JPH09187886A - Coated metal plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the stainproofness by sequentially laminating a plastic film layer and a stainproof layer in this order at least on one surface of a metal plate. SOLUTION: As a metal plate, a stainless steel plate or various plated steel plate is preferably used. To make the adhesive properties of the metal plate and an adhesive layer more rigid, it is desired that the surface of the metal plate has a primer. As a plastic film layer, it is desirable to use a fluorine film having excellent mechanical characteristics, thermal characteristics and further excellent weather resistance and stainproofness. As the stainproof layer, a layer made of composition containing inorganic hydrophilic colloidal substance as a main component due to the durability, and particularly colloidal silica or alumina is desired. They are sequentially laminated at least on one surface of the metal plate with the plastic film layer and the stainproof layer in this order. Thus, the stainproofness and durability are excellent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coated metal plate. More specifically, it relates to a coated metal plate having excellent antifouling property.

[0002]

2. Description of the Related Art Various types of coated metal plates in which the surface of a metal plate is covered with a plastic film have been proposed depending on the combination of the characteristics of each base material. Such a coated metal plate has excellent durability, and furthermore, there are many scratches on the metal surface during the molding process, and there are many advantages such as being able to make a molded product rich in design, It is used for a wide range of applications such as building materials, home appliances, furniture, etc., but in particular, in recent years, there has been an increasing demand for building materials such as building exterior materials and roofing materials. For the application, for example, a coated metal plate using a fluorine film having the best weather resistance, antifouling property, heat resistance, etc. among plastic films has already been put into practical use, and durability, corrosion resistance, etc. have been proved. It's starting.
As such a coated metal plate, for example, JP-A-61-83 is used.
Japanese Patent Laid-Open No. 49, Japanese Patent Laid-Open No. H05-305694 and the like are disclosed.

However, when a conventional coated metal plate is exposed outdoors for a long period of time, even if it is a coated metal plate using a fluorine film, which is the most difficult to stain, adhesion of dust, dust, etc. will increase.
Dirt deposits cannot be easily removed with rainwater. For this reason, there is a concern that dirt may be less noticeable in appearance.

Accordingly, since there is no effective method for solving such inconvenience, it is the actual situation that no measures are taken in practice, but if necessary, the coating may be performed depending on the degree of contamination. A method of cleaning the film surface of the metal plate with a detergent or the like is adopted.

[0005]

However, in the case of the conventional coated metal plate, the surface of the film has to be washed regularly before washing, and a large amount of water is required because stains are hard to remove. And that work took a lot of effort. Further, there is a problem that the film surface is easily scratched during cleaning.

[0006] The present invention solves the above problems,
An object is to provide a coated metal plate having excellent antifouling properties.

[0007]

The coated metal plate of the present invention for this purpose comprises a metal film and a plastic film layer and an antifouling layer laminated in this order on at least one surface of the metal plate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The metal plate referred to in the present invention is iron,
Various alloys such as copper, aluminum, zinc and stainless steel, and various metal such as a metal or alloy laminated on the metal surface by plating or the like are plate-shaped or foil-shaped. In addition, the metal surface is subjected to various chemical treatments such as phosphoric acid treatment and chromic acid treatment, electrolytic chromic acid treatment, electrolytic treatment such as electric tin plating, and hot dipping such as hot tin plating and hot dip galvanizing. Further, it may be subjected to various surface treatments such as rust prevention treatment, hardness treatment, adhesion promotion treatment, and polishing. Among them, in the present invention, it is preferable to use a stainless steel plate, various plated steel plates, and particularly, as the plated steel plate, for example, a galvanized steel plate, an aluminum plated steel plate, a zinc-aluminum alloy plated steel plate, a nickel-based plated steel plate, a zinc-nickel based steel plate. An alloy plated steel plate, a stainless steel plated steel plate, a chrome plated steel plate, etc. can be used.

In the present invention, the metal plate may have an inorganic or organic coating layer on its surface. The inorganic coating layer is a layer made of a coating formed of ceramic, glass or the like by a vapor deposition method, a thermal spraying method, a baking method or the like, and examples thereof include enamel. Further, the organic coating layer is a layer formed of a polymer resin or a polymer resin containing a colorant formed by a laminating method, a coating method, or the like, and examples thereof include polyvinyl chloride, polyacrylonitrile, and polyester. Examples of the metal laminated plate include vinyl chloride coated steel plates and vinyl chloride laminated steel plates.

The thickness of the metal plate is not particularly limited, and generally 0.01 to 3 mm, preferably 0.1 to 1 mm can be used.

In the present invention, in order to make the adhesion between the metal plate and the adhesive layer stronger, it is desirable that the surface of the metal plate has a primer layer.

The primer layer is a layer having an adhesion promoting action made of, for example, a material selected from silane coupling agents, thermoplastic resins, curable resins and the like. In the case of a resin primer, those having less hydrophilic groups or hydrophilic components are preferable in terms of water resistance and moisture resistance of the primer layer, and specific examples thereof include thermoplastic resins such as polyester, polyamide, polyesteramide, and polyvinyl acetal. , Polyvinyl chloride, poly (meth) acrylic acid ester, polyimide, polyurethane, polycarbonate,
Polystyrene, polymethylpentene, polyolefin,
Halogenated polyolefin, alkyd resin, polyamideimide, silicon resin, fluororesin and the like, and copolymers and mixtures thereof can be used. Further, as the curable resin that is cured by light, heat, oxygen, etc., for example, phenol resin, melamine resin, epoxy resin, cross-linked organosilicon resin, etc. can be used. The resin primer is
From the viewpoint of water resistance, solvent resistance, heat resistance, abrasion resistance, mechanical strength and the like of the layer, it is preferable to use a thermosetting resin, and it is more preferable to use a thermosetting resin in combination so that crosslinking can be achieved.

In the present invention, among the above-mentioned primer agents, it is desirable to use a silane coupling agent, an epoxy resin, a polyester resin, or an acrylic copolymer resin. The solvent for the primer agent may be water-based, but alcohol-based, carboxylic ester-based, ketone-based,
It is also possible to use aliphatic hydrocarbons, alicyclic or aromatic hydrocarbons and mixtures thereof.

The thickness of the primer layer is not particularly limited,
0.01 to 100 μm is preferable, and 0.5 to 50 is particularly preferable.
Those in the range of μm are preferable in terms of uniform forming property of the primer layer, adhesion and the like.

Further, in the present invention, it is desirable to provide a printing layer on the surface of the metal plate or on the primer layer in order to give the coated metal plate an aesthetic appearance, a good design, and a high-class appearance. The printing layer is
Printed characters, patterns, etc. are formed by a suitable printing technique using various inks such as ultraviolet curable ink, electron beam curable ink, oil-based ink, water-based ink, thermal transfer ink ribbon, and electrophotographic toner.

The plastic film layer used in the present invention may be any plastic film, but typical ones are polyolefin film, polystyrene film, polyester film, polycarbonate film, triacetyl cellulose. Film, cellophane film, fluorine film, polyamide film, polyimide film, polyphenylene sulfide film, polyetherimide film, polyethersulfone film, polysulfone film, polyacrylonitrile film, polyvinyl acetate film, polyetheretherketone film, etc. alone or in combination The body can be used.

However, it is preferable to use a polyester film, a polypropylene film, a polyphenylene sulfide film, or a fluorine film alone or in combination from the viewpoint of mechanical properties, thermal properties, etc. Among them, fluorine having excellent weather resistance and antifouling property is used. Films are particularly preferred.

The material of the fluororesin film is not particularly limited, and various kinds can be used. Typical examples include tetrafluoroethylene polymer, ethylene-4fluoroethylene copolymer, tetrafluoroethylene-6fluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and 2 Vinylidene chloride polymer, 3
A fluorinated ethylene polymer, a fluorinated ethylene polymer, a chlorotrifluoroethylene polymer, or the like, or a copolymer or a mixture thereof can be used. However, mechanical properties, film formability,
From the viewpoint of processability, it is preferable to use a tetrafluoroethylene-9 fluoropropylene copolymer or an ethylene-4 fluoroethylene copolymer, among which an ethylene-4 fluoroethylene copolymer as a main component is used. Is particularly preferable. In addition, the main component means a substance which is 50% or more in the resin component, more preferably 70% or more, and may appropriately contain other substances. The resin to be added is not particularly limited, and for example, a polyolefin resin, an acrylic resin, or the like can be used.

In the plastic film, if necessary, an appropriate additive such as a heat resistance stabilizer, an oxidation resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, a pigment, etc. may be added in an amount that does not impair the effects of the present invention. Dyes, inorganic or organic fine particles, dispersants, coupling agents, fillers and the like may be added. Further, the plastic film may be used in any of unoriented, uniaxially oriented and biaxially oriented, but the oriented film is desirable when mechanical strength is required.

The thickness of the plastic film layer is not particularly limited, and an appropriate thickness can be set within the range of about 1 to 500 μm according to desired characteristics. Also, regarding the surface roughness and optical characteristics of the plastic film,
It is not particularly limited, and may be appropriately set to a desired value in consideration of required characteristics.

Further, in the present invention, the surface treatment or undercoating treatment on the surface of the plastic film improves the adhesion to the antifouling layer, the ultraviolet absorbing layer, the adhesive layer, water resistance, solvent resistance, etc. It can be preferably used. As the surface treatment, for example, corona discharge treatment (in air, in nitrogen,
Carbon dioxide gas, etc.), plasma treatment (high pressure, low pressure), alkali metal solution treatment, high frequency sputter etching treatment, etc. can be performed.

In the case of surface treatment, the treatment strength is not particularly limited and may be a desired value. As a measure of treatment strength, the surface leak index of the film measured according to JIS-K-6768 is used. Is preferably 35 dyn / cm or more, and more preferably 40 dyn / cm or more.

The antifouling layer of the present invention means a layer having a property of being unstainable or hard to be soiled, a property of easily removing stains even if soiled, and the antifouling layer having the function is as follows.
Fluorine-based, silicone-based, which gives water and oil to the surface
Wax-based compounds or resins, as well as a surfactant that imparts hydrophilicity to the surface and enhances the antistatic action and cleaning action,
Examples of the layer include an aqueous resin and the like, and a mixture and the like in which these are combined. However, in the present invention, it is most preferable to apply a layer composed of a composition containing an inorganic hydrophilic colloid substance as a main component, particularly from the viewpoint of antifouling property and durability. The layer containing the main component refers to a layer that is 30% or more in the antifouling layer, and may appropriately contain other substances.
The substance to be contained is not particularly limited, but in the present invention, especially when a surfactant, a lithium silicate and / or a silane derivative, a polymer resin binder, etc. are contained in the antifouling layer, the antifouling property is improved. It is more preferable because the property is improved. In the present invention, such an antifouling layer is provided on the surface of the film layer.

The inorganic hydrophilic colloidal substance in the present invention includes a metal colloid or an oxide colloid, depending on the element.
Obtained as a hydroxide colloid, a carbonate colloid, a sulfate colloid and the like. Typical examples are colloidal silica, colloidal alumina, and colloidal Fe (OH).
₂ , colloidal Sn (OH) ₄ , colloidal T
Examples include iO ₂ , colloidal BaSO _4, and colloidal lithium silicate. Two or more kinds of these colloidal substances may be used in combination. Incidentally, colloidal silica or colloidal alumina is particularly preferable as the inorganic hydrophilic colloid substance. The above colloidal substance is preferably an aqueous sol type.

As the substances added to the inorganic hydrophilic colloidal substance, the preferred surfactants in the present invention include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. Either is fine. However, it is preferable to appropriately select the surfactant in consideration of compatibility with the above-mentioned inorganic hydrophilic colloid, stability, and the like. For example, when colloidal silica is used, it is preferable to use an anionic surfactant and / or nonionic surfactant, and when colloidal alumina is used, a cationic surfactant and / or nonionic surfactant is used. Is preferred.

Further, in the lithium silicate and / or silane derivative which is a preferable substance to be added, the lithium silicate is obtained by melting silicon dioxide and a lithium salt such as lithium carbonate,
It is represented by the following general formula.

Li ₂ O.SiO ₂

It should be noted that lithium silicates having different water solubility can be obtained depending on the blending ratio of silicon dioxide and lithium salt. For example, when n in the general formula is 6 to 10 is insoluble in water, the lithium silicate in this case can be in a colloidal form and can be used as the above-mentioned inorganic hydrophilic colloid substance. Since the lithium silicates of to 5 are water-soluble, they can be used as a binder together with the above-mentioned inorganic hydrophilic colloid substance.

On the other hand, the silane derivative is represented by the following chemical formula 1.

[0030]

Embedded image In the formula, R ₁ is at least one reactive group selected from an amino group, an epoxy group, an epoxy group-containing group, a ureido group, an ammonium group and an ethylenically unsaturated bond-containing group.
It is an alkyl group or an aryl group having one unit. Also R ₂
And R ₃ each represent an alkyl group having 1 to 3 carbon atoms, and R ₂ and R ₃ may be the same or different. Furthermore, n has shown the integer of 1-3. The silane derivative may be appropriately selected depending on the type of the film support. For example, when the silane derivative is applied to a fluororesin-based base material such as ethylene-4 fluoroethylene copolymer, the following chemical formula 2 It is particularly preferable to use an epoxysilane derivative having a structure represented by 4 or a chlorine-based silane derivative having a structure represented by Chemical Formula 5 as a main component from the viewpoint of coatability or the adhesiveness to a resin substrate. (However, m = 1 to 10 is an integer, n = 0 or 1, R ₂ = a hydrocarbon residue selected from an alkyl group having 1 to 10 carbon atoms, R
₃ = represents a hydrocarbon residue selected from an alkyl group having 1 to 10 carbon atoms, a phenyl group and a cyclohexyl group). In particular, the use of lithium silicate or a silane derivative is preferable because the antifouling layer is unlikely to fall off or peel off and the antifouling effect can be maintained for a long period of time.

[0031]

Embedded image

Embedded image

Embedded image

Embedded image Further, as the polymer resin binder, polyester,
Examples include various substances such as polyvinyl chloride, poly (meth) acrylic acid ester, polyamide, polyurethane, and their copolymers and mixtures. Among them, those using poly (meth) acrylic acid ester are antifouling. It is more preferable in terms of layer adhesion and durability.

The amount of each component in the antifouling layer described above is not particularly limited, but from the viewpoint of antifouling property and durability, 0.5 to 15% by weight of a surfactant, lithium silicate and / or Alternatively, it is preferable that the silane derivative is in the range of 5 to 20% by weight and the inorganic hydrophilic colloid substance is in the range of 65 to 94.5% by weight, and water and / or alcohol and the like are preferably used as the medium of these compositions. When a polymer resin binder is used in combination, the addition amount is preferably 0.05 to 40 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the solid content.

As the antifouling agent, a particularly preferred composition is colloidal silica, an ether type nonionic surfactant, R ₁ is an epoxy group or an alkyl group having at least one epoxy group-containing group, and R ₂ is The dispersion medium is an alcohol having 1 to 4 carbon atoms, which contains the above-mentioned silane derivative in which R ₃ is an alkyl group having 1 to ₃ carbon atoms.

In the antifouling layer, if necessary, an additive such as an antifoaming agent, an ultraviolet absorber, a coatability improving agent, a pigment, a dye, an antioxidant or a crosslinking agent is added in an amount that does not impair the effects of the present invention. You may include an agent etc. The layer thickness of the antifouling layer is not particularly limited, but is preferably 0.01 to 15 μm, and more preferably 0.05 to 5 μm in terms of uniform layer formability, handleability, and antifouling property. It is preferable in terms of stain resistance.

The adhesive layer referred to in the present invention is not particularly limited, and a general adhesive layer, a heat-adhesive resin layer, a pressure-sensitive adhesive layer can be applied, and an adhesive layer having excellent adhesion to each base layer. Can be preferably used.

The general adhesive layer referred to in the present invention is, for example, a thermosetting adhesive such as an epoxy resin type, a urea resin type, a phenol resin type, a polyisocyanate type, a silicone resin type, and various acrylic and methacrylic acid. Examples thereof include thermoplastic adhesives such as ester-based, cyanoacrylic ester-based, and polyamide-based adhesives, and composite polymer-based adhesives such as epoxy resin / nylon resin-based and rubber / phenolic resin-based adhesives.

The term "thermoadhesive resin layer" as used in the present invention means a thermoplastic resin, a mixture thereof, or a resin to which a low molecular weight paraffin or the like is added, which is an adhesive resin that melts when heated and solidifies when cooled. Specifically, for example, ethylene and an ethylene-vinyl acetate copolymer resin as a copolymer thereof, an ethylene-acrylate copolymer resin or an ionomer resin, a polyamide resin, a polyester resin, a polypropylene resin, or a polyurethane resin. Examples include resins, vinyl chloride resins, polymethacrylic resins, and the like.

The adhesive layer referred to in the present invention is not particularly limited, but (1) polymers such as natural rubber, styrene-butadiene rubber, polyisobutylene, polychloroprene, polyacrylate rubber and polyvinyl ether rubber,
(2) A mixture of a polymeric material such as polyvinyl chloride, a copolymer of vinyl chloride and vinyl acetate, polyvinyl butyral, chlorinated rubber, hydrochloric acid rubber, polyacrylic acid ester and its copolymer and a plasticizer, (3) ) Rosin, rosin ester, coumarone resin, terpene resin, hydrocarbon resin, oil-soluble phenolic resin and other tackifiers, (4) fillers,
Representative examples thereof include various additives such as pigments, antioxidants and stabilizers, various combinations of the above (1) to (4), and silicone-based adhesives.

In the present invention, the thickness of the adhesive layer is not particularly limited and may be a desired value, but it is 1 to 500 μm.
m is preferably in the range of 10 to 100 μm in terms of uniform layer formation, processability such as lamination, and adhesion. If necessary, the adhesive layer may contain additives such as a plasticizer, a stabilizer, an inorganic or organic lubricant, and a flame retardant in an amount that does not impair the effects of the present invention.

In the present invention, it is particularly preferable to use a heat-adhesive resin layer as the adhesive layer in terms of the production of the coated metal plate of the present invention, and the composition containing the heat-adhesive resin as a main component is
It refers to that which is 50% or more in the adhesive layer. Among the heat-adhesive resins, polyester resins, vinyl chloride resins and polymethacrylic resins are preferably used in the present invention, and polymethacrylic resins are particularly preferred.

Here, as the polymethacrylic resin,
Resin mainly composed of polymethylmethacrylate, (1) polymethylmethacrylate homopolymer, or (2) methacrylic acid or an ester of methacrylic acid and an aliphatic alcohol having 2 to 8 carbon atoms, or acrylic acid or acrylic acid And a copolymer of one or more kinds of monomers selected from esters of aliphatic alcohols having 1 to 8 carbon atoms with methyl methacrylate and having methyl methacrylate of 60 mol% or more, preferably 85 mol% or more, Alternatively, (3) 50% by weight of the copolymer of (2) in (1), preferably 25% by weight
Examples thereof include those mixed within the following range. As a specific example, a homopolymer of methacrylic acid methyl ester or its and acrylic acid, methacrylic acid, or acrylic acid, methacrylic acid ethyl ester, butyl ester,
Examples thereof include copolymers with isopropyl ester and the like.

In the present invention, when the coated metal plate of the present invention is used outdoors, it is desirable to provide an ultraviolet absorbing layer in order to prevent deterioration of the base film layer due to ultraviolet rays and fading of printed matter and the like. The ultraviolet absorbing layer is not particularly limited as long as it is a layer having an ultraviolet absorbing ability. In the present invention, such an ultraviolet absorbing layer is preferably provided between the film layer and the antifouling layer or the adhesive layer.

In the present invention, as the ultraviolet absorbing layer,
A composition mainly containing a mixture of a general polymer binder and an ultraviolet absorber can be preferably used. The main component refers to one that is 50% by weight or more in the layer.

The polymer binder referred to in the present invention is a resin which is selected from a thermoplastic resin or a curable resin and which is soluble in an organic solvent or the like, and which has a small amount of hydrophilic groups or hydrophilic components is ultraviolet light. It is preferable in terms of water resistance and moisture resistance of the absorbent layer. Specific examples thereof include thermoplastic resins such as polyester, polyamide, polyesteramide, polyvinyl acetal, polyvinyl chloride, poly (meth) acrylic acid ester, polyimide, polyurethane, polycarbonate,
Polystyrene, polymethylpentene, polyolefin,
Examples thereof include halogenated polyolefin, alkyd resin, polyamideimide, silicon resin, fluororesin and the like, and copolymers and mixtures thereof. Further, as a curable resin that is cured by light, heat, oxygen, etc., for example, a phenol resin,
Examples thereof include melamine resin, epoxy resin, and crosslinked organosilicon resin. In the present invention, it is preferable to use a thermosetting resin from the viewpoint of water resistance, solvent resistance, heat resistance, abrasion resistance, mechanical strength, etc. of the ultraviolet absorbing layer, and it is more preferable to use a crosslinking agent in combination to achieve crosslinking. .

Further, in the present invention, it is preferable to use urethane resin and acrylic copolymer resin among the above-mentioned polymer binders, most preferable is acrylic copolymer resin, and among them, poly (meth) acrylic acid ester copolymer is preferable. It is a polymer. What is a poly (meth) acrylic acid ester copolymer?
A poly (meth) acrylic acid ester copolymer containing a reactive monomer, and such a reactive monomer includes:
As the functional group, for example, a carboxyl group (for example, (meth) acrylic acid, etc.), a hydroxyl group ((meth) acrylic acid 2
-Hydroxyethyl, etc.), amide group ((meth) acrylic acid amide, etc.), glycidyl group (glycidyl (meth) acrylate, etc.), amino group ((meth) acrylic acid 2-
Compounds such as diethylaminoethyl) and the like.

Further, the acrylic copolymer resin having a hydroxyl value of 40 or more, preferably 45 or more is preferable in terms of adhesion to a film support, coating film forming property, easy adhesion property and the like. The hydroxyl value in the present invention is defined as follows. That is, it is the number of mg of potassium hydroxide corresponding to the number of moles of hydroxyl groups contained in 1 g of the sample.

Examples of the organic solvent for the polymer binder include alcohol-based, carboxylic acid ester-based, ketone-based, aliphatic hydrocarbon, alicyclic or aromatic hydrocarbon-based solvents, and mixed systems thereof. Therefore, it is preferable to select a material that does not adversely affect the coating property and the like.

The ultraviolet absorber used in the present invention has excellent heat resistance, has good compatibility with the above-mentioned polymer binder, can be uniformly dispersed, has little coloring, and does not adversely affect the resin. Is desirable. As the ultraviolet absorber, various known applications such as benzophenone-based, benzotriazole-based, hindered amine-based, and oxalic acid-based can be applied, and specifically, bis (5
-Benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-4,4'-tetrahydroxy-benzophenone, 2,2'-dihydroxy-4,
4'-dimethoxy-benzophenone, 2,4-di-t-
Butylphenyl-3 ', 5'-di-t-butyl-4'-
Hydroxybenzoate, 2- (3 ', 5'-ditertariamyl-2'-hydroxyphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2
(2′-Hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2-ethoxy-2′-ethyl oxac acid bisanilide, 2,4-di-t
-Butylphenyl-3 ', 5'-di-t-butyl-4'
-Hydroxybenzoate, bis (2,2,6,6-
Examples thereof include tetramethyl-4-piperidyl) sebacate, dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, and the like.

The ultraviolet absorber is not particularly limited, and may be a single type or a combination of two or more types depending on the case. The content of the ultraviolet absorber in the layer is 0.01 to
It is preferably 50% by weight, more preferably in the range of 0.1 to 20% by weight. If the content is lower than the above range, it is difficult to obtain a sufficient ultraviolet shielding property, and if the content exceeds the above range, the uniform dispersibility tends to decrease.

In the present invention, the laminated thickness of the ultraviolet absorbing layer is
Although not particularly limited, it is preferably from 0.05 to 50 μm, and more preferably from 0.1 to 20 μm in terms of uniform forming property of the ultraviolet absorbing layer, adhesion and the like. If necessary, the ultraviolet absorbing layer may contain additives such as an antifoaming agent, a coatability improving agent, a thickener, an antistatic agent, and a dye in an amount that does not impair the effects of the present invention. .

In the present invention, it is particularly preferable to use an ultraviolet absorbing acrylic resin as the ultraviolet absorbing layer from the viewpoint of durability and the like, and the composition containing the ultraviolet absorbing acrylic resin as a main component is the ultraviolet light itself. 50% by weight in the absorption layer
This refers to the above, and other substances may be added as appropriate. The resin to be added is not particularly limited, and for example, a polyester resin, an acrylic resin, or the like can be used.

The ultraviolet-absorbing acrylic resin referred to in the present invention is a resin whose composition, production method and the like have already been disclosed, and the details thereof are described in JP-B-43-27737 and JP-A-63-139958. It is described in JP-A-2-180909 and JP-A-3-281685. Specifically, for example, a copolymer resin of a reactive benzophenone compound having an ultraviolet absorbing ability and an acrylic monomer having a polymerizable unsaturated group can be used. Here, the reactive benzophenone-based compound is a benzophenone-based monomer having an unsaturated group capable of copolymerization in the molecule, such as 2-hydroxy-4-methacryloxybenzophenone and 2-hydroxy-4- (2-hydroxy). −
3-methacryloxy) propoxybenzophenone, 2
-Hydroxy-4- (2-methacryloxy) ethoxybenzophenone, 2-hydroxy-4-vinyloxycarbonylmethoxybenzophenone and the like can be mentioned. Among them, 2-hydroxy-4-methacryloxybenzophenone and 2-hydroxy-4-from the viewpoint of polymerizability and properties.
Preference is given to using (2-methacryloxy) ethoxybenzophenone.

The acrylic monomer having a polymerizable unsaturated group is an alkyl acrylate represented by the following chemical formula 6 (R: hydrogen or methyl group, R'is an alkyl group having 1 to 18 carbon atoms), and Alkyl methacrylate, acrylic acid, methacrylic acid, β-hydroxy acrylate, β-hydroxy methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, polyoxyethylene glycol monomethacrylate, polyethylene polytetramethylene ether glycol monomethacrylate, dimethylaminoethyl Methacrylate, diethylaminoethylmethacrylate, acrylamide, methacrylamide, N-methylmethacrylamide, Nn-butoxymethylacrylamide, acid phosphooxyethyl Methacrylate, 3-chloro -
2-acid phosphooxypropyl methacrylate, 3
-Chloro-2-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, methoxypolyethylene glycol monomethacrylate, 3-acrylamide-2-methylpropanesulfonic acid, N-methylolacrylamide, N-methylol Methacrylamide, polyoxyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
At least one selected from dibromoneopentyl glycol methacrylate, tetramethylol methane triacrylate and the like can be mentioned.

[0054]

[Chemical 6] Above all, the copolymer is preferably an alkyl methacrylate or an alkyl acrylate in terms of its polymerizability, coating film properties, and the like, and examples thereof include methyl methacrylate and ethyl acrylate. Further, it is preferable to use a carboxyl group- or methylol group-containing acrylic monomer in terms of adhesion to the substrate.

In terms of the composition of the ultraviolet absorbing acrylic resin, 2-hydroxy-4-methacryloxybenzophenone or 2-hydroxy-4- (2-methacryloxy) ethoxybenzophenone and an acrylic resin are used as the reactive benzophenone compound. It is preferable in terms of characteristics that the monomer is mainly composed of a combination with methyl methacrylate. Further, when the acrylic monomer is contained in an amount of 20% by weight or more and 80% by weight or less, transparency and coating film characteristics are excellent, and therefore it is more preferable.

As the ultraviolet absorbing acrylic resin, particularly preferable one is UL manufactured by Yushisha Kogyo Co., Ltd.
S-935LH, ULS-680 etc. are illustrated.

The ultraviolet absorbing acrylic resin can be used as a water dispersion or an organic solvent, and when it is an organic solvent, examples of the organic solvent include alcohols, carboxylic acid esters, ketones, and aliphatic hydrocarbons. , Alicyclic or aromatic hydrocarbon systems and mixed systems thereof, and those which do not adversely affect the coatability are preferably selected. In the present invention, in order to further improve the adhesiveness, solvent resistance, heat resistance and the like of the adhesive layer and the ultraviolet absorbing layer, it is preferable that the layer contains a crosslinking binder. The cross-linking agent in the present invention,
A cross-linking agent for cross-linking with a functional group present in the resin or the like constituting the layer, for example, a hydroxyl group, a carboxyl group, a glycidyl group, an amide group, etc. to finally form a layer having a three-dimensional network structure, As a typical example, a methylolated or alkylolated urea-based, melamine-based, acrylamide-based, polyamide-based resin, and epoxy compound,
An isocyanate compound, a coupling agent, an aziridine compound, etc. can be used. In the present invention, of these, it is preferable to use an isocyanate compound because of its adhesiveness to the support and crosslinkability.

These cross-linking agents may be used alone or in combination of two or more depending on the case. The amount of the cross-linking agent to be added is appropriately selected depending on the kind of the cross-linking agent, but is usually preferably 0.01 to 50 parts by weight, more preferably 0.2 to 30 parts by weight, based on 100 parts by weight of the resin solid content. . Further, it is more preferable to use a crosslinking catalyst together with the crosslinking binder because crosslinking will proceed further. As the crosslinking catalyst, salts, inorganic substances, organic substances, acid substances, alkaline substances and the like can be used. The amount of the crosslinking catalyst added is preferably 0.001 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin solid matter. The coating agent containing the additive is crosslinked by heating, ultraviolet rays, electron beams, etc. after coating on the support.
Usually, the method of heating is common.

In the present invention, for example, in the production of the coated metal sheet of the present invention, when workability is deteriorated due to insufficient stickiness or slipperiness during laminating of the metal sheet and the film layer, for example, the adhesive layer It is desirable to incorporate inorganic or organic fine particles in the ultraviolet absorbing layer.

Examples of the inorganic particles include zinc carbonate, zinc oxide, zinc sulfide, talc, carion, mass / light weight or synthetic calcium carbonate, titanium oxide, silica, colloidal silica, lithium fluoride, calcium fluoride, barium sulfate. , Alumina, alumina sol, zirconia, calcium phosphate, natural or synthetic swelling or non-swelling mica, etc. can be used, and as the organic particles,
For example, polystyrene, polymethylstyrene, polymethoxystyrene, polyvinyl chloride, polyethylene, polypropylene, polyvinylidene chloride, polymethacrylate,
Polymethylmethacrylate, polychloroacrylate,
Styrene-divinylbenzene copolymer, melamine resin,
An epoxy resin, a phenol resin, a fluororesin, or the like can be used, and at least one selected from these can be used, but it is not particularly limited. Further, the fine particles may be in a hollow porous state or a non-hollow porous state. Further, the fine particles may be subjected to a treatment such as adding a functional group such as a glycidyl group or a methylol group to the surface thereof in order to improve the dispersibility in the resin.

The average particle size of the fine particles is 0.01 to 500 μm.
Are preferable, and those in the range of 0.1 to 50 μm are more preferable from the viewpoint of handleability, coatability and the like. The content of the fine particles in the layer is preferably 0.1 to 50% by weight,
5% by weight is more preferred. If the content is outside this range, workability is likely to be deteriorated and the adhesion of the laminated product is likely to be deteriorated.

Next, some examples of the method for producing a coated metal plate of the present invention will be described, but the present invention is not limited to these examples.

(1) In the film forming process of a plastic film, a base film is coated with each coating solution adjusted to a predetermined amount, and then dried to have an antifouling layer, an ultraviolet absorbing layer and an adhesive layer. Make a composite film. This is a method in which the composite film and a metal plate or a preheated metal plate are pressure-bonded or pressure-heat bonded with a laminating roll, passed through a heating open as required, and then cooled.

(2) After winding the plastic film as a single film, a coating-drying step is provided to remove the stain-proof layer,
A composite film having an ultraviolet absorbing layer and an adhesive layer is prepared. Hereinafter, a method similar to the above (1) is used.

(3) After a coating-drying process is provided on a metal plate to form a metal plate / adhesive layer composite, a plastic film on which an antifouling layer and an ultraviolet absorbing layer are formed is added by a laminating roll. This is a method in which pressure or pressure heat bonding is performed to integrate them.

(4) A method in which a plastic film is heat-sealed on a metal plate that has been subjected to adhesion promotion, and an antifouling layer is provided on the film surface after cooling.

The coating method is not particularly limited, and extrusion laminating method, melt coating method and the like may be used.
A method such as a gravure coating method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method or a metalling bar coating method can be used because a thin film can be coated at a high speed.

It should be noted that it is desirable that the conditions for drying the coating film and the conditions for heat and pressure bonding be such that they do not adversely affect the various characteristics of each substrate.

Next, when a thermo-adhesive resin layer is applied as the adhesive layer, the resin pellets are fed to an extruder and melted at a temperature above the melting temperature and below the temperature at which the resin decomposes, and the above-mentioned film is formed by an extrusion laminating method. A method of forming on the surface or a metal plate, or a method of uniformly dissolving a resin in an organic solvent to adjust to a predetermined amount and applying it on each layer or the metal plate can be preferably used. The coating method may be the same as that for forming the antifouling layer.

[0070]

[Method of measuring and evaluating characteristics] The characteristic value of the present invention is as follows.
According to the following measurement methods and evaluation criteria.

(1) Antifouling property JIS-A-1410 with the antifouling layer of the coated metal plate as the outside.
According to the above, the sample was exposed outdoors and the degree of dust adhering to the surface of the layer was compared and observed over time, and evaluated according to the following criteria. The location was about 5 m from the road, and the exposure period was 6 months.

◯: Good Δ: Slightly inferior (slightly noticeable stain) X: Poor (stainable stain is noticeable)

(2) Easy cleaning property The outdoor exposed sample of (1) above was washed with running water and evaluated as follows.

4: Dirt can be removed simply by applying water 3: Dirt can be wiped off with a cloth soaked in water 2: Dirt can be wiped off using a neutral detergent 1: Dirt will not stain and fall off

(3) Adhesion of Antifouling Layer The adhesion of the antifouling layer / base film layer was determined by applying cellophane tape (CT-24 manufactured by Nichiban Co., Ltd.) on the antifouling layer and using a hand roller. After crimping, apply cellophane tape 18
The layer was forcibly peeled in the direction of 0 °, the degree of peeling of the layer was observed, and the judgment was made as follows.

⊚: Very good (no peeling) ○: Good (peeling area less than 5%) Δ: Slightly inferior (peeling area 5% or more and less than 20%) ×: Poor (peeling area 20% or more)

(4) Bending workability The film-side of the coated metal plate is placed on the outside to perform the contact bending work. A cut was made in the bent portion to reach the surface of the metal plate with a knife, the degree of adhesion between layers was observed, and the decrease in adhesion due to bending was evaluated according to the following criteria.

◯: No decrease in adhesion Δ: Some decrease in adhesion X: No decrease in adhesion and peeling

[0079]

The present invention will be described with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

Examples 1 and 2 Fluorine resin film "TOYOFLON" ET having a thickness of 60 μm
Both sides of FE (manufactured by Toray Industries, Inc.) (Example 1) and a polyester resin film “Lumirror” T60 (manufactured by Toray Industries, Ltd.) having a thickness of 50 μm (Example 2) were treated with a treatment strength of 85 in air.
Corona discharge treatment was carried out at W · min / m ² , and one surface was made to use an antifouling agent and methanol as a diluting medium, and colloidal silica (Catalyst Kasei Co., Ltd. isopropyl alcohol dispersion “OSCAL”) (a), β- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane (b), polyoxyethylene (10 mol) -ularyl ether (c)
Each of them was mixed so that the solid content weight ratio was a: b: c = 85: 4: 11, and a uniform coating material with an active ingredient concentration of 20% by weight was applied, and the coating layer was dried at 100 ° C. to a thickness of 0. 0.3 μm
The antifouling layer was provided.

Further, toluene / methyl ethyl ketone (mixing ratio 1: 1) was used as a diluting solvent on the other surface, and "Vylon" 200 (Toyobo Co., Ltd.) as a saturated thermoplastic polyester resin was uniformly dissolved in this to obtain a concentration of 30. Apply a coating material of weight% and dry the coating layer at 120 ℃ for 2 minutes.
A composite film having m adhesive layers was prepared.

Next, as a metal plate, a steel plate having a thickness of 0.5 mm and having its surface subjected to galvanization is heated up to 150 ° C. in advance, and then the adhesive layer surface of the composite film is superposed on the metal plate, and 180 ° C. The laminated metal roll was pressed and heat-bonded to obtain a coated metal plate. The properties of the obtained coated metal plate are as shown in Table 1 and were excellent in each property.

Example 3 Based on Example 1, first, toluene / methyl ethyl ketone (mixing ratio 1: 1) was used as a coating material on the surface of the film subjected to corona discharge treatment, and a heat-crosslinking acrylic resin "Cotax" was used. Concentration 1 in which "LH681 (manufactured by Toray Industries, Inc.) and UV absorber" Adeka Stub "LA-31 (manufactured by Asahi Denka Co., Ltd.) were mixed at a solid content weight ratio of 90:10.
After applying 0% by weight of the uniform coating material, the coating layer was dried at 120 ° C. for 2 minutes to form an ultraviolet absorbing layer having a thickness of 7.0 μm. A coated metal plate was obtained in the same manner as in Example 1 except that the stain layer was applied. The properties of the coated metal plate were excellent in each property as shown in Table 1.

Example 4 Based on Example 1, toluene / methyl ethyl ketone (mixing ratio 1: 1) was used as a coating material on the side opposite to the side where the antifouling layer was provided, and a diluent solvent was used. After applying a uniform coating material having a concentration of 15% by weight, which is a mixture of Yushi Kogyo Co., Ltd. ULS-935LH), the coating layer is 1 at 120 ° C.
The coated metal sheet was dried by the same method as in Example 1 except that the ultraviolet absorbing layer having a thickness of 2.8 μm was provided and then the adhesive layer was provided on the ultraviolet absorbing layer by the same method as in Example 1. Obtained.
As shown in Table 1, the characteristics of the coated metal plate were excellent in each characteristic.

Example 5 In the coating material for the ultraviolet absorbing layer of Example 4, an isocyanate compound "Coronate" HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was used as a cross-linking agent for the resin solid content of the coating material.
A coated metal plate was obtained in the same manner as in Example 1 except that 5 parts by weight of was added. As shown in Table 1, the coated metal plate was excellent in each characteristic.

Example 6 Based on Example 1, in the antifouling layer coating material of Example 1, an acrylic ester adhesive "Cybinol" EK1005 (manufactured by Saiden Chemical Co., Ltd.) was used with respect to the solid content of the coating material. Was applied, and a coated metal plate was obtained in the same manner as in Example 1 except that the same amount of water was added and uniformly dispersed. As shown in Table 1, the characteristics of the coated metal plate were excellent in each characteristic.

Example 7 Based on Example 6, as a metal plate, the surface of the metal plate of Example 1 was coated with a silane coupling agent (Toray Dow Corning.
A coated metal plate was obtained in the same manner as in Example 6, except that the product was treated with a 1% aqueous solution of SH6040 manufactured by Silicone Co., Ltd., dried and then baked at 160 ° C. for 1 minute to form a primer layer. It was As shown in Table 1, the coated metal plate was excellent in each characteristic.

Example 8 Based on Example 6, toluene was used as a diluting solvent for the adhesive layer, and a silicone adhesive "Trefirm" SD45 was added thereto.
70 PAS and a crosslinking agent "Catalyst" SRX212 (both manufactured by Toray Dow Corning Silicone Co., Ltd.) (100: 0.9) were applied at a concentration of 20% by weight, and then the coating layer was at 120 ° C. And dried to form an adhesive layer having a thickness of 15 μm. Further, a commercially available fluorine-treated release film was laminated on the adhesive layer surface to obtain a composite film.

Next, the release film of the composite film was peeled off on the same metal plate as in Example 6 and the adhesive layer was laminated, and at room temperature,
The coated metal plate was obtained by pressure bonding with a laminating roll. As shown in Table 1, the coated metal plate was excellent in each characteristic.

Example 9 Based on Example 6, polyester urethane resin "Vylon" UR1400 (manufactured by Toyobo Co., Ltd.) was used as an adhesive layer in an isocyanate crosslinking agent "Coronate" H per resin solid content.
As the coating material and metal plate to which 5 parts by weight of X was added, a coated metal plate was prepared in the same manner as in Example 6 except that a 0.4 mm-thick stainless plate (SUS304) having a roughened surface and chromate treatment was applied. Obtained. As shown in Table 1, the characteristics of the coated metal plate were excellent in each characteristic.

Example 10 In a commercially available metal plate obtained by heat-sealing an ethylene-4fluoroethylene copolymer film on an aluminum plate, the same protection as in Example 1 was applied after corona discharge treatment on the film surface. A stain agent was applied in the same manner to obtain a coated metal plate. As shown in Table 1, the coated metal plate was excellent in each property.

Comparative Example 1 and Comparative Example 2 As shown in Table 1, it can be seen that the characteristics of the coated metal sheets prepared in Example 1 and Example 2 without providing the antifouling layer are inferior to the respective characteristics.

Examples 11 and 12, Comparative Example 3 A coated metal plate (Example 11) obtained by using a white steel plate having a thickness of 0.5 mm as the metal plate in Example 6 (Example 11), having a thickness of 0.5 mm as the metal plate A coated metal plate (Example 12) obtained by using a vinyl chloride laminated steel plate in which a white vinyl chloride film having a thickness of 200 μm was coated on a galvanized steel plate (Example 12) and the coated metal plate without an antifouling layer (Comparative Example 3) ), After 1 month of outdoor exposure, the whiteness of the surface of the coated metal plate was measured by a reflection method using an SM color computer (SM-6 manufactured by Suga Test Instruments Co., Ltd.). When the whiteness is represented by a ΔL value, Example 1
1 is 0.62, Example 12 is 0.58, and Comparative Example 3 is 7.
23, it can be seen that the coated metal plate of the present invention has excellent antifouling property.

[0094]

[Table 1]

[0095]

In the coated metal plate of the present invention, since the plastic film layer and the antifouling layer are sequentially laminated on at least one surface of the metal plate, the following excellent effects can be obtained. It was

First, the coated metal plate of the present invention has excellent antifouling properties and, moreover, its durability.

Further, in the coated metal sheet of the present invention, not only is the antifouling layer excellent in easy washability, but the weather resistance of the layer is exhibited without impairing the transparency.

Further, since the coated metal sheet of the present invention is excellent in formability, it does not cause peeling or tearing due to processing and can be processed with a large degree of processing deformation.

Since the coated metal sheet of the present invention has the above-mentioned excellent properties, it can be used in a wide range of materials such as ornamental parts, fixtures, cooking and processing equipment, kitchen equipment, indoor interior materials, etc. Although it can be used in various fields, it is particularly suitable for outdoor building materials such as roofing materials and wall materials.

Claims (11)

[Claims] 1. A coated metal plate, comprising a plastic film layer and an antifouling layer laminated in this order on at least one surface of the metal plate. 2. The coated metal plate according to claim 1, wherein an adhesive layer is provided between the metal plate and the plastic film layer. 3. The coated metal plate according to claim 2, wherein the adhesive layer is made of a composition containing a heat adhesive resin as a main component. 4. The ultraviolet absorbing layer is provided between the antifouling layer and the plastic film layer or between the plastic film layer and the adhesive layer, according to any one of claims 1 to 3. Coated metal plate. 5. The coated metal plate according to claim 4, wherein the ultraviolet absorbing layer is composed of a composition containing an ultraviolet absorbing acrylic resin as a main component. 6. The coated metal plate according to claim 1, wherein the metal plate has an inorganic or organic coating layer on its surface. 7. The coated metal plate according to any one of claims 1 to 6, wherein the metal plate has a primer layer and / or a printed layer on its surface. 8. The coated metal plate according to claim 1, wherein the antifouling layer is composed of a composition containing an inorganic hydrophilic colloid substance as a main component. 9. The coated metal plate according to claim 2, wherein the adhesive layer and / or the ultraviolet absorbing layer is crosslinked. 10. The coated metal plate according to claim 1, wherein the plastic film layer is composed of a composition containing a fluororesin as a main component. 11. The coated metal plate according to claim 10, wherein the fluororesin is composed of a composition containing ethylene-tetrafluoroethylene copolymer as a main component.