance, and surface appearance of molded articles, and is excellent in flame retardancy by adding a flame retardant.

Claims (2)

[Claims] 1. Oxidation wherein (B) 0.1 to 1 part by weight of a silver-based antibacterial agent and (C) specific surface area is ² to 12 m ² / g with respect to 100 parts by weight of a rubber-reinforced thermoplastic resin. Zinc 0.
An antibacterial thermoplastic resin composition containing 1 to 2 parts by weight. 2. An antibacterial / flame retardant thermoplastic resin composition comprising (D) 3 to 60 parts by weight of a flame retardant per 100 parts by weight of the composition according to claim 1.