JPH11277672A - Metallic plate with superb antibacterial and antimildew properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance durability under various environments with satisfactory antibacterial and antimildew properties by laminating an antibacterial and antimildew layers containing a polymer substance and a hydrophilic substance with a phosphonium base bonded to a main chain and a side chain on at least, one of the faces of a metallic plate. SOLUTION: An antibacterial and antimildew layer containing a polymer substance and a hydrophilic substance with a phosphonium base bonded to a main chain and a side chain, is laminated on at least, one of the faces of a metallic plate. The hydrophilic substance is a polyalkylene oxide and/or a derivative thereof. Alternatively, the hydrophilic substance consisting of a vinyl polymer with a hydrophilic group bonded to the side chain is graft-polymerized to a polymer material, or a chemical compound which contains a sulfonic metallic base and can form an ester, is copolymerized with the main chain of the polymer material. The metallic plate is aluminum, steel or an alloy composed mainly of these metals. The ratio of the hydrophilic substance is preferably 0.1-40 wt.% to the total amount of the hydrophilic substance and the polymer material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial agent containing a polymer substance containing a phosphonium base and a hydrophilic substance.
Metal sheet laminated with anti-fungal layer has excellent antibacterial and antifungal properties, especially building materials such as walls, floors, ceilings, window frames, door knobs, handrails, cooking equipment, home appliances, metals Containers, water supplies, air conditioning equipment, furniture such as desks and shelves,
A metal plate with excellent antibacterial and antifungal properties, which is suitably used as a constituent material for medical equipment, stationery, decorative boards such as trains, automobiles, ships, aircrafts, etc., interior and exterior panels, structures, accessories, parts, etc. It is about.

[0002]

2. Description of the Related Art Thermoplastic resins, especially polyethylene,
Polypropylene, polyvinylidene chloride, nylon, polyethylene terephthalate, ethylene terephthalate and the like have excellent physical and chemical properties and are used for fibers, films, sheets, molded products, adhesives and the like. Recently, antibacterial products in which an inorganic or organic antibacterial agent is filled or coated have been devised, and the uses thereof have been diversified.

At present, antibacterial agents mainly studied or used include natural products such as chitin, chitosan, wasabi extract mustard extract, hinokitiol, tea extract antibacterial agent, photooxidation catalyst titanium oxide particles, and zinc oxide superoxide. Examples include inorganic compounds such as fine particles, silver-containing zeolite, and silver-containing zirconium phosphate, and synthetic products such as organic ammonium salt-based and organic phosphonium salt-based compounds. Inorganic antibacterial agents typified by natural and silver are safe in terms of toxicity and have recently received attention, and the following inventions have already been disclosed.

JP-A-3-83905 discloses a phosphate-based antibacterial agent containing silver ions, 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. An antimicrobial agent comprising:

[0005] Fibers, films, sheets and molded articles are prepared according to the inventions disclosed therein, and Staphylococcus aureus,
Antibacterial activity against Escherichia coli and fungus against black mold and black yeast-like fungi were evaluated, but antibacterial activity was insufficient if the amount added was relatively low to maintain transparency, and it was attempted to improve antibacterial activity. Then, transparency must be sacrificed, and the antifungal property is insufficient and there is room for improvement in practical use.

On the other hand, antibacterial and antifungal agents of organic synthetic products are generally superior in the antifungal performance against fungi and the like to natural products and inorganic products, but the antibacterial agent is coated on a substrate such as a film. Or, when filled, the antibacterial and fungicide has a low molecular weight, so it is easy to volatilize, desorb and separate from substrates such as films. It is not preferable in respect of the point.

When an antibacterial / antifungal agent is used for a film or the like, the antibacterial / antifungal agent does not dissolve in water or an organic solvent,
It is preferable from the viewpoint of long-term stability of antibacterial and antifungal properties and safety to human bodies that the film is hardly released, detached, peeled, or dropped off from the film surface.

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. JP-A-54-86584 describes an antibacterial material mainly composed of a polymer substance containing an antibacterial agent component having a quaternary ammonium base ionically bonded to an acidic group such as a carboxyl group or a sulfonic acid. Have been. 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. JP-A-57-204286, JP-A-63-60903, JP-A-62-114903, JP-A-1-93596, JP-A-2-240
No. 090, etc., various phosphonium salt compounds are known as biologically active chemicals having a broad activity spectrum against bacteria and fungi.

An invention in which the above phosphonium salt is immobilized on a polymer substance to expand the use thereof has been disclosed. JP-A-4-266912 discloses an antibacterial agent of a phosphonium salt-based vinyl polymer, and JP-A-4-814365 discloses an antibacterial agent of a vinylbenzylphosphonium salt-based vinyl polymer.

Furthermore, JP-A-5-310820 discloses an antibacterial material mainly composed of a polymer substance containing an antibacterial component having an acidic group and a phosphonium base ionically bonded to the acidic group. . In that example,
Polyesters using phosphonium salts of sulfoisophthalic acid are disclosed.

Japanese Patent Application Laid-Open No. 6-41408 does not mention any antibacterial action, but it is useful for photographic supports, packaging, general industrial use, magnetic tapes, and the like, in which polyesters of phosphonium sulfonate salts are used. Modified polyesters and polyester films comprising a polyalkylene glycol and a polyalkylene glycol are disclosed.

The alkyl group bonded to the phosphonium salt described in the specification of the above patent is disclosed in Japanese Patent Application Laid-Open No. 5-31082.
Unlike the publication No. 0, it is a type having a relatively short carbon number such as a butyl group, a phenyl group, or a benzyl group.

Further, Japanese Patent Application Laid-Open Nos. Hei 4-266912, Hei 4-814365, Hei 5-310820
Nos. 1 and 2 were studied diligently to synthesize fibers, films, sheets, etc. by synthesizing phosphonium base-containing vinyl copolymers and copolyesters according to the examples, and applying the antibacterial polymer thereof on the fibers and film sheet surfaces. The antibacterial and antifungal properties were evaluated, but the antibacterial and antifungal properties were insufficient. Furthermore, in order to improve the antibacterial and fungicidal properties, a polyester in which tri-n-butyldodecylphosphonium base was bonded at 50 mol% or more was synthesized, and films and sheets were formed therefrom. The antibacterial and antifungal properties were insufficient as well as the decrease in mechanical properties due to the decrease in points.

Further, the above-mentioned organic antibacterial agents are used alone or in combination to form fibers, films, sheets, etc., which have antibacterial properties against Staphylococcus aureus, Escherichia coli, etc. and fungicides against Aspergillus niger, Black yeast-like fungi, etc. I evaluated the sex,
The antibacterial and antifungal properties were insufficient, and the practicality was insufficient.

[0015]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional metal plate having excellent antibacterial and antifungal properties, and has both practical antibacterial and antifungal properties. An object of the present invention is to provide an antibacterial / mold-resistant metal plate.

[0016]

In order to achieve the above object, the present invention provides a metal plate having excellent antibacterial and antifungal properties, comprising a polymer substance and a hydrophilic substance each having a phosphonium base bonded to a main chain or a side chain. Wherein an antibacterial / fungus-proof layer containing is laminated on at least one surface of a metal plate.

The antibacterial and antifungal metal plate of the present invention having the above-mentioned constitution has a remarkable antibacterial and antifungal property by allowing a hydrophilic substance to be present in a polymer substance containing a phosphonium base. Can be enhanced.

In order to achieve the above object, the present invention provides a metal plate having excellent antibacterial and antifungal properties, wherein a hydrophilic substance is chemically bonded to a polymer substance having a phosphonium base bonded to a main chain or a side chain. An antibacterial / antifungal layer containing a bonded hydrophilic polymer substance is laminated on at least one surface of a metal plate.

The metal plate excellent in antibacterial and antifungal properties of the present invention having the above-mentioned constitution has a remarkable antibacterial and antifungal property by including a hydrophilic substance in a polymer substance containing a phosphonium base. Can be enhanced.

In a preferred embodiment, the macromolecular substance having a phosphonium base bonded to a main chain or a side chain can have an acid group and a phosphonium base ionically bonded to the acid group.

In a preferred embodiment, a polymer in which a phosphonium base is bonded to a main chain or a side chain comprises a dicarboxylic acid component and a glycol component as main components and a sulfone represented by the following general formula (1): It can be a polyester resin having a phosphonium base of an acid group-containing aromatic dicarboxylic acid.

[0022]

Embedded image

In a preferred embodiment, the polyester resin is obtained by copolymerizing 1 to 50 mol% of a phosphonium base of a sulfonic acid group-containing aromatic dicarboxylic acid represented by the above general formula (1) with respect to all acid components. It can be a copolyester.

Further, as a preferred embodiment, the hydrophilic substance can be a polyalkylene oxide and / or a derivative thereof.

In a preferred embodiment, the hydrophilic high molecular substance can be obtained by graft-polymerizing a hydrophilic substance comprising a vinyl polymer having a hydrophilic group in a side chain to the high molecular substance.

In a preferred embodiment, the hydrophilic polymer substance may be one obtained by copolymerizing a compound capable of forming an ester containing a metal sulfonate group into the main chain of the polymer substance.

Further, as a preferred embodiment, the metal plate can be made of a material selected from the group consisting of aluminum, steel and an alloy containing these as a main component.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a metal plate excellent in antibacterial and antifungal properties of the present invention will be described in detail.

The polymer substance of the present invention having a phosphonium base bonded to a main chain or a side chain may be any polymer compound as long as the phosphonium base is bonded to the main chain or a side chain. Specific examples are shown below, but the present invention is not limited thereto.

In a preferred embodiment of the polymer substance of the present invention having a phosphonium base bound to a main chain or a side chain, in a preferred embodiment, a polymer substance containing an acidic group and a phosphonium base ionically bound to an acidic group, more preferably In a preferred embodiment, a polyester resin having a phosphonium group of a sulfonic acid group-containing aromatic dicarboxylic acid represented by the following general formula (1), and in a more preferred embodiment, a polyester resin is represented by the following general formula (1) A polyester resin obtained by copolymerizing a phosphonium base of a sulfonic acid group-containing aromatic dicarboxylic acid with 1 to 50 mol% based on all acid components.

[0031]

Embedded image

In addition, one of the high molecular substances having a phosphonium base bonded to a main chain or a side chain is a phosphonium salt vinyl polymer represented by the general formula (2).

[0033]

Embedded image Specific examples of R1, R2, and R3 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and dodecyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenyl; Substituted with a group, an alkoxy group, etc., and an alkyl group, an aryl group, etc. are particularly preferred. R
1, R2 and R3 may be the same group or different groups.
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 and the like, and a halogen ion is particularly preferable. n is not particularly limited, but is 2 to 500, preferably 10 to 300.

The dicarboxylic acid component used in the polyester resin includes terephthalic acid, isophthalic acid,
Examples thereof include 6-naphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. 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 carboxylic acid and its derivatives. Further, an oxycarboxylic acid such as p-oxybenzoic acid and a polyvalent carboxylic acid such as trimellitic anhydride and pyromellitic anhydride may be used in combination as long as the content of the invention is not impaired.

Of these, from the viewpoint of practical durability when formed into a coating film, it is preferable to contain at least 70 mol% of an aromatic dicarboxylic acid. Other dicarboxylic acids include 1,4-
Dicarboxylic acid, adipic acid and sebacic acid are particularly preferred.

The glycol components used in the polyester resin include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,
3-propanediol, 1,4-butanediol, 1,
5-pentadiol, neopentyl glycol, 1,6
-Hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,
Alkylene glycols such as 2-diethyl-1,3-propanediol, 1,9-nonanediol and 1,10-decanediol; alicyclic glycols such as 1,2-cyclohexanedimethanol; alkylene oxides of bisphenol A or F Adducts, diethylene glycol, polyethylene glycol, neopentyl glycol of hydroxypivalic acid (HPN), polypropylene glycol, polytetramethylene glycol and the like can be mentioned.

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

Among these, ethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, and ethylene glycol, neopentyl glycol,
1,6-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-
Cyclohexanedimethanol.

Further, a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like may be used in combination within a range not to impair the content of the invention.

Examples of the phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid include 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.

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

In order to improve the heat resistance such as the degree of coloring and the degree of gelation, the copolymerized polyester used in the present invention may contain a magnesium salt such as magnesium acetate or magnesium chloride in addition to a polymerization catalyst such as antimony oxide, germanium oxide or titanium compound. , Calcium acetate, calcium salts such as calcium chloride, manganese acetate, manganese salts such as manganese chloride,
A zinc salt such as zinc chloride and zinc acetate, and a cobalt salt such as cobalt chloride and cobalt acetate each having a metal ion of 300 p
pm or less, phosphoric acid or a phosphoric acid ester derivative such as phosphoric acid trimethyl ester, phosphoric acid triethyl ester
, It is also possible to add 200 ppm or less.

When the total amount of metal ions other than the polymerization catalyst is 3
When the content of P exceeds 00 ppm or the content of P exceeds 200 ppm, the coloring of the polymer can be discriminated and the heat resistance and the hydrolysis resistance of the polymer are undesirably affected.

From these facts, in terms of heat resistance, hydrolysis resistance and the like, the molar ratio between the total phosphorus amount and the total metal ion amount is as follows:
It is preferably from 0.4 to 1.0.

[0045]

(Equation 1)

When the 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 used in the present invention is not particularly limited, but a 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. And a polycondensation reaction after transesterification of the compound and the so-called transesterification method. An arbitrary production method can be applied.

The timing of addition of the metal ions, 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, and the addition of phosphoric acids is performed before the polycondensation reaction. Is preferably added.

In order to form the antibacterial / antifungal layer used in the present invention, it is necessary to mix or chemically bond a hydrophilic substance including a polymer substance having a phosphonium base bonded to a main chain or a side chain. In this case, the presence of the hydrophilic substance significantly improves antibacterial and antifungal properties.

In the present invention, a hydrophilic substance is a substance having an excellent affinity for water and is a substance which can be dissolved, dispersed or retained in water, has moisture retention and swells, and is generally an amino group, an amide group or a carboxyl group. Or a hydrophilic group such as an alkali metal salt, a sulfonic acid group or an alkali metal salt thereof, or a derivative thereof, or an organic compound or a polymer compound containing two or more ether bonds in one molecule. Specific examples thereof include polyvinyl alcohol, starch, a homopolymer or copolymer of polyacrylic acid, a homopolymer or copolymer of polymethacrylic acid, and a homopolymer or copolymer of maleic anhydride (for example, maleic anhydride. Styrene copolymer), polyvinyl sulfonic acid or its copolymer or an alkali metal salt thereof, polyalkylene glycol such as polyethylene glycol (also known as polyethylene oxide) polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, glycerin, polyglycerin Polyols or polymers thereof, glycerin, polyglycerin, water-soluble modified celluloses such as hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, carboxy cellulose Sodium and cellulose nitrate carboxymethyl ether. These are used as a mixture with a polymer substance having a phosphonium base bonded to a main chain or a side chain.

The molecular weight of the hydrophilic substance used in the present invention is not particularly limited. In the case of polyethylene glycol, the number average molecular weight is preferably 200 to 30,000, more preferably 1,000 to 25,000. .

The proportion of the hydrophilic substance (in the case of a copolymer, the hydrophilic substance contained in the copolymer) used in the present invention is preferably 0.1 to 40% by weight based on the total amount of the high molecular substance. Is 0.5 to 20% by weight, more preferably 1 to 10% by weight. If the amount is less than 0.1% by weight, the effect of increasing the antibacterial and antifungal activity is insufficient, and if it exceeds 40% by weight, the mechanical properties and the heat resistance and weather resistance of the antibacterial and antifungal layer are undesirably reduced. The method of mixing the hydrophilic substance and the high molecular substance can be any method, and any method can be adopted depending on the production method, chemical properties and physical properties of the high molecular substance. 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.

In addition, as a method for producing a hydrophilic polymer substance by introducing a hydrophilic substance into the polymer substance, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof is added to a polymer substance containing a phosphonium base. , A hydrophilic group such as a sulfonic acid group or an alkali metal salt thereof, or a derivative thereof is copolymerized into the main chain or the immediate chain. By copolymerization, the compatibility is improved, and the appearance, storage stability, and physical properties of the coating film are improved.

Methods for copolymerizing these hydrophilic groups include 5-sulfoisophthalic acid, 4-sulfonaphthalene-
Metal salts such as 2,7-dicarboxylic acid, 5 (4-sulfophenoxy) 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, polyethylene glycol,
Examples thereof include a method of copolymerizing an alkylene glycol such as polypropylene glycol and polytetramethylene glycol with a polyester resin, and a method of graft-polymerizing a vinyl-based monomer containing a hydrophilic group onto the polyester resin.

The vinyl monomer having a hydrophilic group that can be grafted onto a polymer substance, particularly a polyester resin, used in the present invention includes a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group and the like.
Examples of the group that can be converted into a hydrophilic group include an acid anhydride group, a glycidyl group, and a chloro group. 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, and alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate and 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 and 2-hydroxyethyl methacrylate, acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N- Examples include amide group-containing monomers such as methylol methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N, N dimethylol acrylamide, 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 to produce a hydrophilic substance. 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 ratio between the monomer having a hydrophilic group and the other monomer is preferably in the range of 30/70 to 100/0 in molar ratio. When the ratio of the monomer having a hydrophilic group is 30
If it is less than mol%, the effect of enhancing antibacterial and antifungal properties 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 polymer of the main chain by light, heat, radiation or the like and then graft-polymerized with a monomer, or AlCl 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. Examples of the monomer having a polymerizable unsaturated double bond used therein include fumaric acid, maleic acid, maleic anhydride, tetrahydromaleic anhydride and the like. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid.

Further, there is a method in which a main chain of a polymer 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 the side chain -OH group, -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 a —N ＝ C ＝ O group, a —C ＝ C ＝ O group,

[0062]

Embedded image

And the like, and a reaction in the reverse combination.

In the present invention, the preferred weight ratio of the main chain polyester to the grafted vinyl monomer is in the range of 95/5 to 40/60, more preferably 93/7 to 55/45, and most preferably. 90 / 10-6
It is in the range of 0/40. When the weight ratio of the main chain polymer substance is 4
If the amount is less than 0%, 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 significant difference in the antibacterial and fungicidal effects between the case where the hydrophilic substance is mixed with the polymer substance and the case where the hydrophilic substance is copolymerized with the polymer substance.
Fungicidal properties are obtained.

A curing agent capable of reacting with either the polymer substance or the hydrophilic substance forming the antibacterial / mold-proof layer of the antibacterial / mold-proof metal plate of the present invention may be incorporated in the antibacterial / mold-resistant layer. . By blending a curing agent, better coating film properties can be obtained. The preferred compounding amount of the curing agent is 5 to 35% by weight, more preferably 10 to 20%, based on the total of the polymer substance and the hydrophilic substance. As a curing agent,
Examples thereof include an alkyl etherified amino formaldehyde resin, an epoxy compound and an isocyanate compound.

The alkyletherified aminoformaldehyde resin is, for example, formaldehyde or paraformaldehyde alkylated with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol and urea. , N, N-ethylene urea, dicyandiamide, aminotriazine, and the like; methoxylated methylol benzoguanamine, methoxylated methylol-N, N-ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, butoxylated methylol Melamine, butoxylated methylol benzoguanamine, methoxylated / butoxylated mixed type methylol melamine, etc., are preferred. Melamine, butoxy methylol melamine, or a methoxylated / butoxylated mixed melamine, may be used alone or in combination.

As the epoxy compound, bisphenol A
Diglycidyl ether and its oligomer, hydrogenated bisphenol A diglycidyl ether and its oligomer, orthoisophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydro Diglycidyl phthalate, Diglycidyl hexahydrophthalate, Diglycidyl succinate, Diglycidyl adipate, Diglycidyl sebacate, Ethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, 1,4-butanediol Diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellit Triglycidyl tolate, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether adduct Glycidyl ethers can be mentioned.

Further, as the isocyanate compound, there are aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, and either low molecular weight compounds or high molecular weight compounds may be used. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds The amount and, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, low molecular active hydrogen compounds such as triethanolamine or various polyester polyols, polyether polyols, polyamides By reacting with a high molecular weight active hydrogen compound, etc. Terminal isocyanate group-containing compounds, and the like to be.

The isocyanate compound may be a blocked isocyanate. As isocyanate blocking agents, for example, phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol,
Phenols such as chlorophenol, acetoxime,
Oximes such as methyl ethyl ketoxime and cyclohexanone oxime; alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; t-butanol and t-pen And lactams such as tertiary alcohols such as tertanol, ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propyrolactam, and aromatic amines, imide rings, acetylacetone, and acetoacetic acid. Esters, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds, sodium bisulfite and the like are also included. The blocked isocyanate can be obtained by subjecting the above isocyanate compound to an isocyanate blocking agent to undergo an addition reaction by a known appropriate method.

A known curing agent or accelerator selected according to the type can be used in combination with these crosslinking agents.

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

The metal plate excellent in antibacterial and antifungal properties of the present invention is obtained by laminating the above antibacterial and antifungal 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 steel, aluminum,
Aluminum alloy, tin plated steel, nickel plated steel,
Representative examples include chrome-plated steel, hot-dip galvanized steel, electrolytic galvanized steel, hot-dip zinc-aluminum alloy-plated steel, and aluminum-plated steel. These metal plates may be appropriately subjected to an organic or 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.

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

As a method of laminating an antibacterial / antifungal layer on a metal plate, a high molecular substance having a phosphonium base bonded to a main chain or a side chain and a hydrophilic substance or a high molecular substance having a phosphonium base bonded to a main chain or a side chain are used. A film obtained by extruding a hydrophilic polymer substance in which a hydrophilic substance is chemically bonded to a molecular substance into a sheet with a melt extruder and then uniaxially or biaxially stretching, or an unstretched film Method of laminating a film on a metal plate by heat fusion; thermosetting resin of polyurethane, phenol, furan, urea, melamine, polyester, epoxy, silicone, vinyl acetate, ethylene-acetic acid Vinyl copolymers and their hydrolysates, ethylene-acrylic acid-based copolymers, acrylic resins, thermoplastic resins such as polyamides, butadiene-acrylonitrile A method of laminating on a metal plate via an adhesive layer made of rubber, neoprene, other rubber derivatives, other adhesives such as lacquer, glue, casein, natural resin, etc .; melting a polymer forming an antibacterial / antifungal layer A method of extruding and laminating a metal plate directly on an extruder or via the adhesive layer; dissolving or dispersing a polymer for forming an antibacterial / antifungal layer in a solvent, and providing a primer coating layer directly or on the metal plate. Method of applying and drying on top;
Coating and drying a polymer that forms an antibacterial / antifungal layer dissolved or dispersed in a solvent on a film of polyethylene, polypropylene, polyvinyl chloride, nylon, polyester, polycarbonate, polystyrene, polyurethane, polyamide, polyimide, polyamideimide, etc. After that, a method of laminating the film on a metal plate with the non-coated surface side as an adhesive surface may be mentioned, but it is not limited thereto. In addition, when extruding a polymer forming an antibacterial / mold-proof layer into a sheet by a melt extruder, the polymer can be coextruded with another thermoplastic resin and then laminated on a metal plate.

The thus obtained metal sheet having excellent antibacterial and antifungal properties may be subjected to processing such as bending, drawing, and ironing according to its use.

The metal plate excellent in antibacterial and antifungal properties of the present invention includes, for example, building materials such as walls, floors, ceilings, window frames, door knobs, handrails, cooking appliances, home appliances, metal containers, and water supplies. It is suitable as a constituent material for air conditioners, furniture such as desks and shelves, medical equipment, stationery, decorative boards such as trains, automobiles, ships, and aircrafts, interior / exterior boards, structures, accessories, parts and the like. .

[0078]

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. In addition, below, the measuring method of the physical property of the metal plate excellent in antibacterial property and fungicidal property obtained by the Example and the comparative example is shown.

1. Antibacterial test S.I. diluted with 1/50 broth aureus (Staphylococcus aureus) 0.1 c of bacterial solution (concentration: 10 ⁶ cells / cc)
c was dropped onto a 5 cm x 5 cm sample metal plate which had been sterilized by high pressure steam in advance, and a polyethylene film sterilized by high pressure steam was adhered to the sample metal plate. The test piece was transferred to a sterile petri dish and cultured at 37 ° C. for 24 hours. Then, the bacteria on the film were washed with 10 cc of the SCDLP medium, diluted 10-fold, and plated on a normal agar plate, and the number of bacteria was counted 24 hours later.

2. Mold resistance test A sample metal plate having a size of 5 cm x 5 cm was stuck on an inorganic salt agar medium plate by a method according to JIS-Z-2911-6.2.2, and spore suspension of the following five mold strains was used. The suspension was sprayed with 0.2 cc of a mixture obtained by adding 5% of sucrose to the suspension to obtain 27 ±
After culturing at 1 ° C. for 28 days, the growth state of the mold was evaluated.

(Test strain) Aspergillus niger ATCC 62
75 Penicillium citrinum ATCC
9849 Chaetomium globosum ATCC
6205 Rhizopus stolonifer ATCC
10404 Aureobasidium pullulans I
FO 6353

(Indication of mold resistance) (1) Mold growth is 1/3 or more of sample area (2) Mold growth is within 1/3 of sample area (3) Mold growth is not recognized

3. Water resistance A test piece was prepared by cutting a sample metal plate into a size of 10 cm × 5 cm, immersed in 1 liter of distilled water controlled at 20 ° C. ± 1 ° C. for 24 hours, taken out, dried at room temperature, and then subjected to antibacterial and fungicidal properties Was evaluated.

4. Hot water resistance A test piece cut into a 10 cm x 5 cm sample metal plate, immersed in 1 liter of distilled water controlled at 80 ° C ± 1 ° C for 2 hours, taken out, dried at room temperature, and then antibacterial and fungicidal Was evaluated.

5. Acid resistance Sample metal plate is cut into 5cm x 5cm test piece, 10% hydrochloric acid solution is applied on the antibacterial and antifungal layer of the test piece, and after 60 minutes, the test piece is washed with water and dried and then antibacterial The properties and fungicidal properties were evaluated.

6. Alkali resistance A test piece was prepared by cutting a sample metal plate into a size of 5 cm × 5 cm, a 10% aqueous solution of sodium hydroxide was applied on the antibacterial and mold-proof layer of the test piece, and after 60 minutes, the test piece was washed with water and dried. Post-bacterial and fungicidal properties were evaluated.

"Production Example 1 of Polyester Resin"
Dimethyl terephthalate 485 in a stainless steel autoclave equipped with a thermometer and a partial reflux condenser
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. Then, 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 polyester is as shown below. Dicarboxylic acid component Terephthalic acid 50 mol% Isophthalic acid 40 mol% C ₁₂ phosphonium salt 5 mol% Fumaric acid 5 mol% Diol component Ethylene glycol 65 mol% Neopentyl glycol 35 mol%

Various polyesters (A-2, A-3) shown in Table 1 were produced in the same manner.

"Production Example 1 of Graft Polymer" In a reactor equipped with a stirrer, a thermometer, a reflux device and a metered addition device, 300 parts of polyester (A-1) and 360 parts of methyl ethyl ketone were placed.
And 120 parts of isopropyl alcohol, and heated and stirred to dissolve the resin under reflux. After the resin is completely dissolved, a mixture of 65 parts of acrylic acid and 35 parts of ethyl acrylate, 1.5 parts of octyl mercaptan, and 6 parts of azobisisobutyronitrile are mixed with a mixture of 90 parts of methyl ethyl ketone and 30 parts of isopropyl alcohol. The dissolved solution was added dropwise to the polyester solution over 1.5 hours, and allowed to react for another 3 hours to obtain a graft polymer solution (B-
1) was obtained.

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

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

"Production Example 3 of Graft Polymer" In Production Example 1 of the graft polymer, 35 parts of N-methylacrylamide and 65 parts of acrylamide
Except that part was used, a graft polymer solution (B-5) was obtained in the same manner as in Production 1.

"Production Example 4 of Graft Polymer" A production method similar to that of Production Example 1 except that the grafting monomer used in Preparation Example 1 was 15 parts of styrene and 85 parts of vinyl acetate. With the graft polymer solution (B-
6) was obtained.

Example 1 A graft polymer solution (B-1) was applied on a 0.2 mm-thick taine-free steel plate so that the applied amount of the solid content was 5.0 g / m ^2, and then 80%.
This was set at 10 ° C. for 10 minutes, and then heat-treated at 150 ° C. for 1 minute to produce a resin laminated metal sheet. Table 2 shows the characteristics of the resin laminated metal plate.

Comparative Example 1 The procedure of Example 1 was repeated, except that the polyester (A-1) was dissolved in a mixture of methyl ethyl ketone and isopropyl alcohol in place of the graft polymer solution. A resin laminated metal plate having a coating film on the surface layer was produced. Table 2 shows the characteristics of the resin laminated metal plate.

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

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

(Example 3) A resin laminated metal plate having a coating film on the surface layer was formed in the same manner as in Example 1 except that the graft polymer solution (B-4) was used. . Table 2 shows the characteristics of the resin laminated metal plate.

Example 4 A resin-laminated metal plate having a coating film on its surface was formed in the same manner as in Example 1 except that the graft polymer solution (B-5) was used. . Table 2 shows the characteristics of the resin laminated metal plate.

Comparative Example 3 A resin-laminated metal plate having a coating film on its surface was formed in the same manner as in Example 1 except that the graft polymer solution (B-6) was used. . Table 2 shows the characteristics of the 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 436.
5 parts, 436.5 parts of dimethyl isophthalate, 322 parts of tri-n-butyldodecylphosphonium 5-sulfodimethylisophthalate, 682 parts of ethylene glycol, and 0.55 part of zinc acetate were charged, and the temperature was raised to 160 to 220 ° C. The transesterification reaction was carried out for 4 hours while distilling off the methanol produced by the reaction outside the system. After the transesterification reaction, 55 parts of polyethylene glycol having a molecular weight of 1,000 (manufactured by Nacalai Co.) at 250 ° C., 0.44 parts of antimony oxide and 0.28 of trimethyl phosphate were added.
The mixture was stirred for 15 minutes, and the pressure of the reaction system was gradually reduced. Then, the mixture was reacted under a reduced pressure of 0.2 mmHg for 1 hour 30 minutes.
Polyester (A-4) was obtained. Polyester (A-
The composition of 4) is as shown below. Dicarboxylic acid component Terephthalic acid 45 mol% Isophthalic acid 45 mol% C ₁₂ phosphonium salt 10 mol% Diol component Ethylene glycol 98.9 mol% Polyethylene glycol 1.1 mol%

Various polyesters (A-5, A-6) shown in Table 1 were produced in the same manner.

Example 5 Polyester (A-4) was melt-extruded at 260 ° C. using an extruder, and then cast with a cooling roll at 30 ° C. to obtain a 170 μm-thick unstretched film. This was stretched 3.5 times in the longitudinal direction by heating at 65 ° C. by the difference in speed between a pair of rolls having different peripheral speeds, and then stretched in the transverse direction in a tenter heated to 80 ° C.
Stretched 0 times, heat-set at 180 ° C while relaxing 5%,
A biaxially stretched film having a thickness of about 12 μm was obtained. 2 obtained
The axially stretched film is coated with an adhesive (trade name: Byron 200:
It was laminated on an aluminum plate having a thickness of 0.2 mm via a Toyobo Co., Ltd.) to obtain a resin-laminated metal plate. Table 2 shows the characteristics of the resin laminated metal plate.

Comparative Example 4 A biaxially stretched film was prepared in the same manner as in Example 5 except that polyester (A-5) was used in Example 5, and then laminated on an aluminum plate in the same manner. Thus, a resin laminated metal plate was obtained. Table 2 shows the characteristics of the resin laminated metal plate.

Comparative Example 5 A biaxially stretched film was prepared in the same manner as in Example 5 except that polyester (A-6) was used in Example 5, and then laminated on an aluminum plate in the same manner. Thus, a resin laminated metal plate was obtained. Table 2 shows the characteristics of the 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 436.
5 parts, 388 parts of dimethyl isophthalate, 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 0.55 zinc acetate
Then, the mixture was heated to 160 to 220 ° C., and transesterification was carried out for 4 hours while distilling off the methanol generated from the system outside the system. After completion of the transesterification reaction, 0.44 part of antimony and 0.28 part of trimethyl phosphate were added, and the mixture was stirred for 15 minutes.
Reaction was performed for 1 hour and 30 minutes under reduced pressure of 2 mmHg, and intrinsic viscosity η
= 0.50 polyester (A-7) was obtained. The composition of the polyester (A-7) is as shown below. Dicarboxylic acid component Terephthalic acid 45 mol% Isophthalic acid 40 mol% C ₁₂ phosphonium salt 10 mol% 5-sulfodimethylisophthalic acid sodium 5 mol% Diol component Ethylene glycol 65 mol% Neopentyl glycol 35 mol%

In the same manner, various polyesters (A-8, A-9) shown in Table 1 were produced.

Example 6 Polyester (A-7) was dissolved in a mixed solution of methyl ethyl ketone and isopropyl alcohol, and the applied amount of the solid content was 5.0 g / m ² on a 0.2 mm thick tein-free steel plate. After application so that
Set at 80 ° C for 10 minutes, then at 150 ° C for 1 minute.
A partial heat treatment was performed to produce a resin laminated metal plate. Table 2 shows the characteristics of the resin laminated metal plate.

Comparative Example 6 A resin-laminated metal plate having a coating film on the surface layer was formed in the same manner as in Example 6, except that polyester (A-8) was used in Example 6.
Table 2 shows the characteristics of the resin laminated metal plate.

Comparative Example 7 A resin-laminated metal plate having a coating film on the surface layer was formed in the same manner as in Example 6, except that polyester (A-9) was used in Example 6.
Table 2 shows the characteristics of the resin laminated metal plate.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

From the results shown in Table 2, it is understood that the resin-laminated metal plates of Examples 1 to 6 have good antibacterial and antifungal properties. Furthermore, the durability of the resin-laminated metal plates of Example 5 and Example 6 was evaluated. Table 3 shows the results.

From Table 3, it was found that the resin laminated metal plates of Examples 5 and 6 had good durability.

[0116]

The metal plate of the present invention having excellent antibacterial properties and antifungal properties has good antibacterial properties and antifungal properties, and also has excellent durability in various environments.

Claims (9)

[Claims] 1. An antibacterial property comprising an antibacterial and antifungal layer containing a polymer substance and a hydrophilic substance each having a phosphonium base bonded to a main chain or a side chain and laminated on at least one surface of a metal plate. And a metal plate with excellent mold resistance. 2. An antibacterial / antifungal layer containing a hydrophilic polymer substance in which a hydrophilic substance is chemically bonded to a polymer substance in which a phosphonium base is bonded to a main chain or a side chain, is provided on at least a metal plate. A metal plate with excellent antibacterial and antifungal properties characterized by being laminated on one side. 3. The antibacterial property according to claim 1, wherein the polymer substance having a phosphonium base bonded to a main chain or a side chain has an acid group and a phosphonium base ionically bonded to the acid group. And a metal plate with excellent mold resistance. 4. A sulfonic acid group-containing aromatic dicarboxylic acid represented by the following general formula (1), wherein the polymer substance having a phosphonium base bonded to a main chain or a side chain has a dicarboxylic acid component and a glycol component as main components. 4. The metal plate having excellent antibacterial and antifungal properties according to claim 1, which is a polyester resin having an acid phosphonium base. Embedded image 5. A polyester resin represented by the following general formula (1):
5. A copolymerized polyester obtained by copolymerizing a phosphonium base of a sulfonic acid group-containing aromatic dicarboxylic acid represented by the formula (1) to 1 to 50 mol% with respect to all acid components.
A metal plate having excellent antibacterial and antifungal properties as described. Embedded image 6. The metal plate having excellent antibacterial and antifungal properties according to claim 1, wherein the hydrophilic substance is a polyalkylene oxide and / or a derivative thereof. 7. The hydrophilic polymer substance is obtained by graft-polymerizing a hydrophilic substance comprising a vinyl polymer having a hydrophilic group in a side chain onto the polymer substance. 4. A metal plate having excellent antibacterial and antifungal properties according to 4 or 5. 8. The polymer material according to claim 2, wherein the hydrophilic polymer substance is obtained by copolymerizing a compound capable of forming an ester containing a metal sulfonate group into the main chain of the polymer substance. Or a metal plate having excellent antibacterial and antifungal properties according to 5. 9. The method according to claim 1, wherein the metal plate is made of a material selected from the group consisting of aluminum, steel, and alloys each containing them as a main component.
5. A metal plate having excellent antibacterial and antifungal properties according to 5, 6, 7 or 8.