JP2001001438A - Film and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make the surface of a base material highly hydrophilic over a long period of time, in a multilayered film having first and second substrate layers, by forming the first substrate layer from a material excellent in flexibility and forming a surface layer containing photocatalyst particles to the surface thereof. SOLUTION: In a photocatalytic hydrophilic film suitable for an anti-fogging film for making the surface of a transparent base material such as a mirror, a lens or glass highly hydrophilic and preventing the formation of fog or waterdrops, a first substrate layer 4 is formed from a film excellent in flexibility such as an acrylic resin film comprising polymethyl methacrylate or the like. A second substrate layer 6 having thermal deformation temp. higher than that of the first substrate layer 4 is formed on the rear surface of the first substrate layer 4 through a self-adhesive layer 5 and a surface layer 1 containing photocatalyst particles is formed on the surface of the first substrate layer 4 through a primer layer 3 and an intermediate layer 2 and shows hydrophilicity corresponding to light excitation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for making and maintaining a surface of a substrate highly hydrophilic and a method for producing the same. More specifically, the present invention relates to an antifogging film that prevents fogging and water droplet formation on a substrate by highly hydrophilizing the surface of a mirror, lens, glass, prism or other transparent substrate, and a method for producing the same. . The present invention also prevents the surface from being stained by highly hydrophilizing the surface of a building, a window glass, a mechanical device or an article,
The present invention also relates to a film capable of self-cleaning (self-cleaning) or easily cleaning the surface and a method for producing the same.

[0002]

2. Description of the Related Art It is often experienced that in cold weather, windshields and windows of automobiles and other vehicles, window glasses of buildings, lenses of glasses and goggles, and cover glasses of various instrument panels are fogged by condensed moisture. is there. In addition, mirrors and eyeglass lenses in bathrooms and washrooms are often fogged by steam. Furthermore, when windshields and windowpanes of vehicles, windowpanes of buildings, lenses of glasses and goggles, shields of masks and helmets receive rain and splashes, and a large number of discrete water droplets adhere to the surface, those surfaces become dark, Blurred, mottled, or cloudy, again losing visibility. As used herein, the term "anti-fog" broadly refers to a technique for preventing optical hindrance due to such fogging, growth of condensed water droplets, and adhesion of water droplets. Needless to say, the above "clouding" has a profound effect on safety and efficiency of various operations. For example, if the windshield, window glass, or rearview mirror of a vehicle is exposed to cold or rainy weather, becomes blurred, spotted, or fogged, it becomes difficult to secure a view, and traffic safety is impaired. When endoscope lens and dental mirror become cloudy, accurate diagnosis, surgery,
Obstruct treatment. If the cover glass of the instrument panel becomes cloudy, it will be difficult to read the data.

As is well known, a conventionally used anti-fog method is to apply an anti-fog composition containing a hydrophilic compound such as polyethylene glycol or a water-repellent compound such as silicone to the surface. . However, this kind of anti-fog coating is only temporary, and has the drawback that it is easily removed by washing or contact and loses its effect early.

[0004] On the other hand, in the fields of construction and paints, stains on building exterior materials, outdoor buildings and their coatings have become a problem with environmental pollution. Dust and particles suspended in the air accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater as it rains and flows down the building's outer walls. Furthermore, in the rain, the floating dust is carried by the rain and flows down on the outer wall of the building or the surface of the outdoor building. As a result, pollutants adhere to the surface along the path of rainwater. When the surface dries, striped stains appear on the surface. Dirt on building exterior materials and coatings consists of combustion products such as carbon black, and inorganic pollutants such as urban dust and clay particles. It is believed that the diversity of such contaminants complicates antifouling measures (Yoshinori Tachibana,
"Method for Accelerated Testing of Exterior Wall Finishing Material Contamination", Architectural Institute of Japan Structural Transactions, No. 404, October 1989,
p. 15-24).

According to conventional wisdom, in order to prevent dirt on the building exterior and the like, polytetrafluoroethylene (PT) is used.
Water-repellent paints such as FE) have been considered preferable, but recently it has been considered desirable to make the surface of the paint film as hydrophilic as possible for urban dust containing a large amount of hydrophobic components. (Polymer, Vol. 44, May 1995, p. 307). Therefore, it has been proposed to paint the building with a hydrophilic graft polymer (newspaper "Chemical Industry Daily", January 30, 1995). According to reports, this coating exhibits a hydrophilicity of 30 to 40 ° in contact angle with water. However, the contact angle of inorganic dust represented by clay minerals with water is from 20 ° to 50 °, and has an affinity for the graft polymer having a contact angle with water of 30 to 40 ° and adheres to the surface. Therefore, it is considered that this graft polymer coating film cannot prevent contamination by inorganic dust.

In view of such a situation, the applicant of the present application
According to T / JP96 / 00733, the surface of the member becomes 10 ° or less in terms of the contact angle with water due to the hydrophilic action in response to light excitation, and condensed even when moisture or steam in the air is condensed. A hydrophilic member excellent in antifogging property and self-cleaning property is proposed because water forms a uniform water film without forming individual water droplets. Furthermore, Japanese Patent Application No. 8-28
At 4534, the proposal of a hydrophilic film allows its application on various substrates.

[0007]

SUMMARY OF THE INVENTION The hydrophilic member and the hydrophilic film proposed by the applicant of the present invention can be provided by a member excellent in anti-fogging property and self-cleaning property. However, there are still technical problems to be solved in order to apply them to actual components. In order to form a photocatalytic hydrophilic film on a resin film, it is necessary to dry the film preferably at a temperature of 100 ° C. or higher. On the other hand, since the resin film is also assumed to be stuck on a curved surface, it is preferable to select a material having good flexibility, but such a material having good flexibility generally has a low heat deformation temperature, Deformation is apt to occur in the drying step, and special consideration is required to prevent the deformation. The present invention has been made in view of such a situation, and an object of the present invention is to provide a film that makes a surface of a base material highly hydrophilic for a long period of time simply by sticking it to the surface of the base material, and a method for producing the same.

[0008]

A first invention is a multilayer film having a first base layer and a second base layer, wherein the first base layer is excellent in flexibility. By providing a characteristic multilayer film, for example, the second substrate layer can be separated at the time of use, and the excellent flexibility of the first substrate layer can be maximized. Good flexibility
Although not particularly limited numerically, when the film according to the present invention is applied to a mirror of an automobile having a three-dimensional curved surface, the modulus of longitudinal elasticity is 5000 MPa or less.
It is preferably at least 00 MPa, more preferably at most 4000 MPa and at least 2500 MPa. A second invention is a multilayer film having a first base layer and a second base layer, wherein the heat deformation temperature of the second base layer is higher than the heat deformation temperature of the first base layer. By providing a multilayer film characterized by the above feature, it is possible to heat and process at a higher temperature than the film of the first base layer single layer. When a multilayer film having both the contents of the first invention and the second invention is formed, it is needless to say that both characteristics can be provided.

A third invention is a multilayer film having a first base layer and a second base layer, wherein an adhesive layer is formed between the first base layer and the second base layer. By providing the multilayer film according to the first invention or the second invention, in addition to the effects of the first invention or the second invention, after removing the second base layer The first substrate layer can be attached to the surface of the substrate of a window glass, a signboard or an article.

[0010] A fourth invention is a multilayer film having a first base layer and a second base layer, wherein the second base film has a thickness higher than that of the second base layer. By providing a multilayer film according to the third invention, wherein the adhesive force at the interface between the base layer and the adhesive layer is weak.
In addition to the effects of the third aspect, only the second base layer can be easily removed.

A fifth invention provides the multilayer film according to any one of the first to fourth inventions, wherein the first base layer has a surface layer containing photocatalyst particles on the surface of the first base layer. By doing so, in addition to the effects of the above-described respective inventions, it is possible to exhibit effects such as hydrophilicity specific to the photocatalyst. In this case, a primer layer and / or an intermediate layer can be provided between the surface layer containing the photocatalyst particles and the first base layer. Can be reduced, and the adhesion between the base layer and the surface layer can be improved.

In a sixth aspect based on the fifth aspect, the step of forming the surface layer and / or the primer layer and / or the intermediate layer is performed at a temperature equal to or higher than a thermal deformation temperature of the first base layer.
Preferably, by providing a multilayer film characterized by being capable of being heat-treated at a temperature of 100 ° C. or more and 140 ° C. or less, in addition to the effect of the fifth aspect, the curing of the surface layer is promoted, And the first base layer can be improved in adhesion.

A seventh invention provides a multilayer film according to the fifth or sixth invention, wherein the surface layer exhibits hydrophilicity in response to light excitation.
In addition to the effects of the above inventions, even when the effect of hydrophilization is reduced by use, hydrophilicity is regenerated by photoactivity again.

In an eighth aspect based on the seventh aspect, the surface layer is substantially transparent, and condensed water and / or moisture adhering to the surface layer is formed by hydrophilization in response to the light excitation.
Or by providing a photocatalytic hydrophilic film in which water droplets spread evenly on the surface of the surface layer and are prevented from being clouded or shaded by moisture condensed water and / or water droplets,
When the surface of a window glass, signboard, or article is coated with the film, even if moisture or water droplets of the atmosphere adhere to the surface, the film does not form a water droplet, but becomes a uniform water film, and becomes visible. Can be prevented from being lost.

In a ninth aspect based on the seventh aspect, the surface layer is substantially transparent, and the surface layer is made hydrophilic when the surface layer is exposed to rainfall by hydrophilization in response to the light excitation. By providing a photocatalytic hydrophilic film having self-cleaning properties that allow contaminants to be washed away by raindrops, when the film is coated on the surface of a window glass, signboard or article, the surface is exposed to rainfall. At this time, attached deposits and / or contaminants can be washed away by raindrops, and self-cleaning by rainfall becomes possible. Furthermore, when the surface exhibits a high degree of hydrophilicity, the surface can be washed with water rinsing or simple water wiping, which facilitates water washing.

A tenth invention is directed to the photocatalytic hydrophilic film according to any one of the fifth to ninth inventions, wherein the surface layer further contains amorphous silica. By providing, the surface has a water wetting angle of 0 °
And a high degree of hydrophilicity, which is close to, and the hydrophilicity when held in a dark place is improved.

An eleventh invention provides a photocatalytic hydrophilic film according to any one of the fifth to tenth inventions, wherein the surface layer further contains silicone. As a result, by photoexcitation of the photocatalyst, at least a part of the organic group bonded to the silicon atom in the silicone is replaced with a hydroxyl group, and a physisorption water layer is further formed thereon.
In addition to exhibiting a high degree of hydrophilicity close to °, the hydrophilicity when held in a dark place is improved.

According to a twelfth aspect, in any one of the fifth to eleventh aspects, the thickness of the surface layer is 0.4
By providing a photocatalytic hydrophilic film having a thickness of not more than μm, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent.

According to a thirteenth aspect, in any one of the fifth to eleventh aspects, the thickness of the surface layer is 0.2.
By providing a photocatalytic hydrophilic film having a thickness of not more than μm, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency. Further, when the film thickness is reduced, the wear resistance of the surface layer is improved.

According to a fourteenth aspect, in any one of the fifth to thirteenth aspects, there is provided a photocatalytic hydrophilic film, wherein the refractive index of the surface layer is 2 or less. Light reflection at the interface between the base layer and the surface layer and between the surface layer and the air can be suppressed.

According to a fifteenth aspect, in any one of the fifth to fourteenth aspects, the hydrophilicity of the photocatalyst in response to photoexcitation is 10 ° or less in terms of a contact angle with water,
By providing a photocatalytic hydrophilic film that is preferably 5 ° or less, even if moisture or water droplets in the atmosphere adhere to the surface, the film does not become water droplets, but becomes a uniform water film, Loss of visibility can be prevented.

According to a sixteenth aspect, a first step of preparing a multilayer film having a first base layer and a second base layer having a higher heat deformation temperature than the first base layer is provided. A second step of forming a primer layer on the surface of the first base layer, a third step of forming an intermediate layer on the surface of the primer layer, and a fourth step of forming a layer containing photocatalyst particles on the surface of the intermediate layer.
By providing a method for producing a film exhibiting hydrophilicity in response to light excitation having the steps of: (a) processing at a temperature equal to or higher than the thermal deformation temperature of the first base layer; The surface layer containing the photocatalyst particles can be firmly adhered, and a film can be produced that has a highly hydrophilic surface over a long period of time.

According to a seventeenth aspect, in the sixteenth aspect,
The step of forming the primer layer includes a first step of applying a primer resin and a drying temperature of 100 ° C to 140 ° C.
By providing a method for producing a film exhibiting hydrophilicity in response to photoexcitation comprising a second step of drying at 115 ° C. to 125 ° C., it is possible to accelerate the curing of the primer resin in addition to the effect of the present invention. The adhesion to the first base layer can be improved.

The eighteenth invention is directed to the sixteenth invention or the seventeenth invention.
In the invention, the step of forming the intermediate layer includes a first step of applying a coating material composed of silicone or a silicone precursor, and a drying temperature of 100 ° C to 140 ° C and 115 ° C to 115 ° C.
A second step of drying at 125 ° C., and a method for producing a film exhibiting hydrophilicity in response to photoexcitation comprising: promoting the curing of a coating comprising silicone or a silicone precursor; Can be improved.

The nineteenth invention is directed to the sixteenth to eighteenth inventions.
In any one of the inventions, the step of forming the layer containing the photocatalyst particles includes a first step of applying a coating material comprising the photocatalyst particles and methyl silicate, and a drying temperature of 100 ° C to
A second step of drying at 140 ° C., preferably 115 ° C. to 125 ° C., and a method for producing a film exhibiting hydrophilicity in response to photoexcitation, comprising: curing of a coating material comprising photocatalyst particles and methyl silicate. Promote
Adhesion with the silicone layer can be improved.

[0026]

Next, a specific configuration of the present invention will be described. One preferred embodiment of the photocatalytic hydrophilic film in the present invention is as shown in FIG. As the first base layer, a layer made of a film having excellent flexibility is formed. As the material of the film having excellent flexibility, for example, an acrylic resin film such as polymethyl methacrylate (PMMA) and a vinyl chloride resin film such as polyvinyl chloride (PVC) are selected. When the film is used outdoors or the like, it is desirable to select an acrylic resin film having excellent weather resistance. On the back surface of the first base layer, the second
Is formed. The material of the second base layer is not particularly limited. For example, by selecting a PET film or the like having excellent heat deformation resistance,
The physical properties of the first base layer can be complemented, and the heat deformation resistance can be improved as a whole. The first substrate layer and the second substrate layer are adhered by an appropriate method. In FIG. 1, the first base layer and the second base layer are adhered to each other by an adhesive layer, and the adhesive layer has an action of bringing the first base layer and the second base layer into close contact with each other. When the film is used, the first base layer can be attached to the base by peeling the second base layer.

On the first base layer, there is formed a primer layer characterized in that the composition contains tetraalkoxysilane, alkyl silicate and liquid alcohol.

By forming the primer layer on the first base layer, the adhesion between the first base layer and the intermediate layer formed thereon can be improved.

Further, on the primer layer, the above-mentioned intermediate layer composed of silicone is formed. Silicone precursors include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, and phenyltrimethoxysilane. Silane, phenyltriethoxysilane, phenyltributoxysilane, phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, Diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldibutoxysilane,
Phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, their hydrolysates, and mixtures thereof can be suitably used.

By forming an inorganic intermediate layer below the photocatalyst layer, it is possible to prevent the deterioration of the base layer and the separation of the photocatalyst layer due to the decomposition of the photocatalyst by organic substances.

On the intermediate layer, there is formed a photocatalyst layer in which the composition is composed of photocatalytic titanium oxide particles and silica which is a hardly decomposable curable binder. The hard-to-decompose curable binder refers to a binder in which the decomposition / degradation reaction due to the oxidizing action of the photocatalyst does not progress or the decomposition rate is extremely slow. Examples of silica include tetrachlorosilane and tetrabromosilane. Hydrolysis, dehydration condensation polymerization of halogenated silanes; or hydrolysis, dehydration condensation polymerization of tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, dimethoxydiethoxysilane, or methylsilike -Ethyl silicate, ethylmethyl silicate, propyl silicate
Silica formed by hydrolysis and dehydration condensation polymerization of alkyl silicates such as butyl silicate and the like can be suitably used.

A photocatalyst, when irradiated with light (excitation light) having an energy (that is, a shorter wavelength) larger than the energy gap between the conduction band and the valence band of the crystal, emits electrons in the valence band. A substance that can generate conduction electrons and holes by excitation (photoexcitation). Examples thereof include anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, bismuth trioxide, tungsten trioxide, and tungsten oxide. Ferrous iron, strontium titanate and the like can be suitably used. Here, as a light source used for photoexcitation of the photocatalyst, a light source in an environment such as sunlight or general indoor lighting may be used, or a light source capable of irradiating excitation light as accessory equipment or portable equipment may be used. . Further, the plastic lens of the present invention, or a spectacle provided with the plastic lens or a storage container dedicated to goggles provided with the plastic lens, may be provided with a light source capable of irradiating excitation light. As the light source used in this case, for example, an incandescent lamp, a metal halide lamp, a mercury lamp, a xenon lamp, a germicidal lamp, a fluorescent lamp and the like can be suitably used. In order for the substrate surface to be highly hydrophilic by photoexcitation of the photocatalyst, the illuminance of the excitation light is 0.0
0.01 mW / cm ² or more, but 0.01 mW / c ² or more.
m ² or more, more preferably 0.1 mW / cm ² or more.

The thickness of the surface layer containing the photocatalyst is 0.4
It is preferable that the thickness be not more than μm. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. More preferably, the thickness of the surface layer containing the photocatalyst is 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency.
Further, when the film thickness is reduced, the wear resistance of the surface layer is improved. The surface of the surface layer may be further provided with a wear-resistant or corrosion-resistant protective layer capable of being made hydrophilic and other functional films.

It is preferable that the refractive index of the surface layer is not so high as compared with that of the substrate. Preferably, the refractive index of the surface layer is 2 or less. Then, light reflection at the interface between the substrate and the surface layer and the interface between the surface layer and air can be suppressed. In order to reduce the refractive index of the surface layer to 2 or less, a substance having a refractive index of 2 or less is used for the photocatalyst. To be added. As a photocatalyst having a refractive index of 2 or less, tin oxide (refractive index: 1.9) or the like can be used. 2
Photocatalysts having the above refractive index include anatase-type titanium oxide (refractive index: 2.5) and rutile-type titanium oxide (refractive index: 2.7). For example, calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), magnesium carbonate (refractive index 1.5), strontium carbonate (refractive index 1.5), dolomite (refractive index 1.7) ), Calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), silica (refractive index 1.5), alumina (refractive index 1.6), silica sand (refractive index 1.6) ), Montmorillonite (refractive index 1.
5), kaolin (refractive index 1.6), sericite (refractive index 1.6), zeolite (refractive index 1.5), tin oxide (refractive index 1.9) and the like may be added to the surface layer.

Metals such as Ag, Cu and Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.

On the surface layer, Pt, Pd, Ru, R
A platinum group metal such as h, Ir, Os can be added. The surface layer to which the metal is added can enhance the oxidation-reduction activity of the photocatalyst and improve the deodorizing and purifying action and the like.

The term "hydrophilic" refers to a property that is easily conformable when water is dropped on the surface, and generally refers to a state where the water wetting angle is less than 90 °. The term “high hydrophilicity” in the present invention refers to a property that is highly compatible when water is dropped on the surface, and more specifically, a state where the water wetting angle on a smooth surface is about 10 ° or less. In particular, PCT / JP9
As disclosed in 6/00734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less.

The film of the present invention can be applied to various substrates. The substrate to which the film according to the present invention can be applied is a transparent substrate when the above antifogging effect is expected, and the material thereof can be suitably used for a substrate such as glass or transparent plastic. Applicable substrates include mirrors such as vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors; spectacle lenses, optical lenses, camera lenses, illumination lenses, lasers. Lenses such as light focusing lenses, semiconductor lenses, and copier lenses; prisms; windows of buildings and towers; automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, ropeway gondolas,
Amusement park gondola, window glass for vehicles like spaceships; cars, railcars, motorcycles, aircraft, ships, submarines,
Snow car, ropeway gondola, amusement park gondola,
Windshield glass for vehicles such as spaceships; protective goggles, sports goggles, shields for protective masks, shields for sports masks, shields for helmets, glass for frozen food display cases; suitable for cover glass for measuring instruments, etc. Available. As a substrate to which the film of the present invention can be applied, when the above surface cleaning effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete,
Fibers, fabrics, combinations thereof, and laminates thereof can be suitably used. Applicable base materials include building materials, building exteriors, building interiors, window frames, windowpanes, structural members, vehicle exteriors and coatings, machinery and articles exteriors, dustproof covers and coatings, traffic signs, various types of Display devices, advertising towers, noise barriers for roads, noise barriers for railways, bridges, guardrail exteriors and coatings, tunnel interiors and coatings, insulators, solar cell covers, solar water heater collector covers, plastic greenhouses, vehicle lighting Covers, housing equipment, toilets, bathtubs, washbasins, lighting fixtures,
It can be suitably used for lighting covers, kitchenware, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, and the like. Since the film in the present invention can maintain a high degree of hydrophilicity for a long period of time, an antistatic function can also be expected. When antistatic effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete,
Fibers, fabrics, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable base materials, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, housing and parts for household electrical appliances, exterior and coating, OA equipment It can be suitably used for housing, parts, exterior and coating of products, building materials, building exterior, building interior, window frames, window glass, structural members, exterior and coating of vehicles, exterior of machinery and articles, dustproof cover and coating, etc. .

Next, an example of the method for producing a film according to the present invention will be described. FIG. 2 is a process flow of the present manufacturing method. FIG. 3 shows a film manufacturing apparatus. Hereinafter, description will be given with reference to the drawings.

First, polymethyl methacrylate (P
A film having a two-layer structure composed of MMA) and polyethylene terephthalate (PET) is prepared.

Next, a paint (Shin-Etsu Chemical Co., Ltd., PC-7A) for forming a primer layer is put in the paint tank 4.
The lower part of the C roll 5 is rotated while being immersed in the paint. Next, the film is unwound at a constant speed, and is brought into contact with the rotating C roll 5 in a state of being immersed in the paint, so that the paint adheres to the film surface. Next, the paint adhered to the surface of the film was applied to a Meyer bar 6 (having a wire diameter of 0.1 to 1.
(A bar around which a wire of 0 mm is wound) to scrape off the paint and adjust the film thickness. Further, 100 ° C. to 140
° C, preferably 115 ° C to 125 ° C, by passing the film through a drying oven 7 to accelerate the curing of the paint, form a primer layer, and finally wind the film out of the drying oven 7 .

Next, a paint (Shin-Etsu Chemical Co., Ltd., KP-85) for forming an intermediate layer is put in the paint tank 4, and the C roll 5 is rotated while being immersed in the paint. Next, the film on which the primer layer has been formed is unwound at a constant speed, and is brought into contact with the rotating C roll 5 in a state of being immersed in the paint, so that the paint adheres to the film surface. Next, the paint adhered to the surface of the film is brought into contact with a Meyer bar 6 (a bar around which a wire having a wire diameter of 0.1 to 1.0 mm is wound) to scrape off the paint and adjust the film thickness. Furthermore, 10
The film is passed through a drying oven 7 set at 0 ° C. to 140 ° C., preferably 115 ° C. to 125 ° C., to accelerate the curing of the paint, form an intermediate layer, and finally emerge from the drying oven 7. Wind the film.

Next, a paint for forming a surface layer containing photocatalyst particles is put in the paint tank 4, and the C roll 5 is rotated in a state where the lower portion is immersed in the paint. Next, the film on which the intermediate layer has been formed is unwound at a constant speed, and is brought into contact with the rotating C roll 5 in a state of being immersed in the paint, thereby causing the paint to adhere to the film surface. Next, the paint adhered to the surface of the film was applied to a Meyer bar 6 (having a wire diameter of 0.1 to 1.
(A bar around which a wire of 0 mm is wound) to scrape off the paint and adjust the film thickness. Further, 100 ° C. to 140
C., preferably 115 ° C. to 125 ° C., by passing the film through a drying oven 7 to accelerate the curing of the paint, form a photocatalytic layer, and finally wind the film out of the drying oven 7 .

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a film

FIG. 2 is a flowchart of a film manufacturing method.

FIG. 3 Film production equipment

[Explanation of symbols]

1: Layer containing photocatalyst particles 2: Intermediate layer 3: Primer layer 4: First base layer 5: Adhesive layer 6: Second base layer 7: Film roll before application of paint 8: Paint applied Later film roll 9: Guide roll for feeding the film 10: Paint tank 11: Stainless steel roll for applying the paint to the film (common name: C roll) 12: Bar for scraping off the paint (common name: Meyer bar) 13: Drying oven for curing paint

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 9/00 B01D 53/36 J CF Term (Reference) 3B117 AA01 AA02 AA08 4D048 AA21 AA22 AB01 AB03 BA07X BA15Y BA16Y BA21Y BA22Y BA27Y BA36Y BA41X BB03 CA06 EA01 4F100 AA20D AH06D AK52D AT00A AT00B BA04 BA07 BA10A BA10D CB05C CC012 DE01D EA021 EH46 EH462 EJ65 EJ651 EJ86 EJ861 EJ863 GB07 GB31 GB51 GB71 GB87 JA04A JA04B JB05D JK17B JL06 JL06D JL07 JL07D JL08D JL13 JL14A JN00D JN18D YY00D

Claims (26)

[Claims] 1. A multilayer film having a first base layer and a second base layer, wherein the first base layer is excellent in flexibility. 2. A multilayer film having a first base layer and a second base layer, wherein a heat deformation temperature of the second base layer is higher than a heat deformation temperature of the first base layer. Multilayer film characterized by 3. The multilayer film according to claim 1, wherein an adhesive layer is formed between the first base layer and the second base layer. 4. The adhesive force at the interface between the second substrate layer and the adhesive layer is lower than the adhesive force at the interface between the first substrate layer and the adhesive layer. 3. The multilayer film according to 3. 5. The method according to claim 3, wherein the second base layer is peeled off and removed, whereby the first base layer is attached to the base material by the adhesive action of the adhesive layer. Multilayer film 6. The multilayer film according to claim 1, further comprising a surface layer containing photocatalyst particles on a surface of said first base layer. 7. A device according to claim 6, further comprising a primer layer and / or an intermediate layer between said first base layer and said surface layer.
The described multilayer film 8. The step of forming the surface layer and / or the primer layer and / or the intermediate layer on the surface of the first base layer, wherein the heat treatment is performed at a temperature not lower than the thermal deformation temperature of the first base layer. The multilayer film according to claim 6 or 7, wherein 9. A process for forming the surface layer and / or the primer layer and / or the intermediate layer on the surface of the first base layer, wherein the heat treatment can be performed at a temperature of 100 ° C. or more and 140 ° C. or less. A multilayer film according to claim 6 or 7, characterized in that: 10. The multilayer film according to claim 6, wherein said surface layer exhibits hydrophilicity in response to photoexcitation. 11. The surface layer is substantially transparent, and condensed water and / or water droplets of moisture adhering to the surface layer are uniformly formed on the surface of the surface layer by hydrophilization in response to the photoexcitation. The multilayer film according to claim 10, wherein the multilayer film is prevented from being clouded or overcast by moisture condensed water and / or water droplets. 12. The surface layer is substantially transparent, and the hydrophilization in response to the photoexcitation causes the sediment and / or contaminants to be washed away by raindrops when the surface layer is exposed to rainfall. The multilayer film according to claim 10, which has a self-cleaning property. 13. The multilayer film according to claim 6, wherein said surface layer further contains amorphous silica. 14. The multilayer film according to claim 6, wherein said surface layer further contains silicone. 15. The multilayer film according to claim 6, wherein the thickness of the surface layer is 0.4 μm or less. 16. The multilayer film according to claim 6, wherein the thickness of the surface layer is 0.2 μm or less. 17. The multilayer film according to claim 6, wherein said surface layer has a refractive index of 2 or less. 18. The multilayer film according to claim 6, wherein the hydrophilicity of the photocatalyst in response to photoexcitation is 10 ° or less in terms of a contact angle with water. 19. The multilayer film according to claim 6, wherein the hydrophilicity of the photocatalyst in response to photoexcitation is 5 ° or less in terms of a contact angle with water. 20. A first step of preparing a multilayer film having a first substrate layer and a second substrate layer having a higher heat distortion temperature than the first substrate layer, and a first substrate of the multilayer film. A second step of forming a primer layer on the surface of the layer, a third step of forming an intermediate layer on the surface of the primer layer, and a fourth step of forming a layer containing photocatalyst particles on the surface of the intermediate layer. Method of producing film having 21. The step of forming a primer layer includes a first step of applying a primer resin and a drying temperature of 100%.
21. The method for producing a film according to claim 20, comprising a second step of drying at a temperature of from 140C to 140C. 22. The step of forming a primer layer includes a first step of applying a primer resin and a drying temperature of 115.
21. The method for producing a film according to claim 20, comprising a second step of drying at a temperature of from 125C to 125C. 23. The step of forming the intermediate layer comprises the step of applying a paint comprising silicone or a silicone precursor.
And a second step of drying at a drying temperature of 100 ° C to 140 ° C.
Manufacturing method of the film described in the item 24. The step of forming the intermediate layer comprises a step of applying a paint comprising silicone or a silicone precursor.
And a second step of drying at a drying temperature of 115 ° C to 125 ° C.
Manufacturing method of the film described in the item 25. The step of forming the layer containing the photocatalyst particles comprises: a first step of applying a coating composed of photocatalyst particles and methyl silicate; and a second step of drying at a drying temperature of 100 ° C. to 140 ° C. 25. The method according to claim 20, wherein
A method for producing a film according to any one of the preceding claims. 26. The step of forming a layer containing photocatalyst particles comprises: a first step of applying a coating material comprising photocatalyst particles and methyl silicate; and a second step of drying at a drying temperature of 115 ° C. to 125 ° C. 25. The method according to claim 20, wherein
A method for producing a film according to any one of the preceding claims.