JPH11267516A - Metal plate obtained by laminating photocatalyst-supporting film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain effects of deodorization, stainproof, and others by using a photocatalyst-supporting film having photocatalytic activity which can decompose a specified quantity of triolein when irradiated with a specific quantity of ultraviolet rays in a UV-A area under specified environmental conditions, when a photocatalyst supporting film is laminated on the surface of a metal plate. SOLUTION: A polymer film having photocatalytic activity which can decompose at least 5 μg/cm<2> .day of triolein when irradiated with 3 mW/cm<2> of ultraviolet rays in a UV-A area in the atmosphere at 25 deg.C at 70% relative humidity is laminated on the surface of a metal plate by heat-press so that the metal plate on which a photocatalyst-supported film is laminated which has good effects of deodorization, stainproof, and others is obtained efficiently. The photocatalyst-supported film to be used is a polymer film on which a photocatalyst layer is supported through an adhesive layer, and the polymer film is preferably a film in which at least two kinds of resin films are laminated. The polymer film comprises a polycarbonate resin and others.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a metal plate, a resin-coated metal plate obtained by laminating a photocatalyst-supporting film having effects such as deodorization, antifouling, antibacterial and antifungal by heating and pressing. The present invention relates to a coated metal plate or an enameled metal plate, a method for producing them, and an application product thereof.

[0002]

2. Description of the Related Art Titanium oxide as an n-type semiconductor is known as a photocatalyst which causes various chemical reactions such as sterilization and decomposition of organic substances by the energy of ultraviolet rays. Various methods for supporting a photocatalyst on glass, metal, plastic, tile, and the like have been proposed (JP-A-62-68661, JP-A-5-309267, EP633064, USP488).
8101). However, a metal plate laminated with a film carrying a photocatalyst, especially a metal plate laminated with a photocatalyst-carrying film carrying a photocatalyst on a widely used polycarbonate resin or woven fabric reinforced polyvinyl chloride resin without reducing the catalytic activity Is not known, and
There is no report on a method for effectively utilizing the photocatalytic action of a metal plate laminated with such a photocatalyst-supporting film to maintain deodorant, antifouling, antibacterial, and antifungal properties for a long period of time.

Conventionally, a resin plate such as a polycarbonate sound insulation wall installed outdoors and a fiber reinforced resin impregnated with polyvinyl chloride are apt to adhere to dust and soot in the outside air, and usually have a thickness of 2 to 3 mm.
In a month, the color changed to black and contamination proceeded. In addition, mold is easily generated due to a plasticizer component contained in a large amount in the polyvinyl chloride resin, and a method of coating the surface with a fluororesin has been adopted as a countermeasure. However, the fluororesin coat has a drawback that oil stains such as soot and smoke easily adhere to the surface because it increases the water repellency of the surface and increases the lipophilicity, as is conventionally known. Titanium oxide has the property of exhibiting hydrophilicity when irradiated with ultraviolet light in the air. By utilizing this effect, the surface of the outdoor installation structure is made hydrophilic, and the oil mist attached A method has also been disclosed for facilitating washing of oils such as water with water (especially rainwater) (JP-A-63-100042, WO96 / 29375). These methods utilize a phenomenon in which water is easily wetted on the surface by making the physical properties of the surface of the structure hydrophilic, and as a result, an oil component floats off the surface and flows down. However, in the method according to the disclosed technology, the photocatalytic decomposition action of the oil attached to the surface is poor, so that a large amount of dirt such as exhaust gas of a diesel vehicle is strongly adhered to a road noise barrier, which is limited in practical use in practical use. There was a big problem.

[0004] WO97-134 has a photocatalyst composed of a photocatalyst particle composite containing a metal oxide gel via a bonding layer made of an acrylic silicon resin added with polysiloxane on a resin substrate by a dipping method or a spray method. An example in which a layer is provided to maintain high photocatalytic activity and excellent durability is disclosed. However, according to the method according to the disclosed technology, it is possible to use a laminated film in which an adhesive is applied to the back surface of the photocatalyst-carrying film. However, when the film is formed at a high speed, the curing of the adhesive layer is insufficient, so that a problem arises in the application of the photocatalyst.

Further, by providing a photocatalyst layer composed of a photocatalyst particle composite containing a metal oxide gel on a polyester film via an adhesive layer composed of an acrylic silicon resin to which polysiloxane is added, high photocatalytic activity and excellent photocatalytic activity can be obtained. The photocatalyst-carrying film maintaining the durability is also described in WO9
As disclosed in JP-A-7-134, polyester films are generally very difficult to be laminated by heating and pressing, and are not suitable for use for the purpose of the present invention.

Further, the composition of the disclosed coating solution has a problem that drying and curing tend to be insufficient at the time of high-speed film formation, and the coated surface tends to stick to the back surface. In particular, a film that can be laminated by heating and pressing has a low heat resistance temperature and heat deformation temperature of 100 ° C. or less.
In the coating solution and the coating method disclosed in 97-134,
It is difficult to perform high-speed film formation on a film suitable for such thermal lamination, and there is a problem that the photocatalytic activity is lost depending on the thermal lamination conditions. Also,
In the case of a coating method such as a dipping method or a spraying method, there is a problem that in the case of a large flat metal plate, it is often difficult to apply the method due to restrictions on production equipment, film forming speed, and drying speed. In particular, a metal plate having a width of 1 m or more has a problem that a large-sized dryer is required, and a drying time and a heat capacity are required for 30 minutes or more.

When a photocatalyst is supported on a metal plate, a coated metal plate, a resin-coated metal plate, or an enameled metal plate for the purpose of antifouling, antibacterial, and deodorizing, a photocatalyst layer is provided via an adhesive layer. Providing the photocatalyst structure directly on the surface of a metal plate or the like can be considered as one method. However, in this method, the drying treatment time after coating is much longer than that in the case of film formation. In the case of film formation, the drying treatment time is on the order of seconds. The film has a heat capacity problem and requires at least a processing time in minutes.If the surface is flat, film lamination is more productive than the film lamination time, and the adhesive layer and photocatalyst layer Depending on the pH of the coating solution, the metal plate is eroded and rusted when the coating is dried, and when the coating process on the metal plate becomes larger than 1 m wide, it is impossible to form a uniform film by dip coating or spray coating. There is a problem that it is difficult and the thickness unevenness of the film easily occurs, and there is a drawback that the kind and size of the applicable metal plate are limited.

[0008]

An object of the present invention is to provide a metal plate, a resin-coated metal plate, and a coated metal plate on which a photocatalyst-supporting film having excellent deodorizing, antifouling, antibacterial, and antifungal effects is laminated. Another object of the present invention is to provide an enameled metal plate.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have found that a transparent film carrying a photocatalyst can be efficiently and thermally laminated at a high speed. We have been conducting intensive studies on items such as not being reduced by laminating, and being able to support photocatalysts on films made of a material that can be laminated at high speed with good productivity. At an atmospheric temperature of 25 ° C and a relative humidity of 70%, 5 μg of triolein when irradiated with 3 mW / cm ² of ultraviolet light in the UV-A region
It has been found that the above-mentioned problems can be solved by laminating a polymer resin film having photocatalytic activity capable of decomposing at least / cm ² · day on the surface of a metal plate by heating and pressurizing treatment, thereby completing the present invention.

[0010] That is, the present invention is obtained by laminating a photocatalyst-supporting film made of a polymer resin film having a photocatalyst layer supported thereon via an adhesive layer on the surface of a metal plate by a heating and pressurizing treatment, and Medium temperature 25
UV rays in the UV-A region at a temperature of 70 ° C. and a relative humidity of 70%.
5 μg / cm of triolein when irradiated with mW / cm ^2
The present invention relates to a metal plate laminated with a photocatalyst-supporting film, which has photocatalytic activity capable of decomposing for at least ² days.

The present invention also provides that the polymer resin film is a film obtained by laminating two or more resin films, and the polymer resin film is a polycarbonate resin, two or more polymethyl methacrylate resins or polyacrylate resins. Is a resin selected from the group consisting of copolymer resins, polyvinyl chloride resins, and cellophane resins; the thickness of the polymer resin film is 5 to 200 μm; and the adhesive layer is a silane coupling agent as a curing agent. And an adhesive layer coating solution containing an agent.
A silicon-modified resin containing 0% by weight or a silicon-modified resin containing 5 to 30% by weight of colloidal silica;
A coating solution containing 0% by weight of a coating solution containing 0.1 to 5% by weight of a silane coupling agent as a curing agent based on the coating solution is used, and a monoalkyltrimethoxysilane is used as the coating solution of the adhesive layer. Alternatively, a coating solution containing 1 to 10% by weight of a polysiloxane, which is a hydrolysis product thereof, and 0.1 to 5% by weight of a silica sol, and a silane coupling agent as a curing agent in an amount of 0.1 to 5% by weight based on the coating solution. %, And the thickness of the adhesive layer is 0.1%.
5 to 5 μm, the photocatalyst layer contains 1 to 10% by weight as a solid content of a metal oxide sol and 1 to 10% by weight of a titanium oxide sol as a solid content, and the photocatalyst layer contains 1 to 10% by weight of a silica sol. %, Containing 1 to 10% by weight of a monoalkyltrimethoxysilane or a hydrolysis product thereof, and 1 to 10% by weight of a titanium oxide sol, wherein the thickness of the photocatalyst layer is 0.1 to 5 μm. That the metal plate is one type of metal plate selected from an iron plate, a steel plate, an aluminum plate, and an aluminum alloy plate; and that the metal plate is a material selected from the group consisting of polyvinyl chloride resin, polyethylene terephthalate resin, and polymethyl methacrylate resin. 1 selected from
A resin-coated metal plate, a coated metal plate, or an enameled metal plate coated with a single layer or a multi-layer by two or more types of resins, or the shape of the metal plate is plate-like, tubular,
Or a metal plate obtained by laminating the photocatalyst-carrying film, wherein the metal plate has a corrugated shape.

Further, the present invention provides a method for applying and drying an adhesive layer coating solution containing a silane coupling agent as a curing agent to a polymer resin film, and then applying and drying a photocatalytic layer coating solution on the adhesive layer. A photocatalyst supporting film comprising a photocatalyst supporting film prepared by supporting a photocatalyst layer on a polymer resin film via an adhesive layer, and laminating the photocatalyst supporting film on the surface of a metal plate by heating and pressing is provided. The present invention relates to a method for manufacturing a laminated metal plate. Further, the present invention provides a reflector for lighting equipment, an outdoor sign or an outdoor sign, a household electrical appliance, a guardrail or a road, wherein the metal plate obtained by laminating the photocatalyst-supporting film described above is used at least in part. Regarding signs.

Further, the present invention is a coating agent for a photocatalyst adhesive layer used for preparing a photocatalyst-supporting polymer resin film in which a photocatalyst layer is supported on a polymer resin film via an adhesive layer. A coating liquid for an adhesive layer containing 50% by weight of a silicon-modified resin or 2 to 20% by weight of a silicon-modified resin containing 5 to 30% by weight of colloidal silica, or monoalkyltrimethoxysilane or a hydrolysis product thereof 1 to 10% by weight of polysiloxane and 0.1 to 5% by weight of silica sol
The present invention relates to a coating agent for a photocatalytic adhesive layer, wherein a silane coupling agent as a curing agent is added in an amount of 0.1 to 5% by weight based on the coating solution.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A metal plate on which a photocatalyst-carrying film of the present invention is laminated is prepared, for example, by applying and drying an adhesive layer coating solution containing a silane coupling agent as a curing agent to a polymer resin film. A coating solution of the photocatalyst layer is applied to the adhesive layer and dried to prepare a photocatalyst supporting film having the photocatalyst layer supported on the polymer resin film via the adhesive layer. It can be manufactured by laminating on the surface. FIG. 1 shows a schematic diagram of a cross section of a metal plate on which the photocatalyst-supporting film of the present invention is laminated.

The polymer resin film of the present invention may be made of a polycarbonate resin, a copolymer resin of two or more polymethyl methacrylate resins or polyacrylate resins, a nylon resin, a polyamide resin, a polyimide resin, a polyacrylonitrile resin, a polyurethane resin. Resin, polyvinyl chloride resin, cellophane resin, polyvinyl alcohol resin, vinyl acetate-ethylene copolymer resin, or ethylene-vinyl alcohol copolymer resin, may include a film made of a resin selected from among, When coating and forming an adhesive layer or a photocatalyst layer, it is not preferable to obtain a uniform and uniform photocatalyst-carrying film due to stretching or wrinkling of the film. Can maintain tensile elongation and elasticity to withstand tension Preferably has a material and thickness.

Among these, polycarbonate resins,
A film composed of a copolymer resin of two or more polymethyl methacrylate resins or polyacrylate resins, a polyvinyl chloride resin, or a cellophane resin can be particularly preferably used, and a photocatalyst-supporting film using these resins has photocatalytic activity, durability, It can be said that it is excellent in terms of film forming property, laminating property, price and the like. Also, 2 of these films
By using a film obtained by laminating more than one kind, it is possible to greatly improve the properties that the film carrying the photocatalyst should have, especially weather resistance, heat resistance, moisture permeability, etc. The ability to design and change the properties of the film carrying the photocatalyst is extremely advantageous for practical use.

The thickness of the polymer resin film to be used is preferably 5 to 200 μm, and if the thickness is less than 5 μm, it becomes difficult to form the adhesive layer and the photocatalyst layer according to the present invention. This is not preferable because it may be difficult or the cost may increase.

In the present invention, the photocatalyst-supporting polymer resin film laminated on the metal plate has a structure in which an adhesive layer is provided between the photocatalyst layer and the film, as shown in FIG. The adhesive layer provided between the photocatalyst layer and the film is formed by applying and drying an adhesive layer coating solution on the film, and the action of firmly adhering the photocatalyst layer to the film and the action of the film or film. It has the function of preventing the photocatalytic activity from decreasing due to the plasticizer component diffused from the laminated polymer resin, preventing the film from deteriorating due to the photocatalytic action, and the adhesive layer itself is not easily degraded by the photocatalytic action. Have.

The adhesive layer coating solution in the present invention is particularly preferably a solution containing a silane coupling agent as a curing agent. By incorporating the silane coupling agent into the adhesive layer coating solution, the adhesive layer at the time of film formation can be used. The photocatalytic activity in the case of laminating the photocatalyst carrying film on the surface of the metal plate by heating and pressing is not only possible because it promotes the curing of the film and enables the film to be wound without sticking to the back surface, enabling high-speed film formation. To prevent
The photocatalytic activity of the photocatalyst-supporting film before lamination can be maintained.

As the adhesive layer coating solution in the present invention, for example, a silicon-modified resin containing 10 to 50% by weight of polysiloxane or 5 to 30% by weight of colloidal silica is used.
Examples of the coating liquid include a coating liquid containing 2 to 20% by weight of a silicon-modified resin to which a silane coupling agent is added in an amount of 0.1 to 5% by weight based on the coating liquid.

In the case of a silicon-modified resin such as an acrylic silicon resin or an epoxy silicon resin having a polysiloxane content of less than 10% by weight, or a silicon-modified resin having a colloidal silica content of less than 5% by weight, the photocatalyst layer at the time of irradiation with light is used. In places where ultraviolet light intensity is strong such as outdoors, the adhesion layer is deteriorated by the photocatalyst, and the photocatalyst layer is easily peeled off. On the other hand, in the case of a silicon-modified resin having a polysiloxane content of more than 50% by weight or a colloidal silica content of more than 30% by weight, the adhesion between the adhesive layer and the carrier becomes poor or the adhesive layer becomes porous. The photocatalyst is more easily peeled from the film due to poor adhesion between the base film and the adhesive layer.

In the present invention, the adhesive layer coating solution is a coating solution of a monoalkyltrimethoxysilane or a polysiloxane, which is a hydrolysis product thereof, and silica sol, and a silane coupling agent as a curing agent is a coating solution. An example of the coating liquid is 0.1 to 5% by weight. As the monoalkyltrimethoxysilane that can be used, monomethyltrimethoxysilane and monoethyltrimethoxysilane are preferable. Further, as the silica sol, those having a fine primary particle diameter are preferable, and particularly when obtaining a transparent film, those having a diameter of 20 nm or less are preferable.
The coating liquid contains 1 to 10% by weight of a monoalkyltrimethoxysilane or a polysiloxane that is a hydrolysis product thereof.
And 0.1 to 5% by weight of silica sol,
It is preferable from the viewpoint of adhesiveness and catalytic activity. The ratio of the monoalkyltrimethoxysilane or a hydrolysis product thereof to the silica sol is preferably 20/80 to 60/40 by weight, and an acid catalyst such as a mineral acid can be added to promote curing.

Regardless of whether the coating liquid for the adhesive layer is a polysiloxane-silicon-modified resin or colloidal silica-silicon-modified resin, or a monoalkyltrimethoxysilane-silica sol, the silane coupling agent added as a curing agent is It is desirable to add 0.1 to 5% by weight to these coating solutions. If the addition amount of the silane coupling agent is less than 0.1% by weight based on the coating solution, a blocking phenomenon occurs in which the coated surface sticks to the back surface of the film when the film is dried and then wound up, and the photocatalytic layer is coated. It is not preferable because it becomes difficult. On the other hand, when the addition amount of the silane coupling agent is 5% by weight or more based on the coating solution, it is not preferable because phenomena such as too fast curing and gelation of the solution during film formation occur. In addition, by adding 0.1 to 5% by weight of the silane coupling agent to the coating solution, the photocatalytic activity decreases when the photocatalyst-carrying film is laminated on the surface of the metal plate by heating and pressing. In addition, the photocatalytic activity of the photocatalyst-carrying film before lamination can be maintained.

In the present invention, among the adhesive layer coating liquids, in particular, a silicon-modified resin containing 10 to 50% by weight of polysiloxane or a silicon-modified resin containing 5 to 30% by weight of colloidal silica is preferably used. An adhesive layer coating liquid containing -20% by weight, or 1-10% by weight of a monoalkyltrimethoxysilane or a polysiloxane which is a hydrolysis product thereof and 0.1-5% by weight of a silica sol
An adhesive layer coating solution obtained by adding a silane coupling agent as a curing agent in an amount of 0.1 to 5% by weight based on the coating solution is referred to as a coating agent for a photocatalytic adhesive layer. The agent is used for preparing a photocatalyst-supported polymer resin film in which a photocatalyst layer is supported on a polymer resin film via an adhesive layer as described above.

The silane coupling agent has the general formula:
RSi (X) ₃ , (R) ₂ Si (X) _2, etc. (where R represents an organic functional group and X represents a chlorine atom or an alkoxy group).
Wherein R is a methyl group, an ethyl group, a vinyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ- (2-aminoethyl) aminopropyl group , Γ-chloropropyl group, γ
-Mercaptopropyl group, γ-aminopropyl group, γ-
In the formula, X represents a chlorine atom, a C1 to C5 alkoxy group such as a methoxy group, an ethoxy group or a β-methoxyethoxy group.

The durability of the coating solution for the adhesive layer, especially the coating agent for the photocatalytic adhesive layer, is improved by mixing a light stabilizer and / or an ultraviolet absorber for the purpose of suppressing deterioration due to photocatalysis. Can be done. As the light stabilizer, a hindered amine type is preferable, but other light stabilizers can also be used. As the ultraviolet absorber, a triazole-based ultraviolet absorber or the like can be used. The amount of addition is 0.005% by weight or more and 10% by weight or less, preferably 0.01% by weight or more and 5% by weight or less based on the coating solution for the adhesive layer, particularly the coating agent for the photocatalytic adhesive layer. By adding a light stabilizer and / or an ultraviolet absorber to the adhesive layer, particularly the coating agent for the photocatalytic adhesive layer, it becomes possible to improve the weather resistance of the polymer resin film supporting the photocatalyst, especially outdoors. It is advantageous when used. The surfactant is contained in the coating solution for the adhesive layer, particularly the coating agent for the photocatalytic adhesive layer, in an amount of 0.00001% by weight to 0.1% by weight.
By adding 1% by weight, a good metal plate laminated with a good photocatalyst-supporting film can be obtained.

As a method for applying the coating solution for the adhesive layer, particularly the coating agent for the photocatalytic adhesive layer, to the film, the coating solution for the adhesive layer is applied by a gravure printing method, a microgravure printing method, a comma coating method, a roll coating method, a reverse roll coating method. , A bar coating method, a kiss coating method, a flow coating method, and a drying method. The drying temperature varies depending on the coating method, the solvent, the type of resin of the film, and the thickness of the film, but is generally preferably 150 ° C. or lower. Also, the thickness of the adhesive layer is desirably 0.5 μm or more. When the thickness is less than 0.5 μm, the effect of firmly adhering the photocatalyst layer to the film is poor, and the photocatalyst layer is likely to peel off during long-term use. In addition, although there is no particular problem when the thickness of the adhesive layer is large, drying during film formation is insufficient, so that unevenness in film formation is likely to occur or the film formation cost is increased. 5 μm or less is preferable.

The photocatalyst-supporting polymer resin film to be laminated on a metal plate in the present invention has a structure in which a photocatalyst layer is provided on an adhesive layer, as shown in FIG.
The photocatalyst layer is, for example, a metal oxide sol having a solid content of 1%.
-10% by weight, titanium oxide sol as a solid content of 1-10
It can be formed by applying and drying a photocatalyst layer coating solution containing a weight% on the adhesive layer. The metal oxide sol in the photocatalyst layer coating solution not only fixes the titanium oxide sol and firmly adheres to the adhesive layer, but also has an adsorptive property because the gel obtained by drying the metal oxide sol is porous. It also has the effect of increasing the photocatalytic activity. The ratio of the metal oxide sol to the titanium oxide sol in the photocatalyst coating solution is 25 /
75-95 / 5 is preferred. If the metal oxide sol is less than 25%, the adhesion to the adhesive layer will be insufficient, while if it is more than 95%, the photocatalytic activity will be insufficient. When the specific surface area of the gel obtained by drying the metal oxide sol is 100 m ² / g or more, the adhesiveness becomes stronger and the catalytic activity is improved. As a material, a metal oxide sol of silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, and tungsten is preferable.
A sol obtained by mixing these or a composite oxide sol prepared by a method such as a coprecipitation method may be used.

When the metal oxide sol is mixed with the titanium oxide sol, it is preferable to mix the sol in a sol state or at the raw material stage before preparing the sol. Methods for preparing the sol include a method of hydrolyzing a metal salt, a method of neutralizing and decomposing, a method of performing ion exchange, a method of hydrolyzing a metal alkoxide, and the like. Titanium oxide sol is uniformly dispersed in the sol. Any method can be used as long as it can be obtained in a state where it is placed. However, the presence of a large amount of impurities in the sol adversely affects the adhesiveness and catalytic activity of the photocatalyst. Therefore, it is preferable to use a sol containing a small amount of impurities. In particular, when an organic substance is present in the gel obtained by drying the sol at 5% or more, the photocatalytic activity is reduced. In particular, when a photocatalyst layer containing an oxide sol of zirconium or aluminum is used, it passes a tape peeling test after a boiling water test for 15 minutes in tap water or 168 hours in a 5% aqueous solution of sodium carbonate. It is particularly preferable because a material that passes the tape peel test after the immersion test is obtained.

Further, as the photocatalyst layer, silica sol was
A photocatalyst layer coating solution comprising a mixture containing 10% by weight, 1 to 10% by weight of a monoalkyltrimethoxysilane or a hydrolysis product thereof, and 1 to 10% by weight of a titanium oxide sol is applied to the adhesive layer and dried. Those obtained can also be particularly preferably used. As the monoalkyltrimethoxysilane, methyltrimethoxysilane and methyltriethoxysilane can be particularly preferably used. The mixing ratio of the silica sol to the monoalkyltrimethoxysilane or its hydrolysis product is preferably 100/0 to 60/40 by weight, and the ratio of the titanium oxide sol to the silicon compound component is titanium oxide / silicon compound. 5 / 95-75 by weight ratio
/ 25 is preferred. When the ratio of the silicon compound is 95% or more, the photocatalytic activity decreases, and when the ratio is 25% or less, the adhesiveness to the adhesive layer decreases.

As the photocatalyst in the photocatalyst layer, TiO ₂ ,
ZnO, SrTiO ₃ , CdS, GaP, InP, Ga
As, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta
₂ O ₅ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O,
SiC, SiO ₂ , MoS ₂ , InPb, RuO ₂ , Ce
O _{2 and the} like can be exemplified, and all known ones in which a metal and a metal oxide such as Pt, Rh, RuO ₂ , Nb, Cu, Sn, and NiO are added to these photocatalysts can be used. As the content of the photocatalyst in the photocatalyst layer increases, the catalytic activity increases, but is preferably 75% by weight or less from the viewpoint of adhesiveness. In order to further improve antibacterial and antifungal properties, the titanium oxide photocatalyst in the photocatalyst layer is 0.05 to
5% by weight of silver or copper metal or metal compound can also be added. If the addition amount is less than 0.05% by weight,
Since the effect of improving the antifungal property is poor and the photocatalyst layer is discolored at 5% by weight or more, it may be difficult to use depending on the color or pattern of the resin laminated with the film.

In order to form the photocatalyst layer on the adhesive layer, a suspension in which the photocatalyst is dispersed in a metal oxide sol or metal hydroxide sol solution is used, and a coating method similar to that for forming the adhesive layer is used. Can be coated. The photocatalyst may be dispersed in a state of a precursor solution of the metal oxide sol or the metal hydroxide sol, and may be hydrolyzed or neutralized and decomposed at the time of coating to form a sol or a gel. When using a sol,
An acid or alkali deflocculant may be added for stabilization. In addition, a surfactant or a silane coupling agent of 5% by weight or less with respect to the photocatalyst may be added to the sol suspension to improve adhesion and operability. The addition of the agent prevents a decrease in photocatalytic activity when the photocatalyst-supporting film is laminated on the surface of the metal plate by heating and pressing, and cannot maintain the photocatalytic activity of the photocatalyst-supporting film before lamination. The drying temperature at the time of forming the photocatalytic layer varies depending on the coating method, the resin material of the film and the resin material in the adhesive layer, but is generally preferably 150 ° C. or lower.

The photocatalyst layer has a higher activity as the thickness is larger, but hardly changes when the thickness exceeds 5 μm. 5
Even when the thickness is 0.1 μm or less, the catalyst layer exhibits high catalytic activity and shows light-transmitting properties, so that the catalyst layer becomes inconspicuous. Therefore, high activity cannot be expected. The thickness of the photocatalyst layer is set to 0.1 μm or more and 5 μm or less,
In addition, when photocatalyst particles having a crystal particle diameter of 40 nm or less and a metal oxide gel or a metal hydroxide gel having a specific surface area of 100 m ² / g or more are used, a metal plate or resin having a high photocatalytic activity and a base film laminated thereon can be obtained. It is preferable from the viewpoint of aesthetics because it does not impair the texture of the coated metal plate, the coated metal plate, or the enameled metal plate.

In the present invention, as the metal plate on which the photocatalyst-carrying film is laminated by heating and pressing,
Any commonly used metal plate can be used, and examples thereof include an iron plate, a steel plate, a plated steel plate, an aluminum plate, and an aluminum alloy plate. As such a metal plate, a simple metal plate can be used as it is, but a single layer of one or more resins selected from polyvinyl chloride resin, polyethylene terephthalate resin, polymethyl methacrylate resin and the like can be used. Alternatively, a metal plate coated with multiple layers, a coated metal plate coated with paint, an enameled metal plate, or the like can be preferably used. The shape of the metal plate may be any shape such as a plate shape, a tubular shape, a corrugated shape, etc., as long as the photocatalyst supporting film can be laminated.

As a method of laminating the photocatalyst-supporting polymer resin film on various metal plates, a method of laminating a metal plate, a coated metal plate, a resin-coated metal plate, or an enameled metal plate while heating and pressing with a hot roll or the like, The method of laminating a photocatalyst-supporting polymer resin film by heat and pressure treatment using the heat of heat treatment in the production of a coated metal plate, a resin-coated metal plate, or an enameled metal plate is industrially efficiently manufactured. It is preferable because it is possible. That is, in order to laminate a photocatalyst-supporting film on a metal plate by heating and pressing, a laminating method in which heating and pressing is usually performed in a temperature range of 60 ° C. to 200 ° C. for a short time, although it depends on the resin material of the base film. A laminating method in which heat and pressure is applied by using heat of a heat drying process in applying a resin coating or paint to a metal plate substrate; and a heat and pressure process is performed by using heat and pressure in forming a metal plate substrate. It is preferable to adopt a laminating method or the like.

When the substrate is a metal plate that has not been subjected to surface treatment such as chemical conversion treatment or coating treatment, an acrylic, urethane-based, or epoxy-based adhesive is applied to the surface of the metal plate to be heated and pressed by a primer. By using a substrate obtained by coating and drying as a layer, the film adhesion and durability of the heat-laminated product can be further enhanced.
In order to heat and press the photocatalyst-carrying film on the surface of the substrate, a method of passing through a normal hot roll laminating apparatus or processing with a hot press can be adopted. By selecting the appropriate temperature, pressure, and time according to the material of the base metal plate or coated metal plate and the material of the film carrying the photocatalyst, it has excellent durability and photocatalytic activity even when used for a long time. Is obtained. Further, in the present invention, since the heating and pressurizing treatment is employed in the laminating process, the photocatalytic layer is very firmly fixed to the adhesive layer, and the durability, adhesion,
There is an advantage that peel resistance is improved.

The metal plate obtained by laminating the photocatalyst-carrying film of the present invention by heating and pressurizing is treated in the UV-A region (4
When irradiated with ultraviolet rays of 3 mW / cm ^{2 (} 00 to 315 nm), triolein can be decomposed by 5 μg / cm ² day or more. The metal plate on which the photocatalyst-supporting film according to the present invention is laminated can be irradiated with black light having an ultraviolet intensity of 3 mW / cm ^{2 at} a temperature of 40 ° C. and a relative humidity of 90% for 1000 hours, even after JIS K5400.
Also, a product exhibiting high durability such that the adhesion of the photocatalyst layer measured by the cross-cut tape method described above maintains an evaluation score of 6 or more can be obtained.

The photocatalyst-carrying film provided with the adhesive layer and the photocatalyst layer according to the present invention has high productivity and can be formed at a speed of several tens of meters per minute, and this photocatalyst-carrying film is laminated on various metal plates. In this case, the processing can be performed at a high speed of several meters per minute or more by optimizing the processing conditions. Therefore, it is possible to form a film at a much higher speed than a method of simply applying and drying a photocatalytic layer on a metal plate by a usual dipping method, a spraying method, or a roll coating method. This has a very great advantage in improving the film formation quality. Further, the metal plate laminated with the photocatalyst film obtained by the present invention can be formed into a metal processed product having a complicated shape by pressing the metal plate after laminating the photocatalyst film and molding or cutting and cutting. Because of this, its application range is extremely wide.

The metal plate laminated with the photocatalyst-carrying film of the present invention is widely used as a general building material or a material for outdoor installation structures, for example, road noise barriers, roadside telephone boxes, road signs, guardrails, etc. It can be used for peripheral equipment structures, metal plates, bathroom vanities, unit baths, system kitchens, toilets, and various sinks used in places such as bathrooms and toilets, washrooms and kitchens, and kitchens.

The metal plate laminated with the photocatalyst-carrying film of the present invention can be used for outdoor signboards, wall surfaces of transport equipment such as train buses, wall surfaces of food factories and catering facilities, refrigerators, washing machines, personal computers, radio televisions, etc. Used in many places where deodorant, antifouling, antibacterial and antifungal functions are required, such as housing for household electrical appliances, various reflectors for lighting fixtures, and internal walls of cold storage and freezer warehouses. And its excellent antifouling property, oil decomposition activity, antibacterial property, and antifungal property can keep its surface in a beautiful state for a long time.

When the metal plate on which the film carrying the photocatalyst according to the present invention is laminated is used for an outdoor display board, a road sign, or a guardrail as described above,
Due to the excellent photocatalytic decomposition activity of this film, soot and oily smoke contained in exhaust gas and the like are decomposed, so that dust, dust, sand, clay, etc. attached to the surface by the adhesive action of soot and oily smoke can be removed. It is easily dropped by wind and rain and the like, and as a result, it is difficult to be stained. Further, when a steel plate obtained by laminating the photocatalyst-supporting polymer resin film according to the present invention to the reflector for lighting equipment is used, oil mist and cigarette smoke in the room adhered to the reflector by ultraviolet rays emitted from the fluorescent lamp. It is decomposed to reduce oil stains on the surface, thereby making the stains less noticeable. Furthermore, when a steel sheet laminated with a photocatalyst-supporting polymer resin film according to the present invention is used for a housing of a household electric appliance such as a refrigerator, a washing machine, a personal computer, a radio / TV, etc., the amount of ultraviolet light irradiated in an indoor environment Although small, oil mist floating in the room and sebum components due to contact with fingers are gradually decomposed by the photocatalytic decomposition action, and as a result, there is an excellent effect that hand stains and darkening attached to the surface are reduced.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 Production of Photocatalyst-Supporting Film An adhesive layer coating solution and a photocatalyst were applied to a 50 μm thick acrylic resin film “Acryprene HBS-006” manufactured by Mitsubishi Rayon Co., Ltd. using a microgravure printing machine manufactured by Yasui Seiki Co., Ltd. The layer coating solution was applied. Silicon content 3
A 20% ethanol solution of methyl silicate MS51 (manufactured by Colcoat Co., Ltd.) as a polysiloxane in an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight of an acrylic silicone resin of 8% by mole as a solid content was added to the acrylic silicone resin. Then, 35% by weight of a solid content and 1% by weight of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent were added to the coating solution to prepare a coating solution for the adhesive layer. After forming the adhesive layer at a temperature of 60 ° C. at a speed of 20 m / min, it was allowed to cool at room temperature. In the presence of a surfactant,
A solution of water / ethanol 50/50 in which a titanium oxide content of 10% by weight is dispersed in a liquid having a weight ratio of water / ethanol 50/50. An equal amount of a dispersion of the silica sol of nitric acid acid was added in an amount of 1% by weight to prepare a coating solution for the photocatalyst layer. Using this solution, a film is formed under the same conditions as the adhesive layer to support the photocatalyst layer, and the photocatalyst supporting film (A)
And In the same manner, the adhesive layer and the photocatalyst layer were formed on other film materials by changing the film forming temperature and drying conditions, and an acrylic film “Sandulen 008N” manufactured by Kaneka Chemical Co., Ltd.
A photocatalyst-carrying film was prepared using a 50 μm thick (B) CT and a 50 μm thick Sumitomo Bakelite PVC film (C).

Example 2 Production of an iron plate laminated with a photocatalyst-carrying film The photocatalyst-carrying film (A) obtained in Example 1 was cut out of a 1 mm-thick iron plate into 5 × 5 cm, and an acrylic adhesive was applied on the surface thereof with a primer. The operation of applying a pressure of 50 kg / cm ² for 10 seconds at a temperature of 120 ° C. for 10 seconds was repeated 5 times to remove air, and then 100 kg for 2 minutes at 50 kg / cm ² at the same temperature.
/ Cm ² for 2 minutes and 150 kg / cm ² for 1 minute, and then cooled to 50 ° C. or less while pressurizing to obtain an iron plate laminated with a photocatalyst-carrying film.
(Sample 1)

Example 3 Production of an aluminum plate laminated with a photocatalyst-carrying film The photocatalyst-carrying film (A) obtained in Example 1 was applied to the surface of an aluminum plate having a thickness of 1 mm using an acrylic adhesive as a primer and dried. An aluminum plate on which a photocatalyst-carrying film was laminated by the same laminating method as in Example 2 was adhered onto a piece cut into a size of × 5 cm. (Sample 2)

Example 4 Production of a stainless steel plate laminated with a photocatalyst supporting film The photocatalyst supporting film (A) obtained in Example 1 was replaced with SU
A 1 mm-thick S-304 plate was coated with an acrylic adhesive as a primer, dried, cut into 5 × 5 cm pieces, and stuck on a piece of 5 × 5 cm. Board. (Sample 3)

Example 5 Production of a coated steel sheet laminated with a photocatalyst-carrying film The photocatalyst-carrying film (B) obtained in Example 1 was baked with an acrylic paint to a thickness of 0.3 mm and a width of 60 mm.
Using a heating / pressing roll laminating apparatus, laminating a coated steel sheet with a nib pressure of 5 kg / cm, a lamination roll at a sheet surface temperature of 150 ° C., and a sheet feeding speed of 10 m / min. Painted steel sheet. The laminated coated steel sheet was cut into a size of 5 × 5 cm and used as a measurement sample. (Sample 4)

Example 6 Production of a coated aluminum plate laminated with a photocatalyst-carrying film The photocatalyst-carrying film (B) obtained in Example 1 was baked and coated with an acrylic paint to a thickness of 1 mm and a size of 5 × 5 cm.
And then treated under the same conditions as in Example 2 to obtain a coated aluminum plate laminated with a photocatalyst-carrying film. (Sample 5)

Example 7 Production of a PVC-coated steel sheet laminated with a photocatalyst-carrying film The PVC-coated steel sheet obtained by cutting the photocatalyst-carrying film (C) obtained in Example 1 into a 1 mm thick 5 × 5 cm coated with a vinyl chloride resin And 50 kg / cm ² for 1
After pressurizing 4 to 5 times for 0 second to remove air, 100 kg / cm ² at 50 kg / cm ² for 30 seconds at the same temperature
² in 1 minute, after heating and pressurization at a temperature pressure at 150 kg / cm ² 30 seconds, pressurized remained 50 ° C. by cooling below, and the photocatalyst carrying film and laminated with PVC coated steel sheet. (Sample 6)

Example 8 Production of Polyester-Coated Steel Sheet Laminated with Photocatalyst-Supporting Film The photocatalyst-supporting film (C) obtained in Example 1 was cut into a 1 mm-thick 5 mm x 5 cm-thick polyester-coated steel sheet coated with a polyester resin. A polyester-coated steel sheet laminated with a photocatalyst-supporting film was laminated in the same manner as in Example 7. (Sample 7)

Example 9 An iron plate on which a copper-added photocatalyst-carrying film was laminated In the presence of a surfactant, a nitric acid-titania sol was dispersed in a liquid having a weight ratio of water / ethanol of 50/50 so that the titanium oxide content became 10% by weight. The same amount of a solution prepared by dispersing a nitric acid-containing silica sol in a liquid having a weight ratio of water / ethanol 50/50 to a silicon oxide content of 10% by weight is added thereto, and further, copper nitrate hydrate is added to titanium oxide. On the other hand, the adhesive layer and the photocatalyst were prepared according to the film, raw materials, and production method used in (A) of Example 1 except that 0.1% by weight of metal copper was added and dissolved to prepare a photocatalyst layer coating solution. A layer coated photocatalyst carrying film was produced. This photocatalyst-supporting film was cut into an iron plate having a thickness of 1 mm, cut into a size of 5 × 5 cm, and adhered in the same manner as in Example 2 to form an iron plate on which a copper-added photocatalyst-supporting film was laminated.
(Sample 8)

Example 10 Reflector for Lighting Apparatus A reflector for a fluorescent lamp was prepared using a coated steel sheet laminated with the photocatalyst-carrying film prepared in Example 5, and a 5 ×
It was cut out to 5 cm to obtain a sample for characteristic evaluation. (Sample 9)

Example 11 Outdoor Signboard An outdoor signboard was produced using a coated steel sheet laminated with the photocatalyst-carrying film prepared in Example 5. A similar outdoor signboard was produced using a coated steel sheet obtained by laminating a film not carrying a photocatalyst, whereas the evaluation of the stain resistance was performed by the method described below. When the stain resistance was similarly evaluated, the evaluation was D.

Example 12 Refrigerator Using an iron plate laminated with the photocatalyst-carrying film prepared in Example 9, a box was placed in a vegetable room case of a refrigerator, and a fluorescent lamp for a photocatalyst, Ecoclean (manufactured by Toshiba Lighting & Technology Corp.) was prepared in the box. FC2BLB / 200T1
2) 3 lit, 5 carrots, 2 cabbage, 1 tomato
0, 10 cucumber, 1 spinach, 1 bell pepper
Zero plants were kept naked, and replaced with fresh vegetables of the same kind every three days and stored. A box of the same size is manufactured using an iron plate laminated with a film not supporting a photocatalyst, and a fluorescent lamp for a photocatalyst made by Toshiba Lighting & Technology Corp. EcoClean (FC2BLB / 200T12) in the box.
Lights up in the same way as three, put the same kind of vegetables in the same
Similarly, every third day, the vegetables were replaced with fresh vegetables of the same kind and stored. As a result, in a vegetable box made of an iron plate laminated with a photocatalyst-carrying film, mold generation and dirt were hardly visually observed, whereas a vegetable box made of an iron plate laminated with a film not carrying a photocatalyst was visually observed. In the box, mold generation and sticking of dirt were remarkably observed.

Example 13 Guardrail A road guardrail was prototyped using a coated steel sheet laminated with the photocatalyst-carrying film prepared in Example 5, and the stain resistance described later was evaluated. Similarly, using a coated steel sheet laminated with a film that does not carry a photocatalyst, a road guardrail was prototyped and the stain resistance was evaluated.
As a result, a guardrail using a coated steel sheet laminated with a photocatalyst-supporting film was evaluated as A, whereas a guardrail using a coated steel sheet laminated with a film not supporting the photocatalyst was evaluated as D.

Example 14 Road Sign A road sign having the same size as a road sign was experimentally produced using the coated steel sheet laminated with the photocatalyst-carrying film prepared in Example 5, and the stain resistance described later was evaluated. Using a coated steel sheet laminated with a film not carrying a photocatalyst, a sign having the same size as a road sign was produced as a trial, and the stain resistance was similarly evaluated. As a result, a road sign prototyped using a coated steel sheet laminated with a photocatalyst-carrying film was evaluated as B, whereas a road sign prototyped using a coated steel sheet laminated with a film not carrying a photocatalyst was evaluated as B. Was D.

Example 15 Evaluation of Durability of Laminated Steel Plate After the guardrail prototype produced in Example 13 was installed outdoors for one year, the adhesion described later was evaluated at 10 different places. 8 points and 6 points gave 10 points.

COMPARATIVE EXAMPLE 1 An acrylic resin film "Acryprene HBS-006" manufactured by Mitsubishi Rayon Co., Ltd. having a thickness of 50 μm shown in Example 1 was cut into a 5 mm × 5 cm thick iron plate by the same method as in Example 2. An iron plate was prepared by laminating a PET film on the cut out piece.

Comparative Example 2 The acrylic film “Acryprene HBS-006” manufactured by Mitsubishi Rayon shown in Example 1 having a thickness of 50 μm was baked with an acrylic paint to obtain a 1 mm thick 5 mm thick film.
Example 2: Laminated on a coated steel sheet cut to 5 cm
Under the same conditions and method as above, a coated steel sheet laminated with an acrylic film was obtained.

Comparative Example 3 The 50 μm thick Sumitomo Bakelite hard PVC film shown in Example 1 was laminated to a 1 mm thick 5 × 5 cm PVC-coated steel sheet coated with a vinyl chloride resin. Under the same conditions and method, a PVC-coated steel sheet laminated with a PVC film was obtained.

(Evaluation of Photocatalytic Activity) Using the samples of Samples 1 to 9 and the sample of Comparative Example, the following photocatalytic activity was evaluated, and the results shown in Table 1 were obtained.

1) Stain resistance (stain resistance) A sample cut into a square of 5 cm × 5 cm is of the same type without a photocatalyst mounted on a fence facing a general road (traffic volume of trucks: about 500 to 1,000 vehicles / day). Three months later, the sample was stuck together with a blank sample of the same size, and the degree of contamination on the sample surface was evaluated with a spectral colorimeter based on a comparative control sample stored in a cool and dark place. The evaluation criteria were as follows.

2) Triolein Decomposition Property (Oil Decomposition Activity) Triolein (special grade reagent, manufactured by Wako Pure Chemical Industries) was added to a sample cut into 5 cm squares using a Kimwipe at 0.1 mg / cm.
After applying so that it becomes ² , temperature 25 ° C, relative humidity 70%
Immersed in a 15W black light fluorescent lamp on the surface of the sample, and the UV light in the UV-A region was 3 m on the sample surface.
The distance between the light source and the sample surface was adjusted so that the intensity was W / cm ² . The amount of decrease in triolein with respect to the light irradiation time was quantified using a precision balance to determine triolein decomposition activity, and the evaluation criteria were as follows. Triolein residual rate after 5 days (%) Evaluation 10% or less A (18 μg / cm ² · day or more) 50 to 10% B (10 to 18 μg / cm ² · day) 75 to 50% C (5 to 10 μg / day) cm ² · day) 95-75% D (1-5 μg / cm ² · day) 95% or more E (1 μg / cm ² · day or less)

3) Evaluation of antibacterial activity A sample cut into a 5 cm square was disinfected with 80% ethanol, dried at 150 ° C. and sterilized, and pre-cultured and diluted to adjust the bacterial concentration to 105 cells / ml. 0.2 ml of the bacterial solution of Escherichia coli was dropped on the sample surface and set in an incubator. Four samples were each set under two kinds of light irradiation conditions, that is, a light irradiated with a white fluorescent lamp (15 W × 2, distance from the light source 10 cm) and a light not irradiated at all. After a predetermined time (1, 2, 3, 4 hours), the sample is taken out, the bacterial solution on the sample is wiped off with sterile gauze immersed in sterile physiological saline, and the wiped sterile gauze is removed by 10 m.
1 ml of sterile physiological saline and sufficiently stirred. The supernatant was inoculated on an autoclave-sterilized 95 mmφ Petri dish agar medium, and cultured at 36 ° C. for 24 hours, followed by counting the number of E. coli colonies. A sample for measuring the standard number of bacteria was prepared in exactly the same manner until the operation until it was put into the incubator, and the supernatant of sterilized saline was inoculated on a Petri dish agar medium, and the number of E. coli colonies after 24 hr culture was counted. . The survival rate of E. coli after a predetermined time of each sample was calculated based on the numerical value. After 4 hours, the sample irradiated with the light of the fluorescent lamp was evaluated based on the residual ratio of Escherichia coli, and the evaluation criteria were as follows. Escherichia coli residual rate after 4 hours Evaluation 20% or less A 20-40% B 40-60% C 60-80% D 80% or more E

4) Antifungal property The degree of the occurrence of green mold on the surface of the sample used for the evaluation of the stain resistance was evaluated by comparison with a sample stored in a cool and dark place according to the following criteria. As expected. Evaluation of the degree of generation of mold on the sample surface Almost no occurrence A Partially slight occurrence B evident occurrence C

(Adhesion) Adhesion was evaluated by a cross-cut tape test specified in JIS K5400.
The interval between cuts was 2 mm, and the number of squares was 25. The evaluation score was based on the standard described in JIS K5400.

(Evaluation of durability) After irradiating the carried sample with light of ultraviolet intensity of 3 mW / cm ^{2 using} a black light in a thermo-hygrostat at a temperature of 40 ° C. and a humidity of 90% for 1000 hours, JIS
The adhesion was measured by a cross cut tape method specified in K5400, and the durability was evaluated. The evaluation score is the same as the evaluation of adhesion.

[0067]

[Table 1]

Comparative Example 4 According to Example 48 described in WO 97-134, an aqueous solution of an acrylic silicone resin emulsion having a silicon content of 20% was added as a coating solution for the adhesive layer to the Si in the dry adhesive layer.
Cataloid SI-350 manufactured by Catalysis Kasei Co., Ltd. was added to adjust the O ₂ content to 10%, and the total dry solid content was adjusted to 20%. Further, as a coating solution for the photocatalyst layer, 30% as a solid content of titanium oxide P-25 for photocatalyst manufactured by Japan Aerosil Co., Ltd., silica sol cataloid SI manufactured by Catalyst Kasei Co., Ltd.
-30% as solid content, Nissan Chemical Co., Ltd. alumina sol-200 as dry solid content, 10% as dry solid content, acrylic silicone resin emulsion aqueous solution with silicon content of 20% by weight as non-volatile residue, 35% as non-volatile residue, silane coupling agent Was prepared so that tri (β-methoxyethoxy) vinylsilane manufactured by Nippon Unicar Co., Ltd. was 5% as a nonvolatile residue and 10% as a whole as a dry residue. Using these coating solutions, an acrylic film “Acryprene HBS-006” manufactured by Mitsubishi Rayon Co., Ltd. was applied to a 50 μm thick film using a microgravure printing machine manufactured by Yasui Seiki Co., Ltd. Film formation was not possible due to insufficient curing. Therefore, the same coating solution for the adhesive layer and the coating solution for the photocatalyst layer were coated on the above-mentioned acrylic film manufactured by Mitsubishi Rayon Co., Ltd. using a desktop bar coater and dried at a drying temperature of 80 ° C. Time was needed for one hour. This photocatalyst-carrying acrylic film was adhered to the surface of a 1 mm-thick polyester resin-coated steel sheet cut out to a size of 5 × 5 cm, and subjected to thermal lamination according to the same method and conditions as in Example 2. Stain resistance of polyester coated steel sheet obtained by thermally laminating this photocatalyst supporting film,
As shown in Table 1 above, the oil decomposition activity, antibacterial property, antifungal property, adhesion and durability were poor in oil decomposition activity, durability and the like. Thus, the application of this photocatalyst-carrying film prepared without containing a silane coupling agent in the coating solution for the adhesive layer to a coated steel plate was inappropriate.

[0069]

The metal plate obtained by laminating the photocatalyst-carrying film of the present invention has high photocatalytic activity, is excellent in durability, and is intended for antifouling, antibacterial, antifungal and the like. It can be used for facilities installed around roads, outdoor signs, outdoor signs, household electrical equipment, various lighting fixtures, kitchens, kitchens, toilets, bathroom equipment, etc.
And it has an excellent price-performance ratio. In addition, the photocatalyst-carrying film provided with the adhesive layer and the photocatalyst layer according to the present invention has high productivity and can be formed at a speed of several tens of meters per minute or more, and when this photocatalyst-carrying film is laminated on various metal plates. By optimizing the processing conditions, processing can be performed at a high speed of several meters per minute or more.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a cross section of a resin laminated with a photocatalyst supporting film of the present invention.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI C09D 183/04 C09D 183/04

Claims (19)

[Claims] 1. A film obtained by laminating a photocatalyst-supporting film on a surface of a metal plate by heating and pressurizing treatment, and emitting 3 mW of ultraviolet light in a UV-A region at an atmospheric temperature of 25 ° C. and a relative humidity of 70%. / cm ² irradiated laminated metal plate photocatalyst carrying film characterized by having a photocatalytic activity capable of decomposing triolein 5 [mu] g / cm ² · day or more when the. 2. The metal plate according to claim 1, wherein the photocatalyst-carrying film is made of a polymer resin film having the photocatalyst layer carried via an adhesive layer. 3. The metal plate according to claim 2, wherein the polymer resin film is a film obtained by laminating two or more resin films. 4. The polymer resin film is a resin selected from a polycarbonate resin, a copolymer resin of two or more kinds of polymethyl methacrylate resins or polyacrylate resins, a polyvinyl chloride resin, and a cellophane resin. A metal plate obtained by laminating the photocatalyst-carrying film according to claim 2 or 3. 5. The polymer resin film has a thickness of 5 to 20.
A metal plate obtained by laminating the photocatalyst-supporting film according to claim 2, wherein the metal plate has a thickness of 0 μm. 6. The photocatalyst-carrying film according to claim 2, wherein the adhesive layer is formed by applying an adhesive layer coating solution containing a silane coupling agent as a curing agent. Metal plate. 7. An adhesive layer coating solution containing a silicone-modified resin containing 10 to 50% by weight of polysiloxane or a coating solution containing 2 to 20% by weight of a silicon-modified resin containing 5 to 30% by weight of colloidal silica. 7. An adhesive layer coating solution containing a silane coupling agent in an amount of 0.1 to 5% by weight based on the coating solution as a curing agent.
A metal plate obtained by laminating the photocatalyst-supporting film according to the above. 8. A coating solution containing 1 to 10% by weight of monoalkyltrimethoxysilane or a polysiloxane which is a hydrolysis product thereof and 0.1 to 5% by weight of silica sol as a coating solution for the adhesive layer, 7. The metal plate laminated with a photocatalyst-carrying film according to claim 6, wherein an adhesive layer coating solution containing 0.1 to 5% by weight of a silane coupling agent based on the coating solution is used. 9. The metal plate obtained by laminating a photocatalyst-carrying film according to claim 2, wherein the thickness of the adhesive layer is 0.5 to 5 μm. 10. The photocatalyst layer according to claim 2, wherein the solid content of the metal oxide sol is 1 to 10% by weight and the titanium oxide sol is 1 to 10% by weight of the solid content. A metal plate obtained by laminating the photocatalyst-supporting film of Example 1. 11. The photocatalyst layer comprises 1 to 10% by weight of silica sol, 1 to 10% by weight of monoalkyltrimethoxysilane or a hydrolysis product thereof, and 1 to 10% by weight of titanium oxide sol.
A metal plate obtained by laminating a photocatalyst-supporting film according to any one of claims 2 to 9, which is contained in an amount of 10% by weight. 12. The metal plate according to claim 10, wherein the thickness of the photocatalyst layer is 0.1 to 5 μm. 13. The photocatalyst-supporting film according to claim 1, wherein the metal plate is one kind of metal plate selected from an iron plate, a steel plate, an aluminum plate, and an aluminum alloy plate. Laminated metal plate. 14. A resin-coated metal plate in which the metal plate is coated with one or more resins selected from one or more resins selected from polyvinyl chloride resin, polyethylene terephthalate resin, and polymethyl methacrylate resin; 14. A metal plate obtained by laminating a photocatalyst-supporting film according to claim 1, which is a painted metal plate or an enameled metal plate. 15. The metal plate obtained by laminating a photocatalyst-carrying film according to any one of claims 1 to 14, wherein the metal plate has a shape of a plate, a tube, or a corrugated plate. 16. An adhesive layer coating solution containing a silane coupling agent as a curing agent is applied to a polymer resin film and dried, and then a photocatalytic layer coating solution is applied to the adhesive layer and dried. A photocatalyst-carrying film in which a photocatalyst-carrying film having a photocatalyst layer carried on a resin film via an adhesive layer is prepared, and the photocatalyst-carrying film is laminated on the surface of a metal plate by heating and pressing. Manufacturing method of a manufactured metal plate. 17. A reflector for lighting equipment, an outdoor signboard or an outdoor signboard, and a household electric appliance, wherein the metal plate obtained by laminating the photocatalyst-supporting film according to claim 1 is used at least in part. Product, guardrail or road sign. 18. A photocatalyst adhesive layer coating agent used for preparing a photocatalyst-supporting polymer resin film in which a photocatalyst layer is supported on a polymer resin film via an adhesive layer, wherein polysiloxane is contained in an amount of 10 to 50% by weight. 5-30% by weight of silicon modified resin or colloidal silica contained
A coating for a photocatalytic adhesive layer, characterized in that a silane coupling agent as a curing agent is added in an amount of 0.1 to 5% by weight based on the coating liquid, to an adhesive layer coating liquid containing 2 to 20% by weight of a silicon-modified resin contained therein. Agent. 19. A coating agent for a photocatalyst adhesive layer used for preparing a photocatalyst-supporting polymer resin film in which a photocatalyst layer is supported on a polymer resin film via an adhesive layer, wherein the coating agent is a monoalkyltrimethoxysilane or a hydrochloride thereof. A coating solution containing 1 to 10% by weight of a polysiloxane as a decomposition product and 0.1 to 5% by weight of a silica sol is coated with a silane coupling agent as a curing agent in an amount of 0.1 to 5%.
A coating agent for a photocatalytic adhesive layer, wherein the coating agent is added by weight.