JPH08109296A - Anti-fungus resin composition - Google Patents

Abstract

PURPOSE: To obtain an anti-fungus resin composition that is excellent in antifungal properties, transparency, and appearance of the surfaces of molted items thereof and can be used in a variety of applications, by adding a glass type anti-fungus agent containing silver or a silver compound to a transparent styrene resin. CONSTITUTION: This anti-fungus resin composition comprises (A) 100 pts.wt. transparent styrene resin and (B) 0.01 to 30 pts.wt. glass type anti-fungus agent containing silver or a silver compound. Herein, in view of the shock resistance and antifungal properties, preferably the component (A) is a rubber-reinforced resin comprising (a) 5 to 60wt.% rubber-like polymer and (b) 95 to 40wt.% aromatic vinyl compound or monomer component made up of an aromatic vinyl compound and other monomer copolymerizable with the aromatic vinyl compound. The component (B) is obtained generally by melting and mixing a silver compound and a glass raw material whose major components are SiO2 and B2 O3 and cooling and grinding the mixture. The composition is excellent in antifungal properties, transparency, and appearance of the surfaces of molded items thereof and can be used in a wide variety of applications, such as parts and housings of various appliances, telephones, etc.

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, transparency and surface appearance of molded articles.

2. Description of the Related Art Styrenic resins such as ABS resins have excellent surface appearance, molding processability, physical properties, and mechanical properties of molded products, so that they are used in the electric and electronic fields, OA and home appliances fields, automobile fields, toilet seats and kitchens. -It is used in a wide range of fields such as sanitary fields around bathrooms and sundries. In recent years, it has been pointed out that bacteria used in products used for these have adverse effects on the human body. Many styrene-based resins are also used in products containing bacteria, and it is desired to impart antibacterial properties to the styrene-based resins. There is a method of kneading a commercially available antibacterial agent as a method for imparting antibacterial properties to a styrene resin, but in the case of a transparent styrene resin, there is a drawback that transparency is impaired.

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

[0002]

The present invention contains (B) 0.01 to 30 parts by weight of a glass-based antibacterial agent containing silver or a silver compound, based on 100 parts by weight of a transparent styrene resin (A). The present invention provides an antibacterial resin composition. The (A) styrene-based resin of the present invention is (b) an aromatic vinyl compound or an aromatic vinyl compound and another monomer which is copolymerizable therewith in the presence or absence of (a) a rubbery polymer. A (graft) polymer resin (rubber-modified aromatic vinyl resin) obtained by (grafting) polymerizing a monomer component composed of a polymer, or obtained by polymerizing the monomer component (b) above. A brand-type graft copolymer resin obtained by blending a thermoplastic resin obtained with the above graft polymer resin, and further, a thermoplastic resin simply comprising (a) a rubber-like aggregate and (b) component It may be a blended product with. From the viewpoint of impact resistance and antibacterial property, the styrene resin (A) is preferably (a) 5 to 60% by weight of a rubbery polymer and (b) an aromatic vinyl compound or an aromatic vinyl compound and copolymerizable therewith. 95 to 40% by weight of a monomer component consisting of another monomer [(a) + (b) = 1
00% by weight].
Here, the rubbery polymer (a) used in the present invention includes, for example, polybutadiene, polyisoprene, butyl rubber, 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, silicone rubber, acrylic rubber,
Butadiene- (meth) acrylic acid ester copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene-based polymer, ethylene-based Examples include ionomers. Further, the styrene-butadiene block copolymer and the styrene-isoprene block copolymer include AB type and A type.
Examples include those having a BA type, a tapered type, and a radial teleblock type structure. Further, the hydrogenated butadiene-based polymer has, in addition to the hydride of the block copolymer, a hydride of a block of a styrene block and a styrene-butadiene random copolymer, and a 1,2-vinyl bond content in polybutadiene. Included are hydrides of polymers composed of blocks of 20% by weight or less and polybutadiene blocks having a 1,2-vinyl bond content of more than 20% by weight. These (a) rubbery polymers are used alone or in combination of two or more. From the viewpoint of impact resistance, a styrene resin obtained in the presence of a rubbery polymer or a styrene resin obtained in the presence of a rubbery polymer and a styrene resin obtained by polymerization in the absence of a rubbery polymer Preference is given to using mixtures with resins. Among these (a) rubbery polymers,
Ethylene-propylene copolymers, acrylic rubbers and hydrogenated butadiene-based polymers are preferred from the viewpoint of antibacterial properties.
The content of the rubber-like polymer (a) in the component (A) is preferably 5 to 60% by weight, more preferably 5 to 50% by weight, and particularly preferably 5 to 40% by weight. If the content of the component (a) is less than 5% by weight, the impact resistance is poor, and if it exceeds 60% by weight, the rigidity is poor. The monomer constituting the component (b) is an aromatic vinyl compound or the aromatic vinyl compound and another monomer copolymerizable therewith.

Examples of the aromatic vinyl compound constituting the component (b) include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene and N, N-diethyl. −
p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and the like, Particularly, styrene and α-methylstyrene are preferable. These aromatic vinyl compounds are used singly or as a mixture of two or more. Further, as the other monomer constituting the component (b), vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, Acrylic acid esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate. , Cyclohexyl methacrylate, dodecyl meta Methacrylic acid esters such as relate, octadecyl methacrylate, phenyl methacrylate and benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic acid anhydride and citraconic acid anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N- Methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide,
Imide compounds of α, β-unsaturated dicarboxylic acids such as N-phenylmaleimide and N-cyclohexylmaleimide;
Epoxy group-containing unsaturated compounds such as glycidyl methacrylate and allyl glycidyl ether: acrylamide,
Unsaturated carboxylic acid amides such as methacrylamide; amino group-containing unsaturated compounds such as acrylic amine, aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate, and 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
-Hydroxyethyl methacrylate, hydroxystyrene, and other hydroxyl group-containing unsaturated compounds; vinyloxazoline, and other oxazoline group-containing unsaturated compounds. Among the above-mentioned monomers copolymerizable with the aromatic vinyl compound constituting the component (b), particularly preferred are vinyl cyanide compounds, (meth) acrylic acid esters, unsaturated acid anhydrides, unsaturated acids, One or more monomers selected from imide compounds of α, β-unsaturated dicarboxylic acids, epoxy group-containing unsaturated compounds, and hydroxyl group-containing unsaturated compounds. Specific examples of other monomers that are particularly preferable as the component (b) include acrylonitrile, methacrylic acid,
Examples include methyl methacrylate, maleic anhydride, N-phenyl maleimide, glycidyl methacrylate, 2-hydroxyethyl methacrylate and the like. The amount of the component (b) used in the component (A) of the present invention is preferably 40 to 95% by weight, more preferably 50 to 95% by weight, and particularly preferably 60 to 95% by weight. The amount of component (b) used is 40
If it is less than 95% by weight, the rigidity is poor, while if it exceeds 95% by weight, the impact resistance is poor. The intrinsic viscosity (measured at 30 ° C. using methyl ethyl ketone as a solvent) of the methyl ethyl ketone soluble component in the component (A) of the present invention is preferably 0.2 to 2 dl / g. If the intrinsic viscosity is less than 0.2 dl / g, the impact resistance is poor, while if it exceeds 2 dl / g, the fluidity is poor. This intrinsic viscosity can be controlled by a chain transfer agent, polymerization time, polymerization temperature and the like.

When the rubber-like polymer (a) of the component (A) of the present invention is polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, etc., emulsion polymerization, solution polymerization, bulk polymerization, etc. Further, in the case of ethylene-propylene rubber, ethylene-propylene-non-conjugated diene rubber, styrene-butadiene block copolymer, hydrogenated product of diene rubber polymer, etc., solution polymerization and bulk polymerization are used. It is preferably a graft polymer resin obtained by grafting a monomer component constituting the component b). Also,
(B) A thermoplastic resin composed only of a monomer component and mixed with the above graft copolymer resin can also be used as the component (A) of the present invention to obtain the thermoplastic resin. Ordinary well-known polymerization method may be used. That is, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization are used. Resin after polymerization [Graft polymer resin comprising component (A) or thermoplastic resin comprising component (b) only]
Goes through a recovery process such as coagulation, washing, and demelting, and after drying,
Use powder or fluid. Including rubber component (A)
The graft ratio of the component is usually 10 to 200% by weight, and if it is less than 10% by weight or exceeds 200% by weight, impact resistance tends to be low, which is not preferable. Here, the graft ratio means 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, the polymerization temperature, and the like. The specific method of obtaining the graft ratio is as follows: 2 g of the styrene resin of the present invention
Is added to methyl ethyl ketone at room temperature and sufficiently stirred to obtain the insoluble matter (w). On the other hand, the amount of the rubber-like polymer in the insoluble matter (w) can be calculated based on the polymerization prescription. Let R be the calculated rubber-like polymer, and determine the graft ratio from the following formula. Graft ratio (% by weight) = [(w−R) / R] × 100 Further, those having a graft ratio in the range of 30 to 150% by weight are particularly excellent in impact resistance and antibacterial property. When a rubbery polymer is used as the component (A) of the present invention, in order to obtain the desired transparency, the refractive index of the rubbery polymer to be used and the resinous polymer weight in the presence of the rubbery polymer are used. There is a method in which the refractive index of the united body is substantially matched or the dispersed particle size of the rubber-like polymer is set to 800 ohm strong or less. (A) of the present invention
A preferred specific example of the styrene resin is polybutadiene-
Styrene-methyl methacrylate- (acrylonitrile)
Copolymer, styrene / butadiene copolymer-styrene-
Methyl methacrylate- (acrylonitrile) copolymer,
Examples thereof include hydrogenated polybutadiene polymer-styrene-methyl methacrylate- (acrylonitrile) copolymer. The composition of the present invention is intended to provide a material having transparency and antibacterial properties by blending a transparent styrene resin with a specific antibacterial agent. When the specific antibacterial agent of the present invention is blended with a general opaque styrene resin, the antibacterial property is inferior. By combining the antibacterial agent of the present invention and the transparent styrene resin, a thermoplastic resin composition having much more excellent antibacterial properties can be obtained.

The component (B) of the present invention is a glass-based antibacterial agent containing silver and a silver compound.
For example, colloidal silver (colloidal silver), silver carbonate, silver chlorate, silver perchlorate, silver bromate, silver iodate, silver periodate, silver phosphate, silver diphosphate, silver nitrate, silver nitrite, sulfuric acid. Silver, silver tungstate, silver vanadate, silver thiocyanate, silver amidosulfate, silver borate, silver thiosulfate, silver oxide, silver peroxide, silver sulfide, silver fluoride, silver chloride, silver bromide, silver iodide , Silver acetate, silver benzoate, silver lactate, silver pyrophosphate, silver citrate, silver behenate, silver diethylcarbamate, silver stearate, silver carboxylate, silver tartrate, silver metasulfonate, silver trifluoroate, phosphoric acid Alternatively, an alkyl ester of phosphorous acid, a silver salt of a phenyl ester or an alkylphenyl ester, silver phosphofluoride, silver phthalocyanine, silver ethylenediaminetetraacetate, protein silver and the like can be mentioned. Of these, preferred is silver oxide. Further, a copper compound, a zinc compound or the like can be used in combination. Examples of the copper compound include copper (II) nitrate,
Examples thereof include copper sulfate, copper perchlorate, copper acetate, potassium tetracyanocuprate, copper chloride and the like. Examples of the zinc compound include zinc (II) nitrate, zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate, zinc chloride and zinc oxide. These metal compounds are used alone or in combination of two or more. The component (B) of the present invention is generally a silver compound and Si.
It can be obtained by melting and mixing glass raw materials containing O ₂ and B ₂ O ₃ as main organisms, followed by cooling and grinding. Specific manufacturing methods include Japanese Patent Publication No. 4-80757 and Japanese Patent Publication No. 5353.
All the methods described in Japanese Patent No. 733 are used. The component (B) used in the antibacterial resin composition of the present invention preferably has an average particle diameter (longest diameter) in the range of 0.1 to 200 μ in order to achieve the object of the present invention. The glass-based antibacterial agent containing Ag ₂ O which is the component (B) of the present invention is SiO ₂
25-60 wt%, B ₂ O ₂ 18~60 wt%, Al ₂
0 to 20% by weight of O ₃ and R ₂ O (R = Li, Na, K) 0
~ 30% by weight, R'O (R '= Ca, Mg, Zn, B
a) 0 to 20% by weight, Ag ₂ O 0.05 to 10% by weight, SiO _{3 0 to} 0.1% by weight, iron oxide (Fe ₂ O ₃
Those having a composition range of 0 to 0.1% by weight (calculated) are preferable. The content of the component (B) of the present invention is 0.01 to 30 parts by weight, preferably 0.1 to 100 parts by weight of the component (A).
-10 parts by weight, more preferably 0.1-5 parts by weight. If the amount of component (B) is less than 0.01 parts by weight, the antibacterial effect is poor, while if it exceeds 30 parts by weight, impact resistance and molding appearance are poor. In the antibacterial resin compound of the present invention, the difference in refractive index between the components (a) and (b) and the difference in refractive index between the components (A) and (B) in the component (A) are preferably 0. It is 0.02 or less, and more preferably 0.01 or less. Further, an organic antibacterial agent and / or another inorganic antibacterial agent may be used in combination with the component (B) within a range that does not substantially impair transparency, and as the organic type, a benzimidazole compound, There are organic iodine compounds, ether compounds, haloalkyl compounds, nitrile compounds, sulfone compounds and the like. As the inorganic antibacterial agents, organic or inorganic metal compounds, substances having a porous structure (porous There are a structure in which a metal compound and / or a metal complex salt are supported, or a structure in which a metal ion is ion-exchanged. As the porous structure, zeolite, zirconium phosphate, silica gel,
For example, hydroxyapatite.

For the purpose of further enhancing the antibacterial effect, the following substances can be added to the thermoplastic resin composition of the present invention within a range not impairing transparency. (1) Polyamide-based and polyester-based elastomers containing polyethylene glycol as a block component (2) Antistatic agent low molecular type and high molecular type Anion and nonionic types are particularly preferable. (3) Molecular weight of 300 to have at least one kind of functional group
10,000 compounds or polymers (4) Metal salts having a divalent or higher valent cationic metal ion such as zinc, gold and copper compounds (5) Polymers having a cationic property The above components can also be used in combination. The antibacterial resin composition of the present invention includes glass fiber, carbon fiber, metal fiber, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass ferry, kaolin, barium sulfate, graphite and disulfide. Fillers such as molybdenum, magnesium oxide, zinc oxide whiskers and potassium titanate whiskers can be used alone or in combination. Of these fillers,
As the shape of the glass fiber and the carbon fiber, those having a fiber system of 6 to 60 μm and a fiber length of 30 μm or more are preferable. These fillers are usually used in the range of 5 to 150 parts by weight with respect to 100 parts by weight of the composition of the present invention. Further, other thermoplastic resins such as polyethylene, polypropylene, polysulfone, polyamide, polyester, polycarbonate, liquid crystal polymer and the like can be blended within a range not losing the transparency. Various known additives may be added to the composition of the present invention. For example, there are coupling agents, flame retardants, antioxidants, plasticizers, colorants, silicone oils and the like. 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. When kneading each component, each component may be kneaded together or may be kneaded by a multi-stage addition method.
The antibacterial resin composition of the present invention thus obtained,
Various molded products can be molded by injection molding, sheet extrusion, vacuum molding, irregular shape molding, foam molding, injection press, press molding, blow molding, and the like. When obtained by injection molding, the antibacterial property tends to be better when the injection speed is increased. Various molded articles obtained by the above-mentioned molding method are used for toilet seats, humidifiers, water purifiers, air conditioners, miscellaneous goods, stationery, other various home appliances, telephone parts and other parts, housings, etc. Can be used.

[0007]

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. Also, various evaluations in the examples,
It is a value measured as follows. 0.2 ml of a bacterial solution of MRSA (mesitillin-resistant staphylococcus aureus) (the number of bacteria per ml is about 10 ⁶ ) was inoculated into an antibacterial specimen (molded product of a resin flat plate), 0.2 ml was inoculated, and a polyethylene film was adhered thereto, and then at 35 ° C. The cells were preserved, and the viable bacteria were washed out with SCDLP agar medium [manufactured by Nippon Pharmaceutical Co., Ltd.] at the start of storage and 24 hours later. The number of viable cells of this washout 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. The initial number of bacteria tested in Examples and Comparative Examples was 3 × 10 ⁵ . Molded Product Surface Appearance A flat plate having a wall thickness of 1.0 mm × 150 mm × 150 mm was molded with two pinpoint gates, and the appearance of the weld portion and the surface other than the weld was visually evaluated according to the following evaluation criteria. ◯: Good appearance ×: Poor appearance. Transparency Using the above-mentioned test piece for surface appearance of a molded product, visual evaluation was performed according to the following evaluation criteria. ○: Transparent ×: Opaque The following components were used as the component (A) of the present invention. In addition,
The resulting injection molded article of component (A) was substantially transparent. Rubbery polymer (a) -1 Polybutadiene latex having an average particle size of 2600 ohm strong obtained by emulsion polymerization (a) -2 Polystyrene (5%) block and a random copolymer block consisting of 80 parts of styrene and 80 parts of butadiene ( 90%) and taper block (5%) consisting of 5 parts of styrene and 3 parts of butadiene and gradually increasing styrene.
Hydrogenation rate of ABC type block copolymer consisting of 99%
Hydrogenated diene polymer of.

[0008]

[Table 1]

Polymers (A) -1 to (A) -3 (A) -1, (A) -3 and (A) -4 were obtained by emulsion polymerization and (A) -2 was obtained by solution polymerization. . Glass-based antibacterial agents (B) -1 and 2, zeolite-based antibacterial agents (B) -3, 4 (B) -1: Amorphulin P-10 (silver type) manufactured by Nippon Glass Fiber Co., Ltd. (B) -2: Ishizuka Glass Ion Pure P (silver type) (B) -3: Shinagawa Fuel Co., Ltd. Zeomic XAW10D (silver type) (B) -4: Kanebo Bactekiller BM103 (silver type)

Examples 1 to 7 and Comparative Examples 1 to 5 Preparation of antibacterial compositions The above components (A) and (B) of the present invention were dried to a water content of 0.1% or less, and the formulation shown in Table 1 was used. The mixture was mixed, melt-kneaded using a twin-screw extruder with a vent, and pelletized. In preparing the antibacterial composition of the present invention, 0.1 part of WAX-E manufactured by Hoechst Co. was added as a lubricant. The obtained pelletized water content was dried to 0.1% or less, and a test piece for evaluation of antibacterial property and surface appearance of a molded product was molded by injection molding, and evaluated by the above evaluation method. The results are shown in Table 2.

[0011]

[Table 2]

Comparative Example 1 is an example in which the amount of the component (B) used in the present invention is small outside the range of the invention, and the antibacterial property is poor. Comparative Example 2 is an example in which the use amount of the component (B) of the present invention is outside the scope of the invention, and the surface appearance of the molded product is poor. In Comparative Examples 3 and 4, the type of the component (B) is outside the scope of the invention, and the transparency is poor. Comparative Example 5 is an example using an opaque styrene resin, and is inferior to Example 8 in antibacterial property.

[0013]

The antibacterial resin composition of the present invention has antibacterial properties,
It is excellent in transparency and surface appearance of molded products, and is useful for a wide range of applications such as humidifiers, water purifiers, air conditioners, toilet seats, stationery, miscellaneous goods, various other home appliances, telephones, and other parts and housings.

Front page continued (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. An antibacterial resin composition containing (B) 0.01 to 30 parts by weight of a glass-based antibacterial agent containing silver or a silver compound, based on 100 parts by weight of a transparent styrene resin (A). .