JP2000109983A - Antibacterial metallic sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the metallic sheet having practically sufficiently high antibacterial properties and antifungal properties by laminating a layer composed of a compsn. contg. a high polymer material in which organic antibacterial agent components are bonded to the main chain or side chain, a hydrophilic material mixed or bonded to the high polymer material and a hardner, then hardening them. SOLUTION: Preferably, a hardener is composed of a photopolymerizing hardening type resin of a photopolymerization starting agent, a photopolymerizing prepolymer and/or photopolymerizing monomer, and a high polymer material in which organic antibacterial agent components are bonded to the main chain or side chain is suitably composed of a polymer in which an ammonium base, a phosphonium base or a sulfonium base is bonded to the main chain and/or side chain. A hydrophilic material is preferably composed of a polymer having a hydroxyl group, an amino group, a carboxyl group or the alkali metal salt thereof, a sulfonic group or the alkali metal salt thereof, a quaternary ammonium base, an amine base, a polyether chain or a polyamine chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal plate on which a layer comprising a composition comprising a polymer substance having an organic antimicrobial agent bonded thereto and a hydrophilic substance and a photopolymerizable curing agent is laminated.
It has excellent antibacterial and antifungal properties and practical durability, especially for kitchen appliances, home appliances, metal containers, air conditioners, air conditioners, etc., such as walls, ceilings, floors, window frames and door knobs of construction materials, handrails, etc. Construction of decorative boards, interior / exterior boards, structures, accessories, parts, etc. for water supplies such as sinks, desks, shelves, furniture, medical equipment, stationery, trains, automobiles, ships, aircrafts, etc. The present invention relates to a metal plate which is suitably used as a material and has excellent antibacterial and antifungal properties.

[0002]

2. Description of the Related Art Thermoplastic resins, especially polyethylene, polypropylene, polyvinylidene chloride, nylon, and polyethylene terephthalate, have excellent physical and chemical properties and are used for fibers, plastics, films, sheets, adhesives and the like. ing. Recently, antibacterial products having an inorganic or organic antibacterial agent filled or applied thereto have been devised.

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 as photooxidation catalyst, Ultrafine zinc oxide particles,
Examples include inorganic compounds such as silver-containing zeolite and silver-containing zirconium phosphate, and organic synthetic products such as organic ammonium salt-based and organic phosphonium salt-based compounds.

[0004] Natural antibacterial agents and inorganic antibacterial agents represented by silver have recently received attention because they are safe in terms of toxicity, and the following antibacterial agents have already been reported. That is, JP-A-3-83905 discloses a silver ion-containing phosphate-based antibacterial agent, and JP-A-3-161409 discloses a method in which a fixed volume of zeolite having a specific ion exchange capacity is replaced with silver ions. Antimicrobial agents are each described.

The present inventors prepared films, sheets, fibers, and plastics to which the respective antibacterial agents were applied according to the descriptions in these publications, and evaluated their antibacterial properties against Staphylococcus aureus, Escherichia coli, and the like. In films, sheets, etc., the antibacterial activity is insufficient if the amount added is relatively low to maintain transparency, but if the antibacterial activity is to be improved, transparency must be sacrificed. Had room for improvement. On the other hand, antibacterial agents of organic synthetic products generally have better antibacterial activity against fungi and the like than natural products and inorganic products.However, due to their low molecular weight, these antibacterial agents are applied to the surface of substrates such as films. Or, when filled, it is easy to volatilize, desorb and separate from the substrate, which is not preferable from the viewpoint of long-term stability of antibacterial property and safety from the human body. When an antibacterial agent is used in films, etc., the antibacterial agent does not dissolve in water or organic solvents, and is unlikely to be released, detached, peeled off, or dropped off from the film surface. It is preferable from all aspects of safety.

Under these circumstances, recently, an immobilized antibacterial agent has been disclosed in which an organic antibacterial agent is bonded to a polymer material as a raw material of a film, a fiber or the like by ionic or covalent bonding. That is, JP-A-54-86584.
Japanese Patent Application Laid-Open Publication No. H11-157, discloses an antibacterial material mainly composed of a polymer substance which contains an antibacterial agent component having a quaternary ammonium base in an acidic group such as a carboxyl group or a sulfonic acid by ionic bonding. JP-A-61-245378 describes a fiber comprising a polyester copolymer containing an antibacterial agent component having a polar group such as an amidine group or a quaternary ammonium base. Further, Japanese Patent Application Laid-Open No. 57-204
No. 286, JP-A-63-60903, JP-A-62-1
14903, JP-A-1-93596, JP-A-2-2-2
From publications such as 40090, phosphonium salt compounds, as well as various nitrogen-containing compounds, are known to be biologically active chemicals having a broad spectrum of activity against bacteria.

[0007] There is also disclosed an invention in which the above phosphonium salt is immobilized on a polymer substance to attempt to expand its use. That is: JP-A-4-266912 discloses an antibacterial agent comprising a phosphonium salt-based vinyl polymer, and JP-A-4-81436.
No. 5 discloses an antibacterial agent comprising a vinylbenzylphosphonium salt-based vinyl polymer. Furthermore,
JP-A-5-310820 describes an antibacterial material mainly composed of a polymer substance containing an acid group and an antibacterial component having a phosphonium base bound to the acid group by ionic bonding. In the examples, polyesters using a phosphonium salt of sulfoisophthalic acid are disclosed. Although JP-A-6-41408 does not mention any antibacterial action, it is useful for photographic supports, packaging, general industrial uses, magnetic tapes, and the like, with copolymerized polyesters of phosphonium phosphonium salts. Modified polyesters and polyester films comprising polyalkylene glycols are disclosed. The alkyl group bonded to the phosphonium salt described in JP-A-6-41408 is a type having a relatively short carbon number, such as a butyl group, a phenyl group, or a pendyl group, unlike the above-mentioned JP-A-5-310820.

The above-mentioned JP-A-4-266912 and JP-A-Hei-4
According to the techniques described in JP-A-814365 and JP-A-5-310820, phosphonium base-containing vinyl copolymers and copolymerized polyesters are synthesized according to the examples to form fibers, films, sheets, and the like. An antimicrobial polymer was coated on the surface of the fiber or film sheet to form a laminate, and their antimicrobial properties were evaluated. However, the antimicrobial activity was insufficient. Further, for the purpose of improving antibacterial properties, a polyester having at least 50 mol% of trinormal butyldodecylphosphonium base bonded thereto was synthesized, and films and sheets were prepared from the polyester. In addition to the decrease in mechanical properties due to the decrease in antibacterial properties, the antibacterial properties were insufficient.

Further, the above-mentioned organic antibacterial agents are used alone or in combination to form fibers, fabrics, films, sheets and the like.
The antibacterial activity against Staphylococcus aureus, Escherichia coli, Aspergillus niger, Aspergillus niger, etc. was evaluated, but the antibacterial activity was insufficient and lacked in practicality.

[0010]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems and provides a metal plate having an antibacterial layer on its surface, which has both a sufficiently high antibacterial property and fungicidal property satisfying practicality. It is another object of the present invention to provide the antibacterial surface layer with sufficient durability for practical use.

[0011]

Means for Solving the Problems The present inventors impart hydrophilicity to a polymer substance in which an organic antibacterial agent component in an antibacterial layer is bonded to a main chain or a side chain, whereby the antibacterial activity is remarkably increased. The present inventors have found that they can be enhanced and also have high durability that can withstand practical use, and based on this finding, have further studied and completed the present invention.

That is, the present invention provides a composition comprising a polymer substance having an organic antibacterial component bound to a main chain or a side chain, a hydrophilic substance mixed or bound to the polymer substance, and a curing agent. Provided is an antibacterial metal plate obtained by laminating a layer made of an object on the surface of a metal plate and curing the layer. The lamination of the layer on the surface of the metal plate may be performed on a desired portion such as one surface, both surfaces, or a part of the surface.

Various organic antibacterial agents may be used. Particularly preferred examples are ammonium bases, phosphonium bases or sulfonium bases, at least one of which is bonded to the main chain or side chain. High molecular substances are particularly preferably used.

Although various curing agents may be used, a particularly preferred example is a photopolymerizable curable resin.

As the hydrophilic substance, various substances may be used. Particularly preferred examples are a hydroxyl group, an amino group, an amide group, a carboxyl group, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, Amine base,
It is a polymer having at least one kind of polyether chain or polyamine chain.

More preferably, a hydrophilic substance is bonded via a covalent bond to a polymer substance in which an ammonium base, a phosphonium base, or a sulfonium base as an organic antibacterial component is bonded to a main chain or a side chain. It is a thing. By doing so, the hydrophilicity of the cured layer is further greatly improved.

A particularly preferred example is that the hydrophilic substance comprises a vinyl polymer having a hydrophilic group in the side chain, and this is graft-polymerized to a polymer substance having an organic antibacterial component bound to the main chain or the side chain. It was made.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the antibacterial metal plate of the present invention will be described more specifically. The organic antibacterial agent used in the present invention is a general term for natural extracts, low molecular weight organic compounds, and polymers having antibacterial performance, and generally contains an element such as nitrogen, sulfur, and phosphorus. For example, natural antibacterial agents include chitin, chitosan, wasabi extract, mustard extract, hinokitiol, tea extract, and the like, and low-molecular-weight organic compounds include allyl isothiocyanate, polyoxyalkylene trialkyl ammonium, and benzal chloride. Quaternary ammonium salts such as ruconium and hexamethylene biguanide hydrochloride, organic silicon quaternary ammonium salts, tri-
n-butylhexadecylphosphonium chloride, tri-
quaternary such as n-butyltetradecylphosphonium chloride
Grade phosphonium salts, phenylamides, biguanides,
Tetraalkylphosphonium sulfoisophthalate or a diester thereof, an imidazole / thiazole compound,
Examples include thiocarbite compounds, pyridine / quinoline compounds, and the like, but are not limited thereto.

Among these organic antibacterial agents, onium salts such as ammonium bases, phosphonium bases and sulfonium bases, and antibacterial active groups such as phenylamide group and biguanide group are selected from the viewpoint of easy binding to a polymer substance. Is preferred, and a phosphonium salt compound having high antibacterial activity and a broad antibacterial spectrum is most preferable.

The polymer substance of the present invention may be any polymer compound as long as an organic antibacterial agent component is bonded to the main chain or side chain. Specific examples are shown below, but the present invention is not limited thereto. A preferred example is a polymer substance containing an acidic group and a phosphonium base ionically bonded to the acidic group, and a more preferred example is a sulfonic acid represented by the following general formula, containing a dicarboxylic acid component and a glycol component as main components. It is a polyester resin in which a phosphonium base of a group-containing aromatic dicarboxylic acid is copolymerized in an amount of 1 to 50 mol% based on all acid components.

[0021]

Embedded image

Wherein A is an aromatic group, X1 and X2 are ester-forming functional groups, R1, R2, R3 and R4 are alkyl groups, at least one of which is an alkyl group having 10 to 20 carbon atoms. Group.)

In addition, one of the high-molecular substances is a phosphonium-based vinyl polymer having a structure represented by the following formula.

[0024]

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(R5, R6, R7 are a hydrogen atom, an alkyl group substituted with a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, a hydroxyl group or an alkoxy group, an aryl group Or an aralkyl group;
^- is an anion, n represents an integer of 2 or more. )

Specific examples of the above R5, R6 and R7 include:
Substituted with an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, an aryl group such as phenyl, tolyl, xylyl, an aralkyl group such as benzyl, phenethyl, a hydroxyl group, an alkoxy group, etc. , An alkyl group and an aryl group are particularly preferred. R5, R6 and R7 may be the same or different groups. X ^- is an anion, for example, fluorine,
Examples thereof include halogen ions such as chlorine, bromine and iodine, sulfate ions, phosphate ions, perchlorate ions, and the like, with halogen ions being preferred. n is not particularly limited, but 2 to 5
00, preferably 10-300.

The dicarboxylic acid component used in the polyester resin includes terephthalic acid, isophthalic acid, 2,6
-Naphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Further, an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, a heterocyclic dicarboxylic acid, or the like may be used in combination within a range not to impair the content of the invention. Examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, sebacic acid,
Dodecanedicarboxylic acid, azelaic acid, eicoic acid, dimer acid and derivatives thereof. Heterocyclic dicarboxylic acids include pyridine dicarboxylic acid and derivatives thereof. An oxycarboxylic acid such as p-oxybenzoic acid or a polyvalent carboxylic acid such as trimellitic anhydride or pyromellitic anhydride may be used in combination as long as the content of the present invention is not impaired.

Among these, from the viewpoint of practical durability when formed into a coating film, it is preferable that the film contains at least 70 mol% of an aromatic dicarboxylic acid. As other dicarboxylic acids, 1,4-dicarboxylic acid, adipic acid and sebacic acid are particularly preferred.

The glycol component includes ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-propanediol.
Butanediol, 1,5-pentaneddiol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1 Alkylene glycols such as 1,3-propanediol, 1,9-nonanediol and 1,10-decanediol, alicyclic glycols such as 1,2-cyclohexanedimethanol, alkylene oxide adducts of bisphenol A or F, diethylene glycol, Neopentyl glycol ester of polyethylene glycol and hydroxypivalic acid (HP
N), polypropylene glycol, polytetramethylene glycol and the like.

In addition, a small amount of a compound containing an amide bond, a urethane bond, an ether bond or a carbonate bond may be contained.

Of these, from the viewpoint of practical durability when formed into a coating film, ethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol,
1,6-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-
Cyclohexanedimethanol is particularly preferred.

Further, a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like may be used in combination as long as the content of the invention is not impaired.

The phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid includes tri-n-sulfoisophthalic acid.
Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexyl sulfoisophthalate Decylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate, n-butyldodecylphosphonium sulfoisophthalate, tri-n-butyldecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate, 4- Sulfonaphthalene-2,
7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexadecylphosphonium salt, 4-
And tris-n-butyltetradecylphosphonium salt of sulfonaphthalene-2,7-dicarboxylic acid, tri-n-butyldodecylphosphonium salt of 4-sulfonaphthalene-2,7-dicarboxylic acid, and the like. Tri-n-butylhexadecylphosphonium isophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, and tri-n-butyldodecylphosphonium sulfoisophthalate are particularly preferred.

[0034] The above phosphonium salt of an aromatic dicarboxylic acid can be obtained by adding tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide to sulfoaromatic dicarboxylic acid or its sodium salt, potassium salt, ammonium salt and the like. Tri-n-
It is obtained by reacting a phosphonium salt such as butyldodecylphosphonium bromide. The reaction solvent at this time is not particularly limited, but water is most preferable.

For the purpose of improving the heat resistance such as the degree of coloring and the degree of gelation, the copolymerized polyester may contain, in addition to a polymerization catalyst such as antimony oxide, germanium oxide, or a titanium compound, an Mg salt such as magnesium acetate or magnesium chloride; Ca salts such as calcium acetate and calcium chloride, manganese acetate,
Mn salts such as manganese chloride, Zn such as zinc chloride and zinc acetate
A salt, a Co salt such as cobalt chloride, cobalt acetate, etc., is added as a metal ion in an amount of 300 ppm or less, respectively, and a phosphoric acid or a phosphoric acid ester derivative such as a phosphoric acid trimethyl ester or a phosphoric acid triethyl ester is added in an amount of 200 ppm or less in terms of phosphorus (P). It is also possible.

When the total amount of metal ions other than the polymerization catalyst is 3
When the amount of P exceeds 00 ppm and the amount of P exceeds 200 ppm, not only the coloring of the polymer becomes conspicuous, but also the heat resistance and hydrolysis resistance of the polymer are significantly reduced.

At this time, in terms of heat resistance, hydrolysis resistance, etc., the molar ratio between the total P amount and the total metal ion amount is 0.4 to 0.4.
It is preferably 1.0. The molar ratio (molar atomic ratio) of these additives is represented by the following formula.

[0038]

(Equation 1)

The above molar atomic ratio is less than 0.4 or 1.0
When the ratio exceeds the above range, coloring of the composition of the present invention and generation of coarse particles become remarkable, which is not preferable.

The method for producing the polyester is not particularly limited, but a dicarboxylic acid and a glycol are directly reacted,
The so-called direct polymerization method in which the obtained oligomer is polycondensed, the so-called transesterification method in which the dimethyl ester of dicarboxylic acid and glycol are subjected to a transesterification reaction and then the polycondensation, and the like, may be used. can do.

The timing of adding the metal ions and phosphoric acid and derivatives thereof 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. Is preferably added before the polycondensation reaction.

The antimicrobial resin composition of the present invention is characterized in that a hydrophilic substance is mixed with a polyester resin containing a phosphonium base or chemically bonded via a covalent bond. The presence of a hydrophilic substance significantly improves antibacterial properties.

The hydrophilic substance in the present invention is a substance having an excellent affinity for water, and can be dissolved, dispersed or retained in water.
It is a moisturizing and swellable substance. Generally, a hydrophilic group such as 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, or a hydrophilic derivative thereof, or two or more ether bonds are contained in one molecule. Organic compounds or high molecular compounds, specific examples include polyvinyl alcohol,
Starch, polyacrylic acid homopolymer or copolymer,
Polymethacrylic acid homopolymer or copolymer, maleic anhydride homopolymer or copolymer (for example, maleic anhydride-styrene copolymer), polyvinyl sulfonic acid or its copolymer or an alkali metal salt thereof, polystyrene Ethylene glycol (also known as polyethylene oxide) Polyalkylene glycol such as polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, polyol such as glycerin, polyglycerin or a polymer thereof, glycerin, polyglycerin, and hydroxyethyl cellulose as water-soluble modified cellulose , Methylcellulose, methylhydroxypropylcellulose, sodium carboxycellulose, cellulose nitrate carboxyl methyl ether and the like. These are mixed and used in the polyester resin containing the phosphonium base.

The molecular weight of the hydrophilic substance is not particularly limited. In the case of polyethylene glycol, the number average molecular weight is preferably from 200 to 30,000, and more preferably from 1,000 to 2,000.
More preferably, it is 5000 or less.

The amount of the hydrophilic substance to be mixed (in the case of a copolymer, the amount of the hydrophilic monomer occupied in the copolymer) is from 0.1 to 20% by weight, based on the polyester resin, preferably. Is 0.5 to 10% by weight, more preferably 1 to 5% by weight. If the amount is less than 0.1% by weight, the effect of increasing the antibacterial activity is insufficient, and if it exceeds 20% by weight, the mechanical properties and the heat resistance and weather resistance of the antibacterial composition are undesirably reduced. The method of mixing with the hydrophilic substance is not particularly limited, and any method can be adopted depending on the method of producing the polyester resin, its chemical properties, and its physical properties. For example, a method in which both are heated and melt-mixed using an extruder, or a method in which a polymer substance and a hydrophilic substance are mixed in an appropriate solvent, for example, water, a water / alcohol mixed solvent, or an organic solvent such as acetone, methyl ethyl ketone, or cyclohexanone. After mixing and dissolving or dispersing, there is a method of drying the solvent to dryness.

Another method for introducing a hydrophilic substance is as follows.
Instead of mixing with the polyester resin as described above, amino groups, amide groups, carboxyl groups or alkali metal salts thereof, hydrophilic groups such as sulfonic acid groups or alkali metal salts thereof or hydrophilic derivatives thereof, including a phosphonium base It can also be copolymerized with the main chain or side chain of the polyester resin. By copolymerization, compatibility is improved, and physical properties such as appearance and storage stability when formed into a coating film are also improved.

Methods for copolymerizing these hydrophilic groups include 5-sulfoisophthalic acid, 4-sulfonaphthalene-
2,7-dicarboxylic acid, 5- (4-sulfophenoxy)
Metal salts such as isophthalic acid or 2-sulfo-1,4-butanediol, 2,5-dimethyl-3-sulfo-2,5
A method of copolymerizing a dicarboxylic acid or glycol containing a sulfonic acid metal base such as a metal salt such as hexanediol with a polyester resin, and copolymerizing an alkylene glycol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol with the polyester resin. And a method of graft-polymerizing a vinyl-based monomer containing a hydrophilic group onto a polyester resin.

The vinyl monomer having a hydrophilic group which can be grafted on the polyester resin in the present invention includes a carboxyl group, a hydroxyl group, a sulfonic acid group,
Examples include groups containing an amide group and the like, and examples of groups that can be converted into a hydrophilic group include groups containing an acid anhydride group, a glycidyl group, a chloro group, and the like. Among them, those having a carboxyl group are most preferred. For example, monomers containing a carboxyl group or a salt thereof such as acrylic acid, methacrylic acid and salts thereof, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Alkyl acrylates such as t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, alkyl methacrylates such as t-butyl methacrylate, hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, N- Methyl acrylamide, N-methyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N
Amide group-containing monomers such as -methoxymethylacrylamide, N-methoxymethylmethacrylamide, N, N-dimethylolacrylamide and N-phenylacrylamide; and epoxy-containing monomers such as glycidyl acrylate and glycidyl methacrylate.

Other monomers having a hydrophilic group include, for example, monomers containing an epoxy group such as allyl glycidyl ether, monomers containing a sulfonic acid group or a salt thereof such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof, Examples include monomers containing a carboxyl group or a salt thereof, such as crotonic acid, itaconic acid, maleic acid, fumaric acid, and salts thereof, and monomers containing an acid anhydride, such as maleic anhydride and itaconic anhydride. These can be used in combination with other monomers. Other monomers include, for example, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl chloride, and the like. Copolymerization can be performed using the type.

The molar ratio of the monomer having a hydrophilic group to the other monomer is preferably in the range of 30/70 to 100/0. If the ratio of the monomer having a hydrophilic group is less than 30 mol%, the effect of enhancing the antibacterial property is not sufficiently exhibited.

As a method for grafting a monomer having a hydrophilic group to the polyester, a known graft polymerization method can be used. The following method is mentioned as a typical example.

For example, a radical polymerization method in which radicals are generated in a main chain polymer substance by light, heat, radiation or the like and then graft-polymerized with a monomer, or AICl ₃ ,
There are a cation polymerization method in which cations are generated using a catalyst such as TiCl _4, and an anion polymerization method in which anions are generated using metal Na, metal Li, or the like.

Further, there is a method in which a polymerizable unsaturated double bond is previously introduced into a main chain polymer substance, and a vinyl monomer is reacted with the polymerizable unsaturated double bond. As the monomer having a polymerizable unsaturated double bond used therein, fumaric acid, maleic acid, maleic anhydride, tetrahydromaleic anhydride,
2,5-norbornene dicarboxylic acid and the like can be mentioned. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid.

Further, there is also a method in which a main chain high molecular substance having a functional group introduced into a side chain is reacted with a branch polymer having a group which reacts with the functional group at the terminal. For example, -OH groups in the side chain, -SH group, -NH ₂ group, -COOH group, -C
A polymer having a hydrogen donating group such as an ONH ₂ group, and one end having —N ＝ C ＝ O group, —C−C ＝ O group,

[0055]

Embedded image

A method of reacting with a vinyl copolymer which is a hydrogen accepting group, and a method of reacting in a reverse combination thereof.

The preferred weight ratio of the polyester as the main chain of the present invention to the grafted vinyl monomer is 95.
/ 5 to 40/60, more preferably 93
/ 7-55 / 45, most preferably 90 / 10-60 /
It is in the range of 40. 40% by weight of main chain polymer
If it is less than 30, the graft-polymerizable vinyl monomer remains without completely reacting, and the properties of the conventional polymer such as heat resistance, processability, and water resistance are impaired. When the weight ratio of the main chain polymer substance exceeds 95%, the effect of improving the antibacterial property, which is the object of the present invention, is not sufficiently exhibited.

There is no substantial difference in the antibacterial properties between the case where the hydrophilic substance is mixed with the polymer substance and the case where the hydrophilic substance is copolymerized, and good antibacterial properties are obtained in both cases.

The present invention is characterized in that a curing agent is blended in addition to the above-mentioned polyester and hydrophilic substance.

The curing agent is roughly classified into a thermosetting resin and an ionizing radiation-curable resin.
Photopolymerizable curable resins are preferred. The reason is that the ionizing radiation-curable resin is superior from the viewpoints of flexibility in resin design, rapid curability, and work environment. Good film properties can be obtained by blending a curable resin.
The ionizing radiation-curable resin is formed from a composition containing at least a resin that is cured by irradiation with an electron beam or ultraviolet rays. Specifically, it contains a photopolymerization initiator, a photopolymerizable prepolymer, and further, if necessary, a photopolymerizable monomer,
It contains additives such as a photosensitizer and a leveling agent, a solvent, and the like.

The photopolymerizable prepolymer undergoes radical polymerization or ionic polymerization when the reactive group inserted into the molecular skeleton is irradiated with ionizing radiation. A typical example of the radical polymerizable prepolymer is an acrylic prepolymer having an acryloyl group, and a typical example of the ionic polymerizable prepolymer is an epoxy prepolymer having an epoxy group. The acrylic prepolymer has two or more acryloyl groups in one molecule, and urethane acrylate, epoxy acrylate, polyester acrylate, and the like can be used. The higher the number of functional groups, the faster the curability and the higher the hardness. As the epoxy-based prepolymer, epoxy oligomers such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, phenol novolak type and alicyclic type can be used. Epoxy-based prepolymers have an epoxy group that undergoes cationic ring-opening polymerization, so that thermal factors affect the curing reaction.
By heating to about 60 ° C., the curing reactivity can be further increased. The preferred amount of the photopolymerizable prepolymer is 5 to 60 based on the total amount of the polyester and the hydrophilic substance.
%, More preferably 15 to 50% by weight.

In the radical polymerizable prepolymer, the photopolymerization initiator is added to start the reaction of the acryloyl group in a short time and promote the reaction, and acts as a catalyst. Photoinitiators include those that undergo radical polymerization by self-cleavage and those that undergo radical polymerization by extracting hydrogen. For the former, benzoin ethers, dialkoxyacetophenones, hydroxyacetophenones, morpholinoacetophenones, etc. are used, and for the latter, benzophenones, cyclic benzophenones, benzyl, etc. are used, and one or more of these are used. it can. In the ionic polymerizable prepolymer, the photopolymerization initiator is a compound that releases a catalyst component that initiates cationic polymerization by absorbing ionizing radiation energy, and includes an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, A metallocene compound or the like is used. The photopolymerization initiator is preferably used in a mixture of 1 to 10% by weight, more preferably 2 to 5% by weight, based on the solid content of the resin.

In the photopolymerizable curable resin, a photopolymerizable monomer is added, if necessary, in addition to the above-mentioned photopolymerizable prepolymer and photopolymerization initiator. Particularly, in the case of a radical polymerizable prepolymer, it is effective for diluting a high-viscosity photopolymerizable prepolymer to improve the workability by lowering the viscosity and for imparting a coating film strength as a crosslinking agent. Examples of the photopolymerizable monomer for radical polymerization include monofunctional acrylic monomers such as 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, and bifunctional monomers such as ethylene glycol diacrylate, neopentyl glycol diacrylate, and 1,6-hexanediol diacrylate. One or more polyfunctional acrylic monomers such as a hydrophilic acrylic monomer and trimethylolpropane triacrylate are used.

The antibacterial composition of the present invention is preliminarily added to calcium carbonate (C) in the antibacterial composition for the purpose of improving physical properties such as slipping property, abrasion resistance, blocking resistance and concealing property.
AC0 _3), calcium phosphate, apatite, barium sulfate (BaS0 _4), calcium fluoride (CaF _2), talc, kaolin, silicon oxide (Si0 _2), alumina (A
1 ₂ 0 _3), titanium dioxide, zirconium oxide (Zr
O ₂ ), iron oxide (Fe ₂ O ₃ ), inorganic particles such as alumina / silica composite oxide, polystyrene, polymethacrylate, polyacrylate, and copolymers thereof.
Alternatively, it is also possible to add organic particles or the like such as a crosslinked product thereof.

When the antimicrobial resin composition of the present invention is irradiated with ionizing radiation such as an electron beam or an ultraviolet ray, the photocurable resin reacts and cures, and good coating film properties can be obtained.
In the case of irradiating an electron beam, a scanning or curtain type electron beam accelerator is used, and has an acceleration turret pressure of 1000 keV or less, preferably 100 to 300 keV, and energy of 10 to 300 keV.
Irradiation with an electron beam in a wavelength region of 0 nm or less can be performed. When irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc, a metal halide lamp, or the like is used, and 100 to 400 nm, preferably 200 to 400 nm.
20 to 1500 mJ / cm ^{2 in} the wavelength region of 400 nm
UV light of the integrated light amount is irradiated.

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, chrome-plated steel, nickel-plated steel, hot-dip galvanized steel,
Electrogalvanized steel, hot-dip zinc-aluminum alloy-plated steel, and aluminum-plated steel can be given as typical examples. These metal plates may be appropriately subjected to an organic treatment or an inorganic treatment, for example, a phosphoric acid treatment, a chromium treatment, a phosphoric acid chromate treatment, an alumite treatment, or the like, on the surface.

As a method of laminating an antimicrobial layer on a metal plate, a solution obtained by dissolving or dispersing the antimicrobial resin composition of the present invention in a solvent is subjected to bar coating, blade coating, gravure coating, spin coating, spray coating, dip coating. A method of coating and drying directly on a metal plate or on a primer coating layer provided by a usual coating method such as coating; polyethylene,
The above-mentioned coating method comprising dissolving or dispersing the antibacterial resin composition of the present invention in a solvent on a film or sheet of polypropylene, polyvinyl chloride, nylon, polyester, polycarbonate, polystyrene, polyurethane, polyamide, polyimide, polyamideimide, etc. And drying the film / sheet on a metal plate with the non-coated surface side as an adhesive surface, but is not limited thereto.

After the antimicrobial layer is laminated on the metal plate by the above method or the like, it is cured by irradiating it with an electron beam or an ultraviolet ray to obtain a metal plate having a curable resin layer having excellent antibacterial properties and durability.

The antibacterial metal plate of the present invention can be used, for example, for walls, floors and ceilings of kitchens, toilets, bathrooms, etc., window frames, door knobs, handrails, etc. of building materials such as hospitals, medical facilities, public facilities, and general houses.
Cooking equipment such as microwave ovens and rice cookers, refrigerators, washing machines,
Home appliances such as telephones and vacuum cleaners, metal containers such as cans, beverage cans, pail cans and drums, water supplies such as system kitchens and sinks, air conditioners such as air conditioners and air purifiers, desks, shelves and tables Furniture, medical equipment in general, stationery,
It is suitable as a constituent material for decorative panels, interior / exterior panels, structures, accessories, parts, and the like in applications such as trains, automobiles, ships, and aircraft.

[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 test E. coli diluted with 1/50 broth 0.1 mL of a bacterial solution of E. coli (Escherichia coli) (concentration: 10 ⁵ cells / mL) was dropped on a sample film of 5 cm × 5 cm in size previously sterilized by high pressure steam, and Saran Wrap (registered trademark) was sterilized by high pressure steam on the film. The film was brought into close contact. The test piece was transferred to a sterile dish and cultured at 37 ° C. for 24 hours. Next, the bacteria on the film were washed out with 10 mL of SCDLP medium,
It was diluted 10-fold, spread on an ordinary agar plate, and the number of bacteria was counted 24 hours later.

2. Hot water resistance A sample having a size of 10 cm X 10 cm is immersed in 1 L of distilled water controlled at 97 ° C. ± 1 ° C. for 2 hours and taken out.
Changes in the appearance of the coating film were evaluated according to the following criteria. ：: No change in appearance △: Slight whitening observed ×: Remarkable whitening observed

3. Surface Hardness The surface of the sample coating film was measured using a high-grade pencil specified in JIS S-6001 according to JIS K-5400, and the presence or absence of scratches was examined.

(Production Example 1 of Polyester Resin) Stirrer,
In a stainless steel autoclave equipped with a thermometer and a partial reflux condenser, dimethyl terephthalate 485 was added.
Parts, 388 parts of dimethyl isophthalate, 161 parts of tri-n-butyldodecylphosphonium salt of 5-sulfodimethylisophthalic acid, 443.3 parts of ethylene glycol, 400.4 parts of neopentyl glycol, and 0.52 of tetra-n-butyl titanate 160-220 ° C
The transesterification reaction was performed over 4 hours until the reaction. Next, 29 parts of fumaric acid was added, the temperature was raised to 200 to 220 ° C. over 1 hour, and the pressure of the reaction system was gradually reduced.
g under reduced pressure for 1 hour and 30 minutes.
-1) was obtained. The composition of the obtained polyester is as follows, when it is divided into dicarboxylic acid components and diol components, and the respective components (mol%) are shown.

<Dicarboxylic acid component> Terephthalic acid 50 mol% Isophthalic acid 40 mol% C12 phosphonium salt 5 mol% Fumaric acid 5 mol% <Diol component> Ethylene glycol 65 mol% Neopentyl glycol 35 mol%

Various polyesters (A-2, A-3) were produced in the same manner. The composition of these polyesters is shown in Table 1 below together with the composition of polyester (A-1).

[0077]

[Table 1]

Production Example 1 of Graft Polymer In a reactor equipped with a stirrer, a thermometer, a reflux device, and a metering dropping device, 300 parts of polyester (A-1), 360 parts of methyl ethyl ketone, and 120 parts of isopropyl alcohol were placed and heated. -The resin was dissolved by stirring and refluxing. After the resin was completely dissolved, a mixture of 65 parts of acrylic acid, 35 parts of ethyl acrylate, 1.5 parts of octyl mercaptan, and 6 parts of azobisisobutyronitrile were added to 9 parts of methyl ethyl ketone 9
A solution dissolved in a mixture of 0 parts and 30 parts of isopropyl alcohol was added dropwise to the polyester solution over 1.5 hours, and further reacted for 3 hours to obtain a graft polymer solution (B-1).

The polyester (A-2,
A-3) is graft-polymerized to form a graft polymer (B-2,
B-3) was obtained.

Preparation Example 2 of Graft Polymer The amount of acrylic acid was 20 parts and the amount of ethyl acrylate was 10
A graft polymer solution (B-4) was obtained in the same manner as in Production Example 1 of the graft polymer, except that the composition was changed to parts.

Preparation Example 3 of Graft Polymer Except that 35 parts of N-methylacrylamide and 65 parts of acrylamide were used as the monomers to be grafted,
A graft polymer solution (B-5) was obtained in the same manner as in Production Example 1 of the graft polymer.

Preparation Example 4 of Graft Polymer A graft polymer solution (B-6) was prepared in the same manner as in Preparation Example 1 of the graft polymer except that 15 parts of styrene and 85 parts of vinyl acetate were used as the monomers to be grafted. ) Got.

The compositions of the polyesters (B-1 to B-6) are shown in Tables 2 to 4 below.

[0084]

[Table 2]

Example 1 35 parts of an acrylic photopolymerizable prepolymer (C-1: beam set 700; manufactured by Arakawa Chemical Co., Ltd.) per 100 solids of the graft polymer solution (B-1), and a photoinitiator (D-
1: Irgacure 907; Ciba-Geigy Corporation)
After adding 2.5 parts, it was diluted with methyl ethyl ketone so that the total solid content concentration became 17% by weight to obtain a coating liquid. Next, a coating solution was applied to one side of a tin-free steel plate having a thickness of 0.2 mm so that the coating amount was 4.5 g / cm ^2.
After drying at 0 ° C. for 5 minutes,
Ultraviolet rays having an integrated irradiation light amount of 0 mJ / cm ² were irradiated and cured to prepare a resin laminated metal plate having a cured coating film on the surface layer. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 1 A polyester (A-1) was dissolved in a mixture of methyl ethyl ketone and isopropyl alcohol in place of the graft polymer solution (B-1) except that a solution was used.
A coating liquid was prepared in the same manner as in Example 1, and then a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Example 2 A coating solution was prepared in the same manner as in Example 1 except that the graft polymer solution (B-2) was used instead of the graft polymer solution (B-1). Then, a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 2 A coating solution was prepared in the same manner as in Example 1 except that the graft polymer solution (B-3) was used instead of the graft polymer solution (B-1). Then, a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Example 3 A coating solution was prepared in the same manner as in Example 1 except that the graft polymer solution (B-4) was used instead of the graft polymer solution (B-1). Then, a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Example 4 A coating solution was prepared in the same manner as in Example 1 except that the graft polymer solution (B-5) was used instead of the graft polymer solution (B-1). Then, a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 3 A coating solution was prepared in the same manner as in Example 1 except that the graft polymer solution (B-6) was used instead of the graft polymer solution (B-1). Then, a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

(Production Example 2 of Polyester Resin) Stirrer,
In a stainless steel autoclave equipped with a thermometer and a partial reflux condenser, dimethyl terephthalate 43 was added.
6.5 parts, 436.5 parts of dimethyl isophthalate, 5-
322 parts of tri-n-butyl dodecylphosphonium salt of sulfodimethylisophthalate, ethylene glycol 682
Parts, and 0.55 part of zinc acetate,
The temperature was raised to 0 ° C., and transesterification was carried out for 4 hours while distilling off generated methanol out of the system. After completion of the transesterification reaction, 55 parts of polyethylene glycol having a molecular weight of 1,000 (manufactured by Nacalai Co., Ltd.), 250 parts of antimony oxide and 0.28 parts of trimethyl phosphate were added at 250 ° C., and the mixture was stirred for 15 minutes. After gradually reducing the pressure, the mixture was reacted under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester (A-4). The composition of the obtained polyester is as follows, when it is divided into dicarboxylic acid components and diol components, and the respective components (mol%) are shown.

<Dicarboxylic acid component> Terephthalic acid 45 mol% Isophthalic acid 45 mol% C12 phosphonium salt 10 mol% <Diol component> Ethylene glycol 98.9 mol% Polyethylene glycol 1.1 mol%

Various polyesters (A) were prepared in the same manner.
-5, A-6). The composition of these polyesters is shown in Table 3 below together with the composition of polyester (A-4).

[0095]

[Table 3]

Example 5 One-pack type epoxy-based photopolymerizable prepolymer (C-2: Adeka KR566; Asahi Denka Co., Ltd.) containing a photoinitiator with respect to 100 parts of solid content of polyester (A-4) 33)
Then, the mixture was diluted with methyl ethyl ketone such that the total solid content concentration became 17% by weight to obtain a coating liquid. Next, a coating solution was applied on one side of a tin-free steel plate having a thickness of 0.2 mm so as to have an application amount of 4.5 g / cm ^2.
Dried for 800 minutes, then 800 mJ / c with an ultraviolet irradiation device
The resin laminated metal plate having a cured coating film on the surface layer was prepared by irradiating ultraviolet rays with an integrated irradiation light amount of m ² and curing. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 4 Instead of polyester (A-4), polyester (A-
A coating liquid was prepared in the same manner as in Example 5 except that 5) was used, and then a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 5 Instead of polyester (A-4), polyester (A-
A coating solution was prepared in the same manner as in Example 5 except that 6) was used, and then a resin laminated metal plate having a cured coating film on the surface layer was formed. Table 6 shows the characteristics of this resin laminated metal plate.

(Production Example 3 of Polyester Resin) Stirrer,
In a stainless steel autoclave equipped with a thermometer and a partial reflux condenser, dimethyl terephthalate 43 was added.
6.5 parts, 388 parts of dimethylisophthalate, 322 parts of tri-n-butyldodecylphosphonium 5-sulfodimethylisophthalate, 74 parts of sodium 5-sulfodimethylisophthalate, 443.3 parts of ethylene glycol,
400.4 parts of neopentyl glycol and 0.1% of zinc acetate.
55 parts were charged, the temperature was raised to 160 to 220 ° C., and a transesterification reaction was carried out for 4 hours while distilling off generated methanol out of the system. After the transesterification, 0.44 parts of antimony and 0.28 parts of trimethyl phosphate were added.
The mixture was stirred for 15 minutes, the reaction system was gradually reduced in pressure, and then reacted for 1 hour and 30 minutes under a reduced pressure of 0.2 mmHg to obtain a polyester (A-7) having an intrinsic viscosity η = 0.50.
The composition of the obtained polyester is as follows, when it is divided into dicarboxylic acid components and diol components, and the respective components (mol%) are shown.

<Dicarboxylic acid component> Terephthalic acid 45 mol% Isophthalic acid 40 mol% C12 phosphonium salt 10 mol% 5-Sulfodimethylisophthalic acid sodium 5 mol% <Diol component> Ethylene glycol 65 mol% Neopentyl glycol 35 mol%

Various polyesters (A) were prepared in the same manner.
-8, A-9). The composition of these polyesters is shown in Table 4 below together with the composition of polyester (A-7).

[0102]

[Table 4]

Example 6 35 parts of an acrylic photopolymerizable prepolymer (C-3: M7100; manufactured by Toagosei Co., Ltd.) per 100 solid components of polyester (A-7), photoinitiator (D-1) After adding 2.5 parts, the total solid concentration was adjusted to 17 with methyl ethyl ketone.
It was diluted so as to be a weight% to obtain a coating liquid. Next, a coating solution was applied on one side of a tin-free steel plate having a thickness of 0.2 mm so as to have an application amount of 4.5 g / cm ² , dried in a hot air oven at 70 ° C. for 5 minutes, and then exposed to ultraviolet light. Irradiation was performed by irradiating an ultraviolet ray with an integrated irradiation light amount of 800 mJ / cm ^{2 by} an irradiation device to prepare a resin laminated metal plate having a cured coating film on the surface layer. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 6 In place of polyester (A-7), polyester (A-
A coating liquid was prepared in the same manner as in Example 6 except that 8) was used, and then a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 7 In place of polyester (A-7), polyester (A-
A coating solution was prepared in the same manner as in Example 6, except that 9) was used, and then a resin laminated metal plate having a cured coating film on the surface layer was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 8 According to Example 1, the coating solution was diluted with the graft polymer solution (B-1) so that the total solid content concentration became 17% by weight. Next, a coating solution is applied to one side of a tin-free steel plate having a thickness of 0.2 mm so as to have an application amount of 4.5 g / cm ^2, and then dried in a hot air oven at 120 ° C. for 3 minutes to obtain a resin having a coating film. A laminated metal plate was made. Table 6 shows the characteristics of this resin laminated metal plate.

Comparative Example 9 According to Example 2, the coating solution was diluted with the graft polymer solution (B-2) so that the total solid content concentration became 17% by weight. Next, after applying a coating solution to one side of a tin-free steel plate having a thickness of 0.2 mm so as to have an application amount of 4.5 g / cm ² , the coating solution is dried in a hot air oven at 120 ° C. for 3 minutes to have a coating film. A resin laminated metal plate was prepared. Table 6 shows the characteristics of this resin laminated metal plate.

Table 5 below summarizes the polymers and photopolymerization initiators used in the above Examples and Comparative Examples.

[0109]

[Table 5]

Table 6 below summarizes the characteristics of the resin-laminated metal plates of the above Examples and Comparative Examples.

[0111]

[Table 6]

[0112]

The antimicrobial resin composition of the present invention has good antimicrobial properties and excellent durability that can withstand practical use. Metallic plates are used in applications where antibacterial properties are desired, for example, electronic devices such as walls, floors and ceilings of kitchens, toilets, bathrooms, etc., window frames, doorknobs, and handrails of building materials such as hospitals, medical facilities, public facilities, and general houses. Cooking appliances such as microwave ovens and rice cookers, home appliances such as refrigerators, washing machines, telephones, and vacuum cleaners, metal containers such as cans, beverage cans, pail cans, and drum cans; water supplies such as system kitchens and sinks; Air conditioners such as air purifiers, furniture such as desks, shelves and tables, medical equipment in general, stationery, decorative boards for trains, cars, ships, aircraft, etc.
It is most suitable as a constituent material for inner and outer panels, structures, accessories, parts, etc.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hideto Ohashi 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Inventor Shigetsugu Konagaya 2-1-1 Katata, Otsu-shi, Shiga Prefecture No.1 Toyobo Co., Ltd. Research Laboratory F term (reference) 4H011 AA02 BB04 BB07 BB17 BB19 BC19 DA08 DD07 DH25 DH28 4K044 AA02 AA03 AA06 BA21 BB02 CA53 CA62

Claims (8)

[Claims] 1. A composition comprising a polymer substance having an organic antibacterial agent component bound to a main chain or a side chain, a hydrophilic substance mixed or bound to the polymer substance, and a curing agent. An antibacterial metal plate obtained by laminating and curing layers on the surface of a metal plate. 2. The antibacterial metal sheet according to claim 1, wherein the curing agent is a photopolymerizable curable resin. 3. A polymer in which an organic antibacterial agent component is bonded to a main chain or a side chain is a polymer in which at least one of an ammonium base, a phosphonium base or a sulfonium base is bonded to a main chain and / or a side chain. The antibacterial metal plate according to claim 1, wherein the metal plate is provided. 4. A hydrophilic substance comprising 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 or a polyamine chain. The antibacterial metal plate according to claim 1, which is a polymer having at least one kind. 5. The method according to claim 1, wherein a hydrophilic substance is bonded via a covalent bond to a polymer substance having an organic antibacterial agent component bonded to a main chain or a side chain. 4. The antibacterial metal plate according to 4. 6. The method according to claim 1, wherein a hydrophilic component is bonded via a covalent bond to a polymer in which a phosphonium base as an organic antibacterial component is bonded to a main chain or a side chain. The antibacterial metal plate according to 3, 4, or 5. 7. The method according to claim 1, wherein the photopolymerizable curable resin comprises at least a photopolymerization initiator, a photopolymerizable prepolymer and / or a photopolymerizable monomer. The antibacterial metal plate as described. 8. The 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 these as a main component. 3. The antibacterial metal plate according to 1.