JPH11138686A - Resin structural body formed of laminated photocatalyst carrying film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a resin structural body formed of a laminated photocatalyst carrying film having the effects of superior deodorization, antifouling, antibacteria, mildewproofing and the like. SOLUTION: A bonded layer coating liquid into which a silane coupling agent is added as a curing agent is applied on a polymer resin film and dried thereon, and then a photocatalyst layer coating liquid is applied on the bonding layer and dried thereon to provide a photocatalyst carrying film formed of the polymer resin film on which a photocatalyst layer is carried through the bonding agent, and the photocatalyst carrying film is laminated on the surface of a resin base by heating and pressurizing treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin structure obtained by laminating a photocatalyst-supporting film having an effect of deodorizing, antifouling, antibacterial, antifungal and the like by heating and pressing, and a method for producing the same. And its applied products.

[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 resin structure obtained by laminating a film carrying a photocatalyst, particularly a resin obtained by laminating a photocatalyst carrying film carrying a photocatalyst onto a widely used polycarbonate resin or woven fabric reinforced polyvinyl chloride resin without reducing the catalytic activity The structure is not known, and deodorizing, antifouling,
There is no report on how to maintain antibacterial and antifungal properties over a long period of time.

Conventionally, resin structures such as sound insulation walls made of polycarbonate installed outdoors and fiber-reinforced resins impregnated with polyvinyl chloride are apt to adhere to dust and soot in the outside air.
In three months, 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. Also,
Titanium oxide inherently has the property of exhibiting hydrophilicity when irradiated with ultraviolet light in the atmosphere, but this effect is used to make the surface of the outdoor installation structure hydrophilic, and to prevent oil mist and the like from adhering. A method of making it easy to wash off oil with water (especially rainwater) is also disclosed (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 large-sized resin substrate having a flat plate shape, it is often difficult to apply the method using a coating method such as a dipping method or a spraying method due to restrictions on production equipment, film forming speed, and drying speed. In particular, a resin substrate having a width of 1 m or more requires a large-sized dryer and requires a drying time of 30 minutes or more due to heat capacity, so that there is a problem that the production speed is low and the cost is high.

When a photocatalyst is supported on a resin plate or a coated resin plate for the purpose of antifouling, antibacterial, and deodorant, a photocatalyst structure having a structure in which a photocatalyst layer is provided via an adhesive layer is directly applied to the resin plate or the like. Provision on the surface is also considered as one method. However, in this method, the drying time after coating is required to be much longer than that in the case of film formation. In the case of film formation, the drying processing 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 resin substrate may be eroded during coating and drying, and when the coating process on the resin substrate becomes large with a width of 1 m or more, it is difficult to form a uniform film by dip coating or spray coating. However, there is a problem that thickness unevenness of the film easily occurs, and there is a drawback that the kind and size of the applicable resin substrate are limited.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin structure in which a photocatalyst-carrying film having excellent deodorizing, antifouling, antibacterial, and antifungal effects is laminated.

[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 resin substrate by heating and pressurizing treatment, thereby completing the present invention.

That is, the present invention is obtained by laminating a photocatalyst-supporting film composed of a polymer resin film having a photocatalyst layer supported thereon via an adhesive layer on the surface of a resin substrate by heating and pressurizing treatment, and Medium temperature 2
When 3 mW / cm ² of ultraviolet light in the UV-A region is irradiated at 5 ° C. and a relative humidity of 70%, triolein is 5 μg / c.
The present invention relates to a resin structure obtained by laminating a photocatalyst-supporting film, which has a photocatalytic activity capable of decomposing at least m ² · day.

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 resin substrate is polyvinyl chloride resin, polyethylene terephthalate resin, polymethyl methacrylate resin,
Polycarbonate resin, polyethylene resin, polypropylene resin, impact-resistant modified polystyrene resin, acrylic
Butadiene-styrene copolymer resin, or a resin selected from the group consisting of a plate, a sheet, a woven fabric, a nonwoven fabric, a resin-impregnated reinforced woven fabric, and a tubular resin. And a resin structure obtained by laminating the photocatalyst-carrying film.

Further, according to the present invention, a coating solution of an adhesive layer containing a silane coupling agent as a curing agent is applied to a polymer resin film and dried, and then a coating solution of a photocatalyst layer is applied to the adhesive layer and dried. Preparing a photocatalyst-supporting film having a photocatalyst layer supported on a polymer resin film via an adhesive layer, and laminating the photocatalyst-supporting film on the surface of the resin substrate by heating and pressing. The present invention relates to a method for producing a laminated resin structure.

Further, the present invention provides an outdoor signboard and an outdoor signboard, a telephone box, an outdoor tent cloth, a vanity stand, and a resin structure obtained by laminating the above-described photocatalyst-carrying film on at least a part thereof. unit bus,
System kitchen, ornamental fish tank, plastic case,
Wallpaper, food trays, or packaging films.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A resin structure having a photocatalyst-carrying film of the present invention laminated thereon is prepared by, for example, applying and drying an adhesive layer coating solution containing a silane coupling agent as a curing agent on a polymer resin film. Thereafter, a coating solution of a photocatalyst layer is applied to the adhesive layer and dried to prepare a photocatalyst supporting film in which the photocatalyst layer is supported on the polymer resin film via the adhesive layer. It can be manufactured by laminating the surface of the base. FIG. 1 shows a schematic diagram of a cross section of a resin structure 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 resin substrate 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 resin substrate by applying heat and pressure to the film, which accelerates the curing of the film and enables the film to be wound without sticking to the back surface, thus enabling high-speed film formation. Can be prevented, and the photocatalytic activity of the photocatalyst-carrying 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. Further, by adding the silane coupling agent to the coating solution in an amount of 0.1 to 5% by weight, the photocatalytic activity decreases when the photocatalyst-supporting film is laminated on the surface of the resin substrate by heating and pressing. In addition, the photocatalytic activity of the photocatalyst-carrying film before lamination can be maintained.

The silane coupling agent has the general formula:
A compound represented by RSi (X) ₃ or (R) ₂ Si (X) ₂ (where R represents an organic functional group and X represents a chlorine atom or an alkoxy group) can be used. R is a methyl group,
Ethyl group, vinyl group, γ-glycidoxypropyl group, γ
-A methacryloxypropyl group, a γ- (2-aminoethyl) aminopropyl group, a γ-chloropropyl group, a γ-mercaptopropyl group, a γ-aminopropyl group, a γ-acryloxypropyl group, and the like, wherein X is , A chlorine atom, and a C1 -C5 alkoxy group such as a methoxy group, an ethoxy group, and a β-methoxyethoxy group.

The durability of the adhesive layer can be improved by mixing a light stabilizer and / or an ultraviolet absorber for the purpose of suppressing the deterioration due to the photocatalytic action. 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 0.0
It is from 0.05% by weight to 10% by weight, preferably from 0.01% by weight to 5% by weight. By adding a light stabilizer or an ultraviolet absorber to the adhesive layer, it becomes possible to improve the weather resistance of the polymer resin film supporting the photocatalyst, which is particularly advantageous when used outdoors. 0.00001% by weight of surfactant in the adhesive layer coating solution
By adding 0.1% by weight, a good resin structure can be obtained by laminating a good photocatalyst-carrying film.

As a method for applying the adhesive layer to the film, a coating solution for the adhesive layer is applied by gravure printing, microgravure printing, comma coating, roll coating, reverse roll coating, bar coating, kiss coating, flow coating. Examples of the method include coating by a method and drying. The drying temperature varies depending on the coating method, the solvent, the type of the resin of the film, and the thickness of the film.
50 ° C. or less is desirable.

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 the resin substrate 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.

The photocatalyst in the photocatalyst layer is TiO._Two ,
ZnO, SrTiO_Three , CdS, GaP, InP, Ga
As, BaTiO_Three , K_Two NbO_Three , Fe_Two O_Three , Ta
_Two O _Five , WO_Three , SnO_Two , Bi_Two O_Three , NiO, Cu
_Two O, SiC, SiO_Two , MoS_Two , InPb, RuO
_Two , CeO_Two And the like.
Pt, Rh, RuO for photocatalyst_Two , Nb, Cu, Sn, N
Known materials to which metals and metal oxides such as iO are added
All can be used. The photocatalyst content in the photocatalyst layer is high
Although the catalytic activity becomes higher, 75
% Or less is preferred. Improved antibacterial and antifungal properties
To make the photocatalyst layer contain 0.1% of titanium oxide photocatalyst.
0.5 to 5% by weight of a metal or metal compound of silver or copper
Can be added. If the addition amount is less than 0.05% by weight,
Poor antibacterial / antifungal effect
The phenomenon that the photocatalyst layer discolors occurs
Difficult to use depending on the color and pattern of the resin on which the lum is laminated
It can be difficult.

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. Addition of the agent prevents a decrease in photocatalytic activity when the photocatalyst-supporting film is laminated on the surface of the resin substrate by heating and pressurizing treatment, 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, the resin substrate on which the base film is laminated has a high photocatalytic activity. Is not impaired, so that it is also preferable from the viewpoint of beauty.

In the present invention, the resin substrate on which the photocatalyst-carrying film is laminated by heat and pressure treatment includes polyvinyl chloride resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polycarbonate resin, polyethylene resin, polypropylene resin, and modified polystyrene resin. And an impact-resistant polystyrene resin and an acrylic-butadiene-styrene copolymer resin. The shape of the resin substrate may be any shape such as a plate shape, a sheet shape, a woven fabric shape, a nonwoven fabric shape, a resin impregnated reinforced woven fabric shape, a tubular shape, etc., as long as the photocatalyst supporting film can be laminated. Good.

As a method for laminating the photocatalyst-supporting polymer resin film to various resin substrates, a method of laminating a resin substrate such as a resin plate or a coated resin plate while heating and pressing with a hot roll or the like, a method of laminating a resin plate or a coated resin plate, For example, a method of laminating a photocatalyst-supporting polymer resin film by heating and pressurizing treatment using heat of heat treatment at the time of producing a resin substrate such as a resin-coated resin plate is preferable because it can be industrially efficiently produced. That is, in order to laminate the photocatalyst-carrying film on the resin substrate by heating and pressurizing, the heating is usually carried out for a short time in a temperature range of 60 ° C. to 200 ° C., although it depends on the resin material of the base film and the material of the resin substrate. It is preferable to employ a laminating method in which pressure treatment is performed, a laminating method in which pressing is performed by using residual heat in extrusion molding of a resin substrate to be a resin structure, a laminating method in which a hot roll is passed or a hot press is used.

The surface of the resin substrate to be heated and pressurized may be obtained by subjecting the surface of the resin substrate to a corona discharge treatment or an ultraviolet irradiation treatment, or by applying and drying an acrylic, urethane or epoxy adhesive as a primer layer. By using the substrate, the film adhesion and durability of the heat-laminated product can be further enhanced. By selecting the appropriate temperature, pressure and time according to the material of the resin base such as resin plate or painted resin plate and the material of the film carrying the photocatalyst, it has excellent durability and photocatalytic activity even when used for a long time. Can be obtained. Also,
In the present invention, since the heating and pressurizing treatment is adopted for the laminating process, the photocatalytic layer is very firmly fixed to the adhesive layer, and the durability, adhesion, and peeling resistance are higher than before the heating and pressurizing treatment. There is an advantage that is improved.

The resin structure obtained by laminating the photocatalyst-carrying film according to the present invention by heating and pressurizing treatment can emit ultraviolet rays in the UV-A region (400 to 315 nm) at 3 mW / at an atmospheric temperature of 25 ° C. and a relative humidity of 70%. When irradiated with cm ^2, triolein can be decomposed by 5 μg / cm ² · day or more. The resin structure laminated with the photocatalyst supporting film according to the present invention has an ultraviolet intensity of 3 mW.
/ Cm ^{2 at} a temperature of 40 ° C. and a relative humidity of 90% for 1000 hours.
A product exhibiting high durability such that the adhesion of the photocatalyst layer measured by a crosscut tape method of K5400 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 or more, and this photocatalyst-carrying film is laminated on various resin substrates. 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 in which a photocatalytic layer is simply applied and dried on a resin substrate by a usual dipping method, a spray method, or a roll coating method. This has a very great advantage in improving the film formation quality. In addition, the resin structure obtained by laminating the photocatalyst film obtained by the present invention can be formed into a resin processed product having a complicated shape by pressing the resin base after laminating the photocatalyst film, molding or cutting and cutting. Therefore, its application range is extremely wide.

The resin structure obtained by laminating the photocatalyst-supporting polymer resin film of the present invention is widely used as a general building material or a material for an outdoor installation structure, for example, an outdoor advertising tower, a road noise barrier, a roadside telephone box, a road sign, and the like. Used as a surface building material for home-use equipment such as road-related equipment structures, resin molded products in places such as bathrooms and toilets, toilets and kitchens, for example, vanities, unit baths, system kitchens, toilets, and various sinks be able to.

The resin structure laminated with the photocatalyst-carrying film of the present invention is a sign made of a polyvinyl chloride marking film used for an outdoor sign.
Resin windows for vehicles such as trains and buses, tent fabric for outdoor use, open stack sheets, tent shelters for tent warehouses, shops, etc., tent roofs for various arcades, tent roofs for exhibition pavilions, etc. Can be used for tent covers, gas station roofs and side covers, waterproof protective sheets, snow-proof sheets, air domes, pool covers, etc., and a resin structure laminated with a photocatalyst carrying film on the surface of wood or mortar. It can be used for walls, doors, ceilings, fixtures, etc. of hospitals and geriatric health facilities. As described above, the resin structure laminated with the photocatalyst-carrying film of the present invention can be used in many places where deodorant, antifouling, antibacterial, and antifungal functions are required. Due to its antifouling property, antibacterial property and antifungal property, the surface can be maintained in a beautiful state for a long time.

When the resin structure laminated with the film supporting the photocatalyst of the present invention is used for an outdoor display panel, an outdoor signboard, an outdoor tent fabric, a telephone box, or the like, the excellent photocatalytic decomposition of the film is obtained. The activity decomposes soot and oil smoke contained in exhaust gas, etc.
Dust and dust adhering to the surface due to their adhesive action,
Sand, clay, etc. are easily removed and dropped by wind and rain, resulting in less soiling. When an acrylic plate water tank laminated with the photocatalyst-supporting polymer resin film according to the present invention is used, the organic substances and bacteria attached to the inner surface of the water tank are decomposed by ultraviolet rays emitted from a fluorescent lamp, and the surface of the water tank is decomposed. The dirt due to the water scale is reduced, and the dirt becomes less noticeable. The resin plate laminated with the photocatalyst-carrying film according to the present invention can be suitably used as a material for kitchens, toilets, system kitchens used in bathrooms, vanities, and unit baths. However, it is preferable because the antifouling and antibacterial functions can be exhibited. Refrigerator, washing machine,
Uses the photocatalyst-carrying polymer resin film of the present invention laminated on the surface of resin-made housings of household electric appliances such as personal computers, radios and televisions, and the surfaces of various plastic cases such as tableware baskets and seasoning cases. In this case, the amount of ultraviolet rays irradiated in the indoor environment is small, but oil mist floating in the room and sebum components due to contact with fingers are gradually decomposed by photocatalytic decomposition action, resulting in reduction of hand stains and darkening adhering to the surface An excellent effect is achieved.

[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 nitric acid-acidified silica sol was added in an amount of 1% by weight to prepare a photocatalyst layer coating solution. 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 Polycarbonate resin laminated with a photocatalyst-carrying film The photocatalyst-carrying film (A) obtained in Example 1 was pressed at room temperature under a pressure of 50 kg / cm ² using a hot plate press manufactured by Toyo Seiki Seisaku-sho, Ltd. Is repeated 5 times to remove air, and then the temperature is raised to 120 ° C. and 50 kg
/ Cm ² for 2 minutes and 100 kg / cm ² at the same temperature
After heating and pressurizing at a temperature and pressure of 150 kg / cm ² for 1 minute, the pressurized product is cooled to 50 ° C. or less, and the polycarbonate resin plate Polycaace E manufactured by Plastics Co., Ltd.
A 100 mm 3 × 10 cm square piece of C100 was cut out into a 10 × 10 cm square to form a polycarbonate plate laminated with a photocatalyst-carrying film. The sample had a haze ratio to visible light of 0.7% and a total light transmittance of 90.2%, which was extremely high in transparency. (Sample 1)

Example 3 Vinyl chloride resin laminated with a photocatalyst-carrying film The photocatalyst-carrying film (C) obtained in Example 1 was subjected to the same method and under the same conditions as in Example 2 to obtain a transparent hard polychloride manufactured by Sekisui Chemical Co., Ltd. A hard vinyl chloride plate was prepared by laminating a photocatalyst film on a 3 × 10 cm square of a 3 mm thick vinyl resin plate. (Sample 2)

Example 4 Acrylic resin laminated with photocatalyst-carrying film The photocatalyst-carrying film (A) obtained in Example 1 was subjected to the same apparatus as in Example 2 using an acrylic plate Delaglass A No. 1 manufactured by Asahi Kasei Corporation. 999 3mm thickness 10 × 10cm
An acrylic resin plate on which a photocatalyst film was laminated was attached by sticking to a corner cut out and hot-pressing at 140 ° C. for 10 minutes at a pressure of 160 kg / cm ² using a heating press device. (Sample 3)

Example 5 ABS Resin Laminated with Photocatalyst-Supporting Film The photocatalyst-supporting film (B) obtained in Example 1 was coated on the back surface with an ABS resin Psycholac EX manufactured by Ube Siccon Corporation.
215 3 mm thick plate was cut into 10 x 10 cm squares and stuck at 120 ° C using a heating press.
For 10 minutes at a pressure of 160 kg / cm ² to obtain an ABS resin plate on which a photocatalytic film was laminated.
(Sample 4)

Example 6 HIPS Resin Laminated with Photocatalyst Carrier Film A 3 mm thick plate of HIPS resin Idemitsu Styrol HT-54 manufactured by Idemitsu Petrochemical Co., Ltd. was placed on the back of the photocatalyst carrier film (B) obtained in Example 1. Was cut into 10 × 10 cm squares, and was attached using a heating press.
It was hot-pressed at 00 ° C. for 10 minutes at a pressure of 160 kg / cm ² to obtain an ABS resin plate on which a photocatalytic film was laminated. (Sample 5)

Example 7 Vinyl chloride resin laminated with a copper-added photocatalyst-carrying film In Example 1, 0.01% by weight of copper nitrate hydrate based on titanium oxide was added and dissolved in the coating solution for the photocatalyst layer. A photocatalyst-carrying film having a base film of a 50 μm-thick acrylic film “Acryprene HBS-006” manufactured by Mitsubishi Rayon Co., Ltd. was prepared by the same method and apparatus as in Example 1 except that the film was used. This photocatalyst-carrying acrylic resin-based film was laminated on a transparent rigid polyvinyl chloride resin plate manufactured by Sekisui Chemical Co., Ltd. in the same manner and under the same conditions as in Example 3 and a copper-added photocatalyst film laminate was cut into a 3 x 10 cm square. A hard vinyl chloride plate was obtained. (Sample 6)

Example 8 A vanity table using an ABS resin plate laminated with a photocatalytic film The same photocatalyst-supporting film as used in Example 5 and A
A vanity table using an ABS resin plate laminated with a BS resin at a nib pressure of 3 kg / cm using a hot roll laminator, a sheet surface temperature of 130 ° C. on a lamination roll, and a sheet feeding speed of 10 m / min. A prototype of a double door at the bottom of the building. 5 × 5 from this plate for evaluation
A sample cut into cm was used. (Sample 7)

Example 9 Outdoor signboard using an acrylic plate laminated with a photocatalyst film An acrylic resin plate cut out into a character shape for a signboard with a colored vinyl chloride marking film for an outdoor display plate manufactured by Sumitomo 3M Co., Ltd. Then, the photocatalyst-carrying film (C) experimentally produced in Example 1 was placed thereon at a nib pressure of 3 kg / cm, a sheet surface temperature of 120 ° C. with a lamination roll, and a sheet feeding speed of 10 m / min in the same manner as in Example 8. An outdoor signboard using a laminated acrylic resin plate was prototyped. For the evaluation, a sample cut into 5 × 5 cm from this plate was used. (Sample 8)

Example 10 Unit bath consisting of a polyester plate laminated with a photocatalyst film A photocatalyst-carrying film (C) prototyped in Example 1 was laminated on a polyester resin plate in the same manner as in Example 8 at a nib pressure of 3 kg / cm and lamination. A unit bath resin plate using a polyester resin plate laminated at a sheet surface temperature of 120 ° C. with a roll and a sheet feeding speed of 10 m / min was prototyped. For the evaluation, a sample cut into 5 × 5 cm from this plate was used. (Sample 9)

Example 11 A water tank composed of an acrylic plate laminated with a photocatalyst film was laminated on an acrylic resin plate by using a heat roll laminating machine and a photocatalyst film (C) produced in Example 1 at a nib pressure of 3 kg / cm and a lamination roll. Acrylic resin plate laminated at a sheet surface temperature of 120 ° C. and a sheet feeding speed of 10 m / min. A water tank was prototyped using an acrylic resin plate obtained by laminating this photocatalyst supporting film. For the evaluation, a sample cut into 5 × 5 cm from this plate was used. (Sample 10)

Example 12 A storage door for system chitin comprising a HIPS plate laminated with a photocatalyst film The photocatalyst film (C) produced in Example 1 was placed on a HIPS resin plate using a hot roll laminating apparatus at a nib pressure of 3 kg / h. cm, sheet surface temperature on lamination roll 120 ° C, sheet feed speed 1
A HIPS resin plate laminated at 0 m / min was manufactured.
HIPS obtained by laminating this photocatalyst supporting film
A storage door for a system kitchen was prototyped using a resin plate. After a sample of 30 cm x 30 cm was pasted on the door of the existing system kitchen, after 6 months, the stain resistance of the portion where the HIPS plate laminated with the photocatalytic film was adhered was checked by the degree of discoloration measured with a spectral colorimeter. In the evaluation, the change in ΔE was 4.5, whereas the portion of the wallpaper where the photocatalytic film was not laminated was 16.5 in the change in ΔE, indicating that the contamination was more advanced. .

Example 13 A wallpaper made of a PVC sheet laminated with a photocatalyst film A hot roll laminating apparatus was used in which a photocatalyst film (C) produced in Example 1 was attached to an embossing roll on a PVC sheet for a wallpaper to which a foaming agent was added. And nib pressure 3k
g / cm, sheet surface temperature with embossing roll 140
A foamed PVC wallpaper laminated at a temperature of 10 ° C. and a sheet feeding speed of 10 m / min was produced. When a sample of 1 mx 1 m was stuck on the indoor wall, and after 6 months, the evaluation of the stain resistance of the portion on which the wallpaper with the photocatalyst film was laminated was evaluated using the degree of discoloration measured with a spectral colorimeter. While the change in ΔE was 6.5, the portion of the wallpaper on which the photocatalytic film was not laminated had a change in ΔE of 26.5, indicating that the contamination was more advanced.

Example 14 A food tray on which a photocatalytic film was laminated A urethane-based adhesive was applied to the surface of a 0.5 mm-thick polypropylene sheet that had been subjected to corona discharge treatment. Using a hot roll laminating apparatus, a polypropylene sheet was produced by laminating a photocatalytic film at a nib pressure of 3 kg / cm, a sheet surface temperature of 140 ° C. on a lamination roll, and a sheet feeding speed of 10 m / min. The sheet was further heated and pressed to produce a tray for food sales. Place 200 g of beef in this tray (length 25 cm × width 10 cm × depth 3 cm), cover it with a polyethylene wrap film, and irradiate four 10 W fluorescent lamps at a temperature of 20 ° C. with four 10 W fluorescent lamps at a distance of 15 cm. The beef was similarly stored in a polypropylene tray with no film laminated. The tray without the photocatalyst film was discolored black and had a little putrid odor after 4 hours, whereas the one with the photocatalytic film had almost no putrid odor even after 4 hours. To a lesser extent.

Example 15 A packaging film on which a photocatalytic film was laminated The surface of a polyethylene film was subjected to corona discharge treatment in the same manner as in Example 14 and an acrylic adhesive was applied, and then the photocatalyst film (A) prototyped in Example 1 was used. Using a hot roll laminating apparatus, a polyethylene sheet laminated with a photocatalytic film was produced at a nib pressure of 3 kg / cm, a sheet surface temperature of 130 ° C. on a lamination roll, and a sheet feeding speed of 10 m / min. Using this polyethylene sheet, wrap a bunch of spinach in a 15W fluorescent light 3
Under this irradiation, the photocatalytic film was compared with spinach wrapped in a polyethylene film without lamination.
After 4 hours, the spinach wrapped with the polyethylene film laminated with the photocatalyst film had almost no discoloration, whereas the spinach wrapped with the polyethylene film without the photocatalyst film was discolored to dark green and withered. Was. It is considered that ethylene gas emitted from spinach was decomposed.

Comparative Example 1 An acrylic film “Acryprene HBS-006” manufactured by Mitsubishi Rayon Co., Ltd. having a thickness of 50 μm was prepared in the same manner and under the same conditions as in Example 2 to produce a film.
A polycarbonate plate made by laminating an acrylic film on a 3 mm-thick 5 mm x 5 cm piece of a polycarbonate resin plate Polycaace ECK100 was cut out.

Comparative Example 2 Acrylic film "Sandulen" manufactured by Kanegafuchi Chemical Co., Ltd.
008NCP ”with a thickness of 50 μm was purchased from Asahi Kasei Corporation
Delaglass A No. 999 3mm thickness 5 × 5c
An acrylic resin plate was formed by laminating an acrylic film by hot pressing under the same conditions and method as in Example 4 by using a hot press device and attaching it to a piece cut into an m-square.

Comparative Example 3 A hard PVC film made of Sumitomo Bakelite having a thickness of 50 μm was prepared by cutting a 3 mm thick transparent hard polyvinyl chloride resin plate made of Sekisui Chemical Co., Ltd. into a 5 × 5 cm square, the same as in Example 3. According to the method and conditions described above, a rigid polyvinyl chloride plate laminated with a polyvinyl chloride film was used.

(Evaluation of Photocatalytic Activity) Using the samples of Samples 1 to 10 and the sample of Comparative Example, the following evaluation was performed, 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. Evaluation of discoloration degree ΔE increase after 3 months Evaluation 5 or less A 5 to 10 B 10 to 20 C 20 or more D

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 coating so as to be ^2, by irradiating a commercial 15W black light fluorescent lamp placed in a thermo-hygrostat at a temperature 25 ° C. and 70% relative humidity, the ultraviolet UV-A region at the sample surface 3 mW /
The distance between the light source and the sample surface was adjusted so that the intensity became cm ² . The amount of decrease in triolein with respect to the light irradiation time was quantified using a precision balance to determine the triolein decomposition activity. 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 to 75% D (1 to 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 5 cm squares 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. A 0.2 ml bacterial solution of the placed E. coli was dropped on the sample surface and set in an incubator. White fluorescent lamp (15W x 2 lines, distance 10 from light source)
cm), and four samples were set under two types of light irradiation conditions, one in which light irradiation was not performed and the other in which no light irradiation was performed. 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 soaked in sterile saline, and the wiped sterile gauze is put into 10 ml of sterile saline. Stir well. The supernatant was inoculated on an autoclave-sterilized 95 mmφ Petri dish agar medium, and cultured at 36 ° C. for 24 hours, and the number of E. coli colonies was counted. 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 E. 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) Mold resistance The degree of occurrence of green mold on the surface of the sample used for the evaluation of the stain resistance was evaluated by comparison with the sample stored in a cool and dark place according to the following criteria. Evaluation of the degree of generation of mold on the sample surface Almost no occurrence A Partially slight occurrence B evident occurrence C

(Evaluation of 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%. As a coating solution for the photocatalyst layer, titanium oxide P-25 for photocatalyst manufactured by Japan Aerosil Co., Ltd. as a solid content of 30% was used.
30 as a solid content of 20%, Nissan Chemical Co., Ltd. alumina sol-200 as a dry solid content of 10%, an aqueous solution of an acrylic silicone resin emulsion having a silicon content of 20% by weight as a non-volatile residue of 35%, as a silane coupling agent Tri- (β-methoxyethoxy) vinylsilane manufactured by Nippon Unicar Co., Ltd. was prepared such that 5% as a non-volatile residue was 10% as a total 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 acrylic film supporting a photocatalyst was converted to a polycarbonate resin plate Polycaace EC manufactured by Tsutsunaka Plastics Co., Ltd.
A 100 mm 3 mm thick piece cut out into a 10 × 10 cm square was attached and subjected to thermal lamination by the same method and conditions as in Example 2. The contamination resistance, oil decomposition activity, antibacterial property, antifungal property, adhesion and durability of the heat-laminated polycarbonate resin plate are as shown in Table 1. This sample was inferior in photocatalytic activity and durability. Thus, the application of this photocatalyst-carrying film prepared without containing a silane coupling agent in the adhesive layer coating liquid to transparent polycarbonate was inappropriate.

[0069]

The resin structure obtained by laminating the photocatalyst-supporting film of the present invention has a high photocatalytic activity, is excellent in durability, and is used for various building materials intended for antifouling, antibacterial, antifungal and the like. It can be used for outdoor signage, outdoor signage, road peripheral equipment, indoor building materials, indoor equipment, kitchen equipment, toilet wash facilities, etc., and has an excellent price-performance ratio. Further, the photocatalyst-supporting 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-supporting film is laminated on various resin substrates. 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 structure laminated with a photocatalyst-supporting film of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuo Ono 345 Takada, Odawara-shi, Kanagawa Nippon Soda Co., Ltd.Odawara Research Institute Co., Ltd. Inventor Kazuji Okabe 1274 Isohara, Isohara-cho, Kitaibaraki-city, Ibaraki Pref. (72) Inventor Yoshiharu Komoda 1274 Isohara, Isohara-cho, Kitaibaraki-city, Ibaraki Pref.

Claims (16)

[Claims] 1. A photocatalyst-carrying film obtained by laminating a surface of a resin substrate by heating and pressurizing treatment, and irradiating 3 mW of ultraviolet light in the UV-A region at an atmospheric temperature of 25 ° C. and a relative humidity of 70%. / cm ² irradiated to the resin structure a photocatalyst-carrying film was laminated, characterized in that it has a photocatalytic activity of triolein can decompose or ² day 5 [mu] g / cm when the. 2. The resin structure 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 resin structure 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 resin structure 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 resin structure obtained by laminating the photocatalyst-carrying film according to claim 2, wherein the resin structure 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. Resin structure. 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 resin structure 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 resin structure according to claim 6, wherein a photocatalyst-carrying film is laminated by using an adhesive layer coating solution in which a silane coupling agent is added in an amount of 0.1 to 5% by weight based on the coating solution. 9. The resin structure 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. Resin structure 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 resin structure obtained by laminating the photocatalyst-carrying film according to any one of claims 2 to 9, which is contained in an amount of 10% by weight. 12. The resin structure according to claim 10, wherein the photocatalyst layer has a thickness of 0.1 to 5 μm. 13. A resin substrate comprising a polyvinyl chloride resin, a polyethylene terephthalate resin, a polymethyl methacrylate resin, a polycarbonate resin, a polyethylene resin,
Polypropylene resin, impact resistant modified polystyrene resin,
13. A resin selected from the group consisting of acrylic-butadiene-styrene copolymer resin.
A resin structure obtained by laminating the photocatalyst-supporting film according to any one of the above. 14. The shape of the resin substrate may be a plate shape, a sheet shape,
The resin structure obtained by laminating a photocatalyst-carrying film according to any one of claims 1 to 13, wherein the resin structure is a woven fabric, a nonwoven fabric, a resin-impregnated reinforced woven fabric, or a tubular one. 15. 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 photocatalyst layer coating solution is applied to the adhesive layer and dried. A photocatalyst-carrying film having a photocatalyst layer supported on a resin film via an adhesive layer is prepared, and the photocatalyst-carrying film is laminated on the surface of the resin substrate by heating and pressing. Manufacturing method of the manufactured resin structure. 16. A resin structure obtained by laminating the photocatalyst-carrying film according to any one of claims 1 to 14,
Outdoor signboards and signboards used at least in part, telephone boxes, outdoor tent fabrics, vanities, unit baths, system kitchens, ornamental fish tanks, plastic cases, wallpapers, food trays, or packaging films.