JPH1110766A - Anti-bacterial metal plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-bacterial activity at a degree to be usable for actual usages by a method wherein an anti-bacterial layer containing at least one kind of anti-bacterial agent which is selected from inorganic and organic anti-bacterial agents and a hydrophilic substance, is laminated on a metal plate. SOLUTION: This anti-bacterial metal plate is constituted by laminating an anti-bacterial layer containing at least one kind of anti-bacterial agent which is selected from a group comprising inorganic anti-bacterial agents and organic anti-bacterial agents, and a hydrophilic substance, on a metal plate. The inorganic anti-bacterial agent is a metal molecule such as silver, which shows an anti-bacterial activity against yellow staphylococcus and coli bacteria, etc., and/or molecules wherein these metal ion species are carried by silica, etc., sol-gel thin film of a metallic oxide having a photooxidation catalyst pacability such as zinc oxide, or molecules of them. The organic anti-bacterial agent is a natural extracted substance, a low molecular organic compound, and a high molecular organic compound having an anti-bacterial activity against yellow staphylococcus, etc., and generally contains atoms of nitrogen, sulfur and phosphorus, etc. For the hydrophilis substance, polyethyleneglycol, etc., can be counted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial metal plate, and more particularly to a decorative plate used for walls, floors and ceilings.
The present invention relates to an antibacterial metal plate suitably used for a molded body such as a metal container such as an exterior plate, a structure of a cooking appliance, a home appliance, a window frame or a door knob of a building material, a handrail, or the like.

[0002]

2. Description of the Related Art Thermoplastic resins, especially polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Nylon, polyethylene terephthalate and polyethylene naphthalate have excellent physical and chemical properties and are used for fibers, plastics, films, sheets, adhesives and the like. Recently, antibacterial goods containing or coated with an inorganic or organic antibacterial agent are appearing on the market. Its uses are diverse. As an example,
Resins containing or coated with these antibacterial agents are laminated on walls, floors and ceilings of kitchens, toilets, bathrooms, and the like. In addition, a metal plate in which a resin containing or applying these antibacterial agents is laminated is used for a structure of a cooking appliance or a home appliance.

At present, antibacterial agents mainly studied or used include natural products such as chitin, chitosan, wasabi extract, mustard extract, hinokitiol, tea extract antibacterial agent; titanium oxide particles with photo-oxidation catalyst, zinc oxide Synthetic products such as ultrafine particles, inorganic compounds such as silver-containing zeolite and silver-containing zirconium phosphate, and organic compounds such as organic ammonium salts and organic phosphonium salts are exemplified. Natural antibacterial agents and inorganic antibacterial agents represented by silver have been recently attracting attention because of their toxicity, and the following inventions have already been disclosed.

For example, JP-A-3-83905 discloses a silver ion-containing phosphate antibacterial agent.
No. 409 discloses an antibacterial agent obtained by replacing a certain volume of zeolite having a specific ion exchange capacity with silver ions.

However, in terms of the antibacterial properties of films, sheets and fibers containing or coated with these antibacterial agents against Staphylococcus aureus, Escherichia coli, and the like, and the transparency of these molded articles, the amount of addition is compared in order to maintain transparency. If the amount is too low, the antibacterial activity is insufficient, and if the amount added is increased to improve the antibacterial activity, transparency must be sacrificed, and there is room for practical improvement.

On the other hand, organic antibacterial agents are generally superior in antibacterial activity against fungi and the like to natural antibacterial agents and inorganic antibacterial agents. However, when such an antibacterial agent is contained or applied to the surface of a substrate such as a film, the antibacterial agent has a low molecular weight, so that it is easily volatilized, desorbed and separated from the surface of the substrate such as a film, and the antibacterial activity has a long-term stability. However, it is not preferable in terms of safety to the human body. As described above, when an organic antibacterial agent is used for a film or the like, the antibacterial agent does not dissolve in water, an organic solvent, or the like, and is free from the film surface, detached, peeled, and hardly falls off. It is preferable from the viewpoint of long-term stability and safety to the human body.

Under these circumstances, recently, an immobilized antibacterial agent has been developed in which an organic antibacterial agent is ionically or covalently bonded to a polymer material as a raw material of a film, a fiber or the like. For example, JP-A-54-86584 discloses that
An antibacterial material mainly composed of a polymer in which an acidic group such as a carboxyl group or a sulfonic acid group of a polymer is ion-bonded to a quaternary ammonium base as an antibacterial component is described. JP-A-61-245378 describes a fiber comprising a polyester copolymer containing an antibacterial agent component having a basic group such as an amidine group or a quaternary ammonium group as a copolymerization component.

However, the antibacterial activity against Staphylococcus aureus, Escherichia coli, etc. was evaluated for fibers, fabrics, films, sheets and the like containing or coated with these antibacterial materials. It was not enough.

On the other hand, it has been disclosed that phosphonium salt compounds are biologically active chemical substances having a broad spectrum of activity against bacteria, and the invention in which this compound was immobilized on a polymer substance and the use of the compound was attempted to be expanded. (JP-A-57-204286, 63-60903, 62-114903, and JP-A-1-93596).
No. 2,240,090).

JP-A-4-266912 discloses a phosphonium salt-based vinyl polymer antibacterial agent.
Japanese Patent Publication No. 4-814365 discloses a vinylbenzylphosphonium salt-based vinyl polymer antibacterial agent. Further, JP-A-5-310820 discloses that
An antibacterial material mainly composed of a polymer in which an acidic group of a polymer and a phosphonium base of an antibacterial component are ionically bonded is described. In that example, a polyester using a phosphonium salt of sulfoisophthalic acid is disclosed.

However, the antibacterial properties of fibers, films, sheets and the like formed from these phosphonium salt polymers or fibers, films and sheets coated with these phosphonium salt polymers on the surface were evaluated. Antibacterial activity was insufficient. Furthermore, in order to improve the antibacterial activity, a polyester in which trinormal butyl dodecylphosphonium base is ion-bonded with 50 mol% or more of all the acidic groups was synthesized and formed into a film, a sheet or the like. The antibacterial properties as well as the mechanical properties were lowered due to the lowering of the coloring and the glass transition point.

Furthermore, fibers, fabrics, films, sheets and the like are formed by using not only the above-mentioned inorganic antibacterial agent and organic antibacterial agent alone but also by mixing two or more kinds thereof, and the molded product is used against Staphylococcus aureus, Escherichia coli and the like. The antibacterial properties were evaluated, but in all cases, the antibacterial activity was insufficient and the practicality was insufficient.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide an antibacterial metal plate having an antibacterial activity of a practical level. .

[0014]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the antibacterial layer has a very high antibacterial activity by containing a hydrophilic substance in addition to the antibacterial agent. It turned out to be.

The present invention is as follows. (1) An antimicrobial metal comprising an antimicrobial layer containing at least one antimicrobial agent selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent and a hydrophilic substance laminated on a metal plate Board. (2) The antibacterial metal plate according to the above (1), wherein the organic antibacterial agent is a polymer antibacterial agent and the hydrophilic substance is contained as one of the polymerization components of the polymer antibacterial agent. (3) The above (1) or (2), wherein the organic antibacterial agent is a polymer antibacterial agent having at least one group selected from the group consisting of ammonium base, phosphonium base and sulfonium base in the main chain or side chain. The antibacterial metal plate as described. (4) The antibacterial property according to the above (1), wherein the inorganic antibacterial agent is at least one kind of metal fine particles selected from the group consisting of silver, zinc and copper and / or inorganic fine particles carrying the metal ions. Metal plate. (5) The antibacterial metal plate according to (1), wherein the inorganic antibacterial agent contains titanium oxide and / or zinc oxide. (6) The hydrophilic substance comprises a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, an amine base, a polyether chain and a polyamine chain. The antibacterial metal plate according to any one of the above (1) to (5), which is a compound having at least one compound selected from the group. (7) The metal plate is made of a material selected from the group consisting of aluminum, steel, and an alloy containing them as a main component.
The antibacterial metal plate according to any one of (1) to (6). (8) Between the metal plate and the layer made of an antibacterial agent or an antibacterial composition, a layer made of a thermoplastic resin is provided (1)
The antibacterial metal plate according to any one of (1) to (7). (9) The thermoplastic resin is polyethylene, polypropylene,
The antibacterial metal plate according to the above (8), which is at least one resin selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, nylon and polyester.

[0016]

Next, the present invention will be described in detail. The antibacterial metal plate of the present invention is obtained by laminating an antibacterial layer containing at least one antibacterial agent selected from the group consisting of an inorganic antibacterial agent and an organic antibacterial agent and a hydrophilic substance on a metal plate. is there.

In the present invention, the term "inorganic antibacterial agent" is a generic term for inorganic compounds containing metals or metal ions and exhibiting antibacterial activity against Staphylococcus aureus, Escherichia coli, and the like, and may be in any form of gas, liquid and solid. Specifically, metal fine particles such as silver, zinc, and copper having antibacterial properties and / or metal ion species thereof are converted into a metal oxide such as silica, zeolite, synthetic zeolite, zirconium phosphate, calcium phosphate, and calcium zinc phosphate. Fine particles supported on inorganic materials such as ceramics, soluble glass powder, alumina silicon, titanium zeolite, apatite, calcium carbonate;
Sol-gel thin films or fine particles of metal oxides having photo-oxidation catalytic activity such as zinc oxide, titanium oxide and molybdenum oxide; and sol-gel thin films and fine particles obtained by surface treatment with an inorganic or organic compound reagent Composite particles obtained by laminating, coating, enclosing / embedding the surface of inorganic compound particles with another inorganic oxide, composite oxide, or the like by a sol-gel method or the like. Further, it is also possible to add the above-mentioned inorganic antibacterial agent to a metal alcoholate as a raw material at the time of forming a metal sol-gel to be used as a composite system. further,
By using a substance having photocatalytic ability and irradiating near-ultraviolet light in an optional step, even stronger antibacterial properties can be exhibited.

As specific examples of such an inorganic antibacterial agent, Novalon (manufactured by Toagosei Co., Ltd.), Bactekiller (manufactured by Kanebo Kasei Co., Ltd.), antibacterial spherical ceramic fine particles S1, S2, S5 (manufactured by ) Admatex), Holon Killer (Nikko Co., Ltd.), Zeomic (Shinagawa Fuel Co., Ltd.), Amenitop (Matsushita Electric Industrial Co., Ltd.), Ion Pure (Ishizuka Glass Co., Ltd.), etc. Agent, Z-No
uv (Mitsui Metal Mining Co., Ltd.) and other zinc-based antibacterial agents;
Titanium dioxide fine particles such as No. 25 (Nippon Aerosil Co., Ltd.) and ST-135 (Ishihara Sangyo Co., Ltd.), sol-gel bodies, and the like, but are not limited thereto. Examples of the composite particles include, but are not limited to, fine particles obtained by coating titanium dioxide with silica, GYT (manufactured by Goyo Paper Industries, Ltd.), and the like.

The above-mentioned inorganic antibacterial agent is contained in the antibacterial layer preferably in an amount of 0.1 to 10% by weight, more preferably 0.3 to 5% by weight. When this content is less than 0.1% by weight,
If the antibacterial layer has insufficient antibacterial activity and exceeds 10% by weight, the antibacterial layer may be colored or heat resistance or transparency may be reduced.

The organic antimicrobial agent is a general term for natural extracts, low molecular weight organic compounds and high molecular weight organic compounds having antibacterial activity against Staphylococcus aureus and Escherichia coli, and generally contains elements such as nitrogen, sulfur and phosphorus. It is a target.

For example, natural antibacterial agents include, for example,
Chitin, chitosan, wasabi extract, mustard extract, hinokitiol, tea extract, and the like.Examples of low-molecular-weight organic antibacterial agents include, for example, allyl isothiocyanate, polyoxyalkylene trialkyl ammonium, benzalkonium chloride, and hexa. 4th such as methylene biguanide hydrochloride
Examples include, but are not limited to, quaternary ammonium salts, organic silicon quaternary ammonium salts, phenylamide-based, biguanide-based, tetraalkylphosphonium sulfoisophthalate salts or diesters thereof.

The above-mentioned organic antibacterial agent is contained in the antibacterial layer in an amount of preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight. When this content is less than 0.1% by weight,
When the antibacterial activity of the antibacterial layer becomes insufficient and exceeds 10% by weight, the mechanical properties and heat resistance / weatherability of the antibacterial layer may decrease.

The high molecular weight organic antibacterial agent is a high molecular compound in which an onium salt such as an ammonium base, a phosphonium base or a sulfonium base, or an antibacterial active group such as a phenylamide group or a biguanide group is bonded to a main chain or a side chain. From the viewpoint of improving the antibacterial property of the hydrophilic substance, a polymer antibacterial agent having at least one of an ammonium base, a phosphonium base and a sulfonium base is preferable, and a polymer antibacterial agent having a phosphonium base is most preferable. Examples are shown below, but are not limited thereto. a) Phosphonium salt vinyl polymer represented by the following general formula

[0024]

Embedded image

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a linear or branched alkyl, aryl or aralkyl group having 1 to 18 carbon atoms, or a hydroxyl or alkoxyl group) Represents a substituted alkyl group, aryl group or aralkyl group, X ⁻ represents an anion, and n represents an integer of 2 or more.)

Specific examples of the above R ¹ , R ² and R ³ include:
Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl and the like. Examples of the aryl group include phenyl, tolyl, xylyl and the like. Examples of the aralkyl group include benzyl, phenethyl and the like. Examples of the alkyl group substituted with a hydroxyl group include 2-hydroxyethyl,
Examples of the aryl group substituted with a hydroxyl group include p-hydroxyphenyl, and examples of the aralkyl group substituted with a hydroxyl group include p-hydroxybenzyl, and an alkyl group substituted with an alkoxyl group. Examples thereof include 2-butoxyethyl.Examples of the aryl group substituted with an alkoxyl group include p-butoxyphenyl.Examples of the aralkyl group substituted with an alkoxyl group include p-butoxy. Benzyl is mentioned. Among them, an alkyl group and an aryl group are preferable.

X ^- is an anion, for example, a halogen ion such as fluorine, chlorine, bromine or iodine, a sulfate ion, a phosphate ion, a perchlorate ion, etc.
Among them, a halogen ion is preferable. The upper limit of n is not particularly limited, but is preferably 2 to 500, more preferably 10
~ 300.

B) Copolymerized polyester having a phosphonium base A copolymerized polyester having a phosphonium salt of an aromatic dicarboxylic acid having a sulfonic acid group as a dicarboxylic acid component.

Examples of the phosphonium salt of an aromatic dicarboxylic acid having a sulfonic acid group include tri-n-butyldecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, and tri-n sulfoisophthalate. -Butylhexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate, tri-n-butyldodecylphosphonium sulfoisophthalate, tri-n-butyldecylphosphonium sulfoterephthalate, tri-n sulfoterephthalate -Butyloctadecylphosphonium salt, tri-n-butylhexadecylphosphonium sulfoterephthalate, tri-n-butyltetradecylphosphonium sulfoterephthalate, tri-n-butyldodecyl sulfoterephthalate Phosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2, 7-dicarboxylic acid tri-n-butylhexadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-
And 2,7-dicarboxylic acid tri-n-butyldodecylphosphonium salt. Among them, tri-n-butylhexadecylphosphonium sulfoisophthalate and sulfoisophthalate tri-n
-Butyltetradecylphosphonium salt and tri-n-butyldodecylphosphonium sulfoisophthalate are particularly preferred.

The polymerization amount of the phosphonium salt of the aromatic dicarboxylic acid having a sulfonic acid group is preferably 1 to 50 m in all the dicarboxylic acid components constituting the polyester.
ol%. When the polymerization amount is less than 1 mol%, the antibacterial activity of the obtained copolymerized polyester is inferior,
If the amount exceeds mol%, the glass transition point of the obtained copolymerized polyester is reduced, and the heat resistance and strength may be insufficient.

The above-mentioned phosphonium salt of an aromatic dicarboxylic acid having a sulfonic acid group includes, for example, tri-n-butylhexadecylphosphonium bromide, an aromatic dicarboxylic acid having a sulfonic acid group or a sodium salt, a potassium salt or an ammonium salt thereof. It is obtained by reacting a phosphonium salt such as tri-n-butyltetradecylphosphonium bromide and tri-n-butyldodecylphosphonium bromide. The reaction solvent at this time is not particularly limited, but water is most preferable.

Examples of other dicarboxylic acid components include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and heterocyclic dicarboxylic acids. Specifically, examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-dicarboxyphenyl, 4,4-dicarboxylbenzophenone, bis (4-carboxy) Phenyl) ethane and derivatives thereof; alicyclic dicarboxylic acids include cyclohexane-1,4-dicarboxylic acid and derivatives thereof; and aliphatic dicarboxylic acids include adipic acid, sebacic acid, and dodecane. Examples include diacid, eicoic acid, dimer acid and derivatives thereof, and examples of the heterocyclic dicarboxylic acid include pyridinedicarboxylic acid and derivatives thereof. In addition to such a dicarboxylic acid component, it is also possible to use oxycarboxylic acids such as p-oxybenzoic acid, and polyfunctional acids such as trimellitic acid, pyromellitic acid and derivatives thereof.

As the glycol component, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexane Examples include dimethanol and an ethylene oxide adduct of bisphenol A. In addition, it may contain a small amount of a compound containing an amide bond, urethane bond, ether bond, carbonate bond or the like.

The method for producing the above-mentioned copolymerized polyester is not particularly limited, but a so-called direct polymerization method in which an oligomer obtained by directly reacting a dicarboxylic acid and a glycol is polycondensed, a dimethyl ester of dicarboxylic acid and a glycol are used. Is subjected to a transesterification reaction followed by polycondensation, for example, a so-called transesterification method, and any production method can be applied. Further, a polymerization catalyst such as antimony oxide, germanium oxide, or a titanium compound may be used during the polymerization.

The production of the above-mentioned copolymerized polyester is not limited to the above-mentioned method. As another synthesis method, an aromatic dicarboxylic acid having a sulfonic acid group is produced as a dicarboxylic acid component, and then the polyester is produced. To
A method of reacting a phosphonium compound such as tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide, or tri-n-butyldodecylphosphonium bromide can also be used.

The molecular weight of the above copolymerized polyester is preferably 5,000 to 50,000, more preferably 1,000.
0 to 30,000, more preferably 15,000 to 250
00. When the molecular weight is 5,000 or less, the mechanical strength of the antimicrobial layer of the present invention is insufficient, which is not preferable for practical use.

For the purpose of improving heat resistance such as prevention of coloring and generation of gel, the above-mentioned copolymerized polyesters include Mg salts such as magnesium acetate and magnesium chloride, Ca salts such as calcium acetate and calcium chloride, manganese acetate, and the like. Mn salts such as manganese chloride; Zn salts such as zinc chloride and zinc acetate; and Co salts such as cobalt chloride and cobalt acetate, each having a metal ion of 300 ppm or less, phosphoric acid or phosphoric acid such as trimethyl phosphate or triethyl phosphate It is also possible to add an ester derivative of 200 ppm or less as P. If the amount exceeds the above range, not only the coloring of the polyester becomes remarkable but also the heat resistance and the hydrolysis resistance of the polyester are significantly reduced. Therefore, the molar ratio of the total P amount and the total metal ion amount represented by the following formula is 0.4 to 1.0 in terms of preventing coloration, heat resistance, and preventing deterioration in hydrolysis resistance and the like. It is preferable to add them.

Molar ratio of additive = total amount of P (molar atom) /
Total amount of the above metal ions (molar atoms)

When the above molar ratio is out of the above range, coloring of the polyester of the present invention becomes remarkable, heat resistance and hydrolysis resistance of the polymer are remarkably reduced, and generation of coarse particles becomes remarkable. Not preferred.

The timing of adding the metal ions and phosphoric acid is not particularly limited, but generally, the metal ions are added at the time of charging the raw materials, that is, before transesterification or esterification.
Phosphoric acids are preferably added before the polycondensation reaction.

The above-mentioned polymer antibacterial agent is contained in the antibacterial layer preferably in an amount of 1 to 100% by weight, more preferably 10 to 100% by weight. If the content is less than 1% by weight, the antibacterial activity of the antibacterial layer may be insufficient.

The antibacterial layer contains a hydrophilic substance in addition to the above antibacterial agent. The hydrophilic substance used in the present invention refers to a substance whose hydrophilicity of the antibacterial layer is increased by containing the substance compared to when the substance is not contained. In the present invention, examples of the hydrophilic substance include at least one of a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, and an amine base. Examples of the compound include a compound having a group, and a compound having at least one kind of a polyether chain and a polyamine chain. here,
The polyether chain refers to a chain containing two or more ether bonds in the main chain, and typically includes, for example, a polyoxymethylene chain, a polyoxyethylene chain, and a polyoxypropylene chain. The polyamine chain is a chain containing two or more basic nitrogen atoms in the main chain, and typical examples include a polyethyleneimine chain and a polyalkylene polyamine chain (for example, a polyethylene polyamine chain).

Specifically, for example, polyvinyl alcohol, polyacrylamide, poly (N, N-dimethylaminomethylacrylamide), poly (N, N-dimethylaminoethyl acrylate), poly (N, N-dimethylaminoethyl methacrylate) ), Polyvinylamine, polyvinylpyridine, polyvinylpyrrolidone, polyvinylimidazole, homopolymer or copolymer of acrylic acid, homopolymer or copolymer of methacrylic acid, homopolymer or copolymer of maleic anhydride (eg, maleic anhydride) Styrene copolymer), a homopolymer of vinylsulfonic acid or a copolymer thereof or an alkali metal salt thereof, a homopolymer of styrenesulfonic acid or a copolymer thereof or an alkali metal salt thereof, and a quaternary ammonia of polystyrene Or a polyalkylene glycol (eg, polyethylene glycol (also known as polyethylene oxide), polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, etc.), a polyol such as glycerin, polyglycerin, or the like. An alkali metal salt or an ammonium salt of sulfoisophthalic acid as a dicarboxylic acid component in the polymer, and 1 to 10 m in the total dicarboxylic acid component
ol% copolymerized polyester and the like. Also,
The above polyalkylene glycols, polyglycerols may be alcohols, alkylphenols, fatty acids, polyether derivatives blocked with amines, etc., for example, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyglycerin alkylene oxide adducts, fatty acids thereof Derivatives such as esters or aliphatic alcohol ethers, polyglycerin fatty acid esters, polyglycerin aliphatic alcohol ethers, polyglycerin glycidyl ethers, and reaction products thereof are given.

Among the above-mentioned hydrophilic substances, polyethylene glycol, polyglycerin and their derivatives are improved in antibacterial properties, and are compatible with resins (especially polyester resins) which can be further incorporated into an antibacterial layer as described later. It is preferred in that respect. Further, a hydrophilic substance can be included as one of the polymerization components of the resin.

As the hydrophilic substance, a substance which is more hydrophilic than the above-mentioned antibacterial agent is selected, and a substance which can increase the hydrophilicity of the whole antibacterial layer by containing it is used as compared with a case where it is not contained. .

The molecular weight of the hydrophilic substance is not particularly limited. For example, in the case of polyethylene glycol, the number average molecular weight is preferably 200 to 30,000, more preferably 1 to 3.
2,000 to 25,000.

The content of the above-mentioned hydrophilic substance is not particularly limited. For example, in the case of polyethylene glycol, it is preferably 0.1 to 20% by weight, more preferably 0.5% by weight, based on the whole composition constituting the antibacterial layer. 10 to 10% by weight, more preferably 1 to 5% by weight. This content is 0.1% by weight
If less than 2, the effect of increasing the antibacterial activity is insufficient,
If it exceeds 0% by weight, the mechanical properties and the heat resistance and weather resistance of the antibacterial layer may be reduced.

The method of compounding the hydrophilic substance includes a method in which the inorganic and / or organic antibacterial agent and the hydrophilic substance are melted by heating using an extruder or the like, a method in which the inorganic and / or organic antibacterial agent is mixed with the hydrophilic substance. There is a method in which a substance is mixed and dissolved or dispersed in an appropriate solvent, for example, water, a mixed solvent of water / alcohol, or an organic solvent such as acetone or methyl ethyl ketone, and then the solvent is evaporated to dryness.

The hydrophilic substance may have a bond such as an ionic bond or a covalent bond with the above-mentioned inorganic or organic antibacterial agent.

When the antibacterial agent is a high-molecular antibacterial agent, it may have a hydrophilic substance as one of its polymerization components. In this case, as the high-molecular antibacterial agent, a high-molecular compound having an antimicrobial active group such as an ammonium salt, a phosphonium salt, an onium salt such as a sulfonium salt, a phenylamide group, or a biguanide group bonded to the main chain or a side chain as described above. From the viewpoint of improving the antibacterial properties of the hydrophilic substance, a polymer antibacterial agent having an ammonium base, a phosphonium base, or a sulfonium base is preferable, and a polymer antibacterial agent having a phosphonium base is most preferable. Specific examples include the above-mentioned phosphonium salt-based vinyl polymers and copolymerized polyesters using a phosphonium salt of an aromatic dicarboxylic acid having a sulfonic acid group as a dicarboxylic acid component.

A hydrophilic substance is used as one of the polymer components of these polymers. For example, when the polymer antimicrobial agent is the above-mentioned copolymerized polyester, at least one of a glycol component and a dicarboxylic acid component is used. Used for at least a part of

As the hydrophilic substance in this case, a substance which is more hydrophilic than the other polymerization components is selected. By using this as a polymerization component, the hydrophilicity of the whole antibacterial layer is reduced as compared with the case where no polymerization component is used. Those that can be enhanced are used. For example, in the case of the above-mentioned copolymerized polyester, a phosphonium salt of an aromatic dicarboxylic acid having a sulfonic acid group, a normal dicarboxylic acid component such as terephthalic acid, and a more hydrophilic component than a normal glycol component such as ethylene glycol and neopentyl glycol. Is selected so that the hydrophilicity of the whole antimicrobial layer can be enhanced.

Specific examples of the hydrophilic substance include polyols such as polyalkylene glycol, glycerin and polyglycerin, sulfoisophthalic acid or an alkali or ammonium salt thereof, vinylpyrrolidone,
Copolymerizable hydrophilic substances (monomers) such as acrylic acid or an alkali or ammonium salt thereof, styrenesulfonic acid or an alkali or ammonium salt thereof, and the like.

Such an antibacterial agent containing a hydrophilic substance as a polymerization component of a high-molecular antibacterial agent is particularly preferable because it can prevent bleeding out of the hydrophilic substance out of the system, that is, can maintain high antibacterial activity for a long period of time.

The content of the hydrophilic substance in the above case varies depending on the kind. For example, in the case of polyalkylene glycol, preferably 0.1 to 20% by weight of the polymer antibacterial agent is used.
More preferably, it is 0.5 to 10% by weight, and still more preferably 1 to 5% by weight. When the content is less than 0.1% by weight, the effect of increasing the antibacterial activity is insufficient, and when it exceeds 20% by weight, the mechanical properties and heat resistance / weatherability of the antimicrobial layer may be reduced. .

The compounding of the hydrophilic substance may be carried out during the production of the high-molecular antibacterial agent, before the polymerization reaction, during the polymerization reaction or after the termination.

For the purpose of improving physical properties such as slipperiness, abrasion resistance, blocking resistance and concealing property, the antibacterial layer is made of calcium carbonate (CaCO ₃ ), calcium phosphate, apatite, barium sulfate (BaSO ₄ ), Calcium fluoride (CaF ₂ ), talc, kaolin, silicon oxide (SiO
₂ ), inorganic particles such as alumina (Al ₂ O ₃ ), titanium dioxide, zirconium oxide (ZrO ₂ ), iron oxide (Fe ₂ O ₃ ), and alumina / silica composite oxide; polystyrene,
Polymethacrylate, polyacrylate,
Organic particles such as a copolymer thereof or a cross-linked product thereof may be contained.

As calcium carbonate, there are three crystal forms: calcite classified into a trigonal or hexagonal system, aragonite classified into an orthorhombic system, and vaterite classified into a hexagonal or pseudo-hexagonal system. However, any crystal form may be used, and the shape thereof can be arbitrarily selected, such as a sphere, a cube, a spindle, a column, a needle, a sphere, and an egg. As kaolin, natural kaolin, synthetic kaolin,
Any type may be used regardless of sinterability or unsinterability, and the shape thereof may be arbitrarily selected, such as plate, column, sphere, spindle, and egg. Examples of the alumina include crystalline alumina hydrates such as gibbsite, bayerite, Nordstrandite, boehmite, diamond bore, todite; amorphous alumina hydrates such as amorphous gel, boehmite gel, bayerite gel; Intermediate activated aluminas such as η, γ, χ, κ, δ, θ types and the like, or α-type aluminas are exemplified.

The average particle diameter of the above-mentioned particles is not particularly limited since it is appropriately selected according to the purpose, but the average primary particle diameter is preferably 0.01 to 5 μm, and the amount of the particles is preferably 5 to 5 μm in the composition. % By weight or less. When the added amount of the particles exceeds 5% by weight, the coarse particles of the particles in the composition become remarkable, coarse protrusions are conspicuous on the surface of the antibacterial layer, and the particles easily fall off, and the quality of the metal plate is deteriorated. There is a risk of lowering.

The method of blending the particles is not particularly limited.
A method of dispersing or dissolving an organic antibacterial agent in a predetermined solvent and dispersing the particles in the system, and a method of adding and dispersing the particles in a synthetic polymerization reaction system of a polymer antibacterial agent,
In particular, when the high-molecular antibacterial agent is a thermoplastic polymer, there is a method in which the particles are added to the polymer and melt-kneading, and when the hydrophilic substance is a polymer, the method is added during the polymerization reaction.

When the polymeric antibacterial agent is polyester,
The particles are usually added to the polyester polymerization reaction system as a slurry in addition to ethylene glycol. The timing of the addition depends on the type of fine particles to be used, the particle diameter, the chloride ion concentration, the slurry concentration, the slurry temperature, and the like, but is usually preferably before the start of the polyester polymerization reaction or at the oligomer formation stage. When the slurry is added to the reaction system, it is preferable to heat the slurry to the boiling point of ethylene glycol from the viewpoint of improving the dispersibility of the particles. It is also possible to mix a predetermined thermoplastic resin to which fine particles have been added in advance with an inorganic and / or organic antibacterial agent.

The antimicrobial layer may further contain a suitable thermoplastic resin or thermosetting resin. Examples of such a resin include polyolefins such as polyethylene and polypropylene; vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; 6-nylon, 6,6-nylon,
Polyamides such as 1 nylon and 12 nylon; aliphatic polyesters; aromatic polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonates, polystyrenes, acrylic resins, polyurethane resins, amino alkyd resins, acrylic silicone resins, and melamine resins. . As described above, a hydrophilic substance can be included as one of the polymerization components of these resins.

Further, the antibacterial layer may further comprise an inorganic compound such as a water-insoluble alkali silicate, an organoalkoxysilane, or a tetrasilane zirconium alkoxide, or a hybrid such as an alkali silicate alkali emulsion, an organoalkoxysilane melamine resin, or a terasilane zirconium alkoxide polyurethane resin. A system may be included. In addition, it is possible to improve the surface strength by adding a crosslinkable substance to the antibacterial layer to give a three-dimensional crosslinked structure.

The antibacterial metal plate of the present invention is obtained by laminating the above antibacterial layer on a metal plate. The metal plate used in the present invention is preferably made of aluminum, steel, or an alloy containing them as a main component.Specifically, mild steel, electroformed steel, stainless steel, tinplate, tin-free steel,
Pure aluminum, aluminum alloy, tin-plated steel, nickel-plated steel, chrome-plated steel, hot-dip galvanized steel,
Representative examples include electrolytic galvanized steel, hot-dip zinc-aluminum alloy-plated steel, and aluminum-plated steel sheet. These metal plates may be appropriately subjected to an organic or inorganic treatment, for example, a phosphoric acid treatment, a chromic acid treatment, a phosphoric acid chromate treatment, an alumite treatment, or the like, on the surface.

In addition, polyethylene, polypropylene, polyvinyl chloride, nylon, polyester, polycarbonate, polystyrene,
A resin layer of polyurethane, polyamide, polyimide, polyamideimide, or the like may be formed.

As a method of laminating the antimicrobial layer on a metal plate, a film obtained by extruding the composition into a sheet with a melt extruder and then uniaxially or biaxially stretching the film,
Or a method of directly laminating an unstretched film to a metal plate by heat fusion; a thermosetting resin of polyurethane, phenol, furan, urea, melamine, polyester, epoxy, or silicone based , Vinyl acetate, ethylene-vinyl acetate copolymer, and its partial hydrolyzate, ethylene-acrylic acid copolymer, acrylic resin, thermoplastic resin such as polyamide, butadiene-acrylonitrile rubber, neoprene, other rubber derivatives, In addition, a method of laminating on a metal plate via an adhesive layer made of an adhesive such as lacquer, glue, casein, natural resin, etc .; laminating the composition directly on a metal plate with a melt extruder or via the above adhesive layer A method of dissolving or dispersing the composition in a solvent, and directly applying and drying the composition on a metal plate; Polypropylene, polyvinyl chloride,
Nylon, polyester, polycarbonate, polystyrene, polyurethane, polyamide, polyimide, polyamide imide, etc., a film obtained by dissolving or dispersing the composition in a solvent is applied and dried, and the film is laminated on a metal plate with the non-coated surface as an adhesive surface. Method, etc.,
It is not limited to these. In addition, when extruding the composition into a sheet with a melt extruder, the composition may be co-extruded with another thermoplastic resin and then laminated on a metal plate.

It is also possible to provide a thin layer of a natural polymer such as gelatin or a linear or crosslinked synthetic polymer such as polyester or polyamide on the surface of the antibacterial layer.

The antibacterial metal plate thus obtained is
Depending on the application, processing such as bending, drawing, and ironing may be performed.

The antibacterial metal plate of the present invention can be used, for example, in kitchens,
Decorative panels used for walls, floors and ceilings such as toilets and bathrooms, inner and outer panels such as tables, cabinets, shelves, cooking appliances such as stoves, microwave ovens, rice cookers, refrigerators, washing machines, telephones, etc. It is suitable as a structure of home electric appliances, window frames, door knobs, handrails, etc. of building materials such as hospitals, medical facilities, public facilities, general houses, vehicles, etc., and also metal containers such as cans and beverage cans. Further, the antibacterial metal plate of the present invention is excellent in water resistance, hot water resistance, acid resistance, and alkali resistance, and thus can be suitably used particularly for applications around water.

[0070]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Hereinafter, methods for measuring the physical properties of the antibacterial metal plates obtained in Examples and Comparative Examples will be described.

1. Antibacterial S. diluted with 1/50 broth aureus (Staphylococcus aureus) 0.1 ml of bacterial solution (concentration: 10 ⁷ / ml)
Was dropped onto an antibacterial metal plate having a size of 5 cm × 5 cm which had been sterilized in advance, and a polyethylene film sterilized by high-pressure steam was adhered onto the plate. The test piece was transferred to a sterile petri dish and cultured at 37 ° C. for 24 hours. Thereafter, the bacteria on the antibacterial metal plate and the polyethylene film were washed with 10 ml of SCDLP medium, diluted 10-fold, and spread on a normal agar plate. After 24 hours, the number of bacteria was counted.

2. Durability Water resistance An antibacterial metal plate cut into a size of 10 cm × 5 cm was used as a test piece. Water was placed in a 1-liter beaker at a height of 8 cm, placed in a thermostat at 20 ° C., and the test piece was immersed in the beaker. After 24 hours, the test piece was taken out, dried at room temperature, and a part immersed in water was cut out and examined for antibacterial properties.

Hot water resistance An antibacterial metal plate cut into a size of 10 cm × 5 cm was used as a test piece. Water was placed at a height of 8 cm in a 1-liter beaker, placed in a thermostat at 80 ° C, and the test piece was immersed in the beaker. After 60 minutes, the test piece was taken out and dried at room temperature, and then the dipped part was cut out and examined for antibacterial properties.

An acid-resistant antibacterial metal plate cut into a size of 5 cm × 5 cm was used as a test piece. A 10% hydrochloric acid aqueous solution was applied on the antibacterial composition layer of the test piece, and after 60 minutes, the test piece was washed with water and dried, and then the antibacterial property was examined.

Alkali Resistance An antibacterial metal plate cut into a size of 5 cm × 5 cm was used as a test piece. A 10% aqueous sodium hydroxide solution was applied on the antimicrobial composition layer of the test piece, and after 60 minutes, the test piece was washed with water and dried, and then examined for antibacterial properties.

Example 1 9 mol of dimethyl terephthalate, 1 mol of tri-n-butyldodecylphosphonium salt of dimethyl 5-sulfoisophthalate, 22 mol of ethylene glycol,
With respect to all the acid components, zinc acetate is used as zinc (Zn) at 0.0
5 mol% was added, and the ester exchange reaction was carried out while evaporating methanol generated by heating from 140 ° C. to 220 ° C. outside the system. After completion of the transesterification reaction, at 250 ° C., 1.1 mol of polyethylene glycol having a molecular weight of 1,000 (Nacalai Co., Ltd.), 0.06 mol% of antimony oxide as antimony (Sb), and 0 as P content of trimethyl phosphate. .04 mol% and stirred for 15 minutes,
Subsequently, a polycondensation reaction is performed at 270 ° C. under vacuum for 90 minutes.
A copolymerized polyester resin having an intrinsic viscosity η = 0.70 was obtained.

The obtained polyester resin was melt-extruded at 260 ° C. by an extruder and cooled on a cooling roll at 30 ° C. to obtain an unstretched film having a thickness of 180 μm. Then, while being heated to 65 ° C., the film is stretched 3.5 times in the longitudinal direction by the speed between a pair of rolls having different peripheral speeds, and further stretched 3.5 times in the transverse direction in a tenter heated to 80 ° C. Then, it was heat-set at 180 to 200 ° C while being relaxed by 10% to obtain a biaxially stretched film.

After the obtained biaxially stretched film was temporarily bonded to a 0.2 mm thick aluminum plate preheated to 220 ° C. by pressing between two rolls, the polyester was melted in an oven at 260 ° C. Immediately after cooling and solidification, a polyester resin laminated aluminum plate was obtained.

Examples 2-3 A polyester resin laminated aluminum plate was obtained in the same manner as in Example 1, except that the kind and amount of the phosphonium salt were changed as shown in Table 1.

Examples 4 to 5 Polyester resin laminated aluminum plates were obtained in the same manner as in Example 1, except that the kind and amount of polyethylene glycol were changed as shown in Table 1.

Example 6 Terephthalic acid dimethyl ester 4.5 mol, isophthalic acid dimethyl ester 4.5 mol, 5-sulfoisophthalic acid dimethyl ester tri-n-butyldodecylphosphonium salt 1 mol, ethylene glycol 22 mol, total acid Zinc acetate was added to the components in an amount of 0.05 mol% as zinc (Zn), and a transesterification reaction was performed while elevating the temperature from 140 ° C. to 220 ° C. and distilling off methanol produced outside the system. After completion of the transesterification reaction, at 250 ° C., a molecular weight of 1
1.1 mol of polyethylene glycol (Nacalai Co., Ltd.) and antimony oxide (S
As b), 0.06 mol% and 0.04 mol% of trimethyl phosphate as P atoms were added, followed by stirring for 15 minutes, followed by a polycondensation reaction at 270 ° C. under vacuum for 90 minutes to obtain an intrinsic viscosity η = 0.40. A copolymerized polyester resin was obtained.

The obtained copolymerized polyester was dissolved in methyl ethyl ketone to obtain a resin solution having a solid content of 2%. After coating a solution of the polyester on one surface of a biaxially stretched polyester film (manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm, the solution was passed through a drying zone at 150 ° C. to dry and remove the solvent. The average coating amount of the resin coating layer on this film was 0.2 g / m ² .

The uncoated surface of the obtained coated film was bonded to one surface of an aluminum plate having a thickness of 0.2 mm with an adhesive (polyester adhesive, trade name: Byron 200, manufactured by Toyobo Co., Ltd.) on one side of the aluminum plate. Thus, a polyester resin laminated aluminum plate was obtained.

Examples 7 to 10 Polyester resin laminated aluminum plates were obtained in the same manner as in Example 6, except that the kind and amount of the phosphonium salt were changed as shown in Table 1.

Examples 11 to 12 Polyester resin laminated aluminum plates were obtained in the same manner as in Example 6, except that the kind and amount of polyethylene glycol were changed as shown in Table 1.

Comparative Examples 1 to 3 Comparative Examples 1 to 3 were completely different from Examples 1 to 3, respectively, except that the polyester having the composition shown in Table 1 was used and polyethylene glycol was not used as a polymerization component of the polyester. Similarly, a polyester resin laminated aluminum plate was obtained.

Comparative Examples 4 to 6 In Examples 6, 9 and 10, except that the polyester having the composition shown in Table 1 was used and polyethylene glycol was not used as a polymerization component of the polyester, respectively. A polyester resin laminated aluminum plate was obtained in exactly the same manner as in Example 1.

The antibacterial properties of the polyester resin laminated aluminum plates obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were evaluated. Table 1 shows the results.

[0089]

[Table 1]

Table 1 shows that the polyester resin laminated aluminum plates obtained in Examples 1 to 12 had good antibacterial properties even after 24 hours.

Example 13 Calcium carbonate fine particles having an average particle size of 0.5 μm
Terephthalic acid dispersed at a concentration of ppm // ethylene glycol / polyethylene glycol (molecular weight 1000)
= (100 // 99/1 molar ratio) Copolyester 9
To 9 parts by weight, 1 part by weight of a silver / zirconium phosphate antibacterial filler (trade name: Novalon, manufactured by Toagosei Co., Ltd.) was added and mixed, then extruded at 280 ° C., and cooled by a cooling roll at 30 ° C. An unstretched film having a thickness of 180 μm was obtained. The unstretched film is stretched 3.5 times in the longitudinal direction between a pair of rolls heated to 85 ° C. and having different peripheral speeds, and then stretched 3.5 times in the transverse direction at 130 ° C. by a tenter. It was heat-set at 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 14.5 μm.

The obtained biaxially stretched film was temporarily bonded to a 0.2 mm thick aluminum plate preheated to 220 ° C. by pressing between two rolls, and then the polyester film was heated in an oven at 260 ° C. Was melted and immediately cooled and solidified to obtain a polyester film laminated aluminum plate.

Examples 14 to 15 Polyester film laminated aluminum plates were obtained in the same manner as in Example 13 except that the type and amount of the inorganic antibacterial agent were changed as shown in Table 2.

Example 16 (A) Preparation of polyester having sulfonic acid groups and aqueous dispersion A polyester having sulfonic acid groups was prepared by the following method. Dimethyl terephthalate 47.5 mol% and dimethyl isophthalate 47.5 as dicarboxylic acid components
A transesterification reaction and a polycondensation were carried out by a conventional method using mol% and sodium 5-sulfoisophthalate 5 mol%, and ethylene glycol 50 mol% and neopentyl glycol 50 mol% as glycol components. The glass transition temperature of the obtained polyester is 65 ° C.
Met. Polyester 30 having this sulfonic acid group
0 parts and 150 parts of n-butyl cellosolve were heated and stirred to form a viscous solution, and 550 parts of water was gradually added with further stirring to obtain a uniform fresh water-colored aqueous dispersion having a solid content of 30%.

(B) Preparation of mixed coating solution 0.05 parts by weight of silver / zirconium phosphate antibacterial filler (trade name: Novalon, manufactured by Toagosei Co., Ltd.) 83.45 parts by weight of an equal mixture of water and isopropanol uniform dispersion is, the (a) sulfonic acid group-containing polyester aqueous dispersion 16.5 parts by weight of additives, having a solid part concentration of 5% antibacterial filler concentration (vs. solids) 1.0% coating on A cloth solution was used.

(C) Preparation of Film The obtained coating solution was coated on one surface of a biaxially stretched polyester film having a thickness of 25 μm (manufactured by Toyobo Co., Ltd.), and then passed through a drying zone at 150 ° C. to dry the solvent. Removed. The average coating amount on the resin coating layer on this film is 0.
It was 5 g / m ² .

(D) Preparation of laminated aluminum plate An adhesive (polyester-based adhesive, trade name: Byron 200, Toyo Co., Ltd.) was attached to one side of an aluminum plate having a thickness of 0.2 mm with the uncoated surface of the obtained coated film as an adhesive surface. (Made by spinning) to obtain a polyester film laminated aluminum plate.

Examples 17 to 18 Polyester film laminated aluminum plates were obtained in the same manner as in Example 16, except that the type and amount of the inorganic antibacterial agent were changed as shown in Table 2.

Comparative Examples 7 to 9 Polyester films were produced in exactly the same manner as in Examples 13, 14, and 15, except that polyethylene terephthalate (PET) was used in place of the copolymerized polyester. A laminated aluminum plate was obtained.

Comparative Examples 10 to 12 In Examples 16, 17 and 18, polyesters were used in which 50 mol% of terephthalic acid and 50 mol% of isophthalic acid were used without using sodium 5-sulfoisophthalate as a dicarboxylic acid component of the polyester. Other than using
A polyester film laminated aluminum plate was obtained in exactly the same manner as in Examples 16, 17, and 18, respectively.

With respect to the polyester film laminated aluminum plates obtained in Examples 13 to 18 and Comparative Examples 7 to 12,
The antibacterial properties were evaluated. Table 2 shows the results. In addition,
For Examples 15 and 18 and Comparative Examples 9 and 12, 2
It was performed while illuminating a 0 watt black light at a distance of 30 cm (0.3 mW / cm ² ).

[0102]

[Table 2]

Table 2 shows that the polyester resin laminated aluminum plates obtained in Examples 13 to 18 had good antibacterial properties even after 24 hours.

Example 19 A non-coated surface of a copolymerized polyester coated film obtained in the same manner as in Example 6 was used as an adhesive surface, and a polyvinyl chloride resin-coated 0.5 mm-thick steel sheet was polychlorinated. Laminated on the vinyl surface via an adhesive (polyester adhesive, trade name: Byron 200, manufactured by Toyobo Co., Ltd.) to obtain a polyester laminated steel sheet.

Example 20 A polyester film coated with a coating liquid containing an inorganic antibacterial agent obtained in the same manner as in Example 16 was coated with a polyvinyl chloride resin at a thickness of 0% with the uncoated surface as an adhesive surface. A polyester laminated steel sheet was obtained by laminating on a polyvinyl chloride surface of a 0.5 mm steel sheet via an adhesive (polyester adhesive, trade name: Byron 200, manufactured by Toyobo Co., Ltd.).

The antibacterial properties of the polyester laminated steel sheets obtained in Examples 19 and 20 were evaluated. Table 3 shows the results. The durability of these polyester laminated steel sheets was evaluated. Table 4 shows the results.

[0107]

[Table 3]

[0108]

[Table 4]

From Table 3, it can be seen that the polyester laminated steel sheets obtained in Examples 19 and 20 have good antibacterial properties and good durability even after 24 hours.

[0110]

As is apparent from the above description, the antibacterial composition of the present invention has good antibacterial properties and excellent durability. The board is used in applications where antimicrobial properties are desired, for example, kitchens,
Decorative panels used for walls, floors and ceilings such as toilets and bathrooms, inner and outer panels such as tables, cabinets, shelves, cooking equipment such as stoves, microwave ovens, rice cookers, refrigerators, washing machines, and dryers , Structures of home appliances such as telephones, windows and doorknobs of building materials such as hospitals and medical facilities, public facilities, general houses, vehicles, handrails, etc., as well as any molded products such as metal containers such as cans and beverage cans Can be suitably used.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI B32B 15/08 B32B 15/08 E 27/18 27/18 F

Claims (9)

[Claims] 1. An antimicrobial comprising an antimicrobial layer containing at least one antimicrobial agent selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent and a hydrophilic substance laminated on a metal plate. Metal plate. 2. The organic antibacterial agent is a polymer antibacterial agent,
The antibacterial metal plate according to claim 1, wherein a hydrophilic substance is contained as one of the polymerization components of the high-molecular antibacterial agent. 3. The organic antibacterial agent having at least one group selected from the group consisting of ammonium base, phosphonium base and sulfonium base in the main chain or side chain thereof. 1 or 2
3. The antibacterial metal plate according to 1. 4. The method according to claim 1, wherein the inorganic antibacterial agent is at least one kind of metal fine particles selected from the group consisting of silver, zinc and copper and / or inorganic fine particles carrying the metal ions. 2. The antibacterial metal plate according to 1. 5. The antibacterial metal plate according to claim 1, wherein the inorganic antibacterial agent contains titanium oxide and / or zinc oxide. 6. The hydrophilic substance is a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, an amine base, a polyether chain and a polyamine chain. The antibacterial metal plate according to any one of claims 1 to 5, which is a compound having at least one selected from the group consisting of: 7. The antibacterial metal plate according to claim 1, wherein the metal plate is made of a material selected from the group consisting of aluminum, steel, and an alloy containing them as a main component. . 8. The antibacterial composition according to claim 1, wherein a layer made of a thermoplastic resin is provided between the metal plate and the layer made of the antibacterial agent or the antibacterial composition. Metal plate. 9. The antibacterial property according to claim 8, wherein the thermoplastic resin is at least one resin selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, nylon and polyester. Metal plate.