JP2003019775A - Anti-contamination sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-contamination sheet which has a photocatalytic surface layer and is capable of retaining anti-contamination properties outdoors for a long time. SOLUTION: This anti-contamination sheet is constituted by forming a surface layer containing a photocatalyst (e.g. titanium dioxide) on a base material layer consisting of at least one thermoplastic resin composition layer and, if necessary, a fibrous base cloth, through a photocatalyst-bonding and protecting layer, if necessary. In addition, 0.01 to 5.0 wt.% of an anti-oxidizing agent is added to the thermoplastic resin composition and, if necessary, the photocatalyst-bonded and protecting layer. Further, the thermoplastic resin composition layer and at least one surface layer containing the photocatalyst and, if necessary, the photocatalyst-bonded and protecting layer are colored by a colorant containing an inorganic pigment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifouling sheet. More specifically, the present invention is
The present invention relates to an antifouling sheet which has excellent antifouling property and durability for a long period of time and is suitably used as an industrial material such as building members such as medium and large tents and tent warehouses, truck hoods and sign sheets for signboards. .

[0002]

2. Description of the Related Art Conventionally, a laminated sheet in which a thermoplastic resin composition is coated on a fibrous base cloth by various methods such as a calender method, a T-die extrusion method, and a coating method is used as a shade tent or a medium or large tent. It is used in various fields and applications as a building material such as a tent warehouse, a building curing sheet, and an industrial material sheet such as a truck hood, a signboard for signboards, and a flexible container. As a thermoplastic resin used for such applications, a soft vinyl chloride resin composition has many advantages such as resin characteristics, durability, flexibility of compounding, processability, high-frequency welder property, and cost efficiency. Therefore, it is widely used as a general-purpose resin in these fields and applications. However, in such applications that are used outdoors for a long period of time, a large amount of a plasticizer is blended in the soft vinyl chloride resin composition, and this plasticizer bleeds and oozes out on the surface of the sheet over time. However, there is a drawback in that pollutants such as soot and dust in the atmosphere are likely to be attached and accumulated, and therefore easily polluted. Moreover, among these stains, especially the streak-like stain called rain streak stain cannot be easily removed by wiping, and the rain streak stain remarkably impairs the beauty, color and design of sunshade tents and medium and large tents. Has caused a serious problem.

Therefore, as a means for avoiding the trouble caused by such bleeding of the plasticizer, for example, an acrylic resin or a urethane resin is dissolved in an organic solvent on the surface of a soft vinyl chloride resin composition molded sheet. A method of forming a plasticizer bleed preventive antifouling layer by topcoating the coating composition prepared by the above method, a method of forming a topcoat antifouling layer with an emulsion solution of the above resin, or a heat lamination method of an acrylic resin film or There has been proposed a method of preventing the soft vinyl chloride resin composition molded sheet from being soiled by a plasticizer bleed by a laminating method using an adhesive. Further, a (meth) acryloyl group-containing acrylic oligoester compound is blended in the soft vinyl chloride resin composition, and the mixture is subjected to a heat curing method, an ultraviolet curing method,
Alternatively, a method has also been proposed in which a crosslinked structure is formed in the resin composition by an electron beam curing method or the like to thereby prevent bleeding of the plasticizer. However, the antifouling effect of the soft vinyl chloride resin composition molded sheet by preventing the bleeding of these plasticizers is that the adhesion of dirt is certainly not conspicuous in the early stage of outdoor use, and the appearance of the tent and the sheet is maintained. Although it makes it possible, with the passage of time, the plasticizer passes through these plasticizer anti-bleeding layers and oozes onto the surface of the sheet, and in the long term, the accumulation of stains and the generation of rain streak stains are again caused. I couldn't prevent it.

On the other hand, by coating the surface of a molded sheet of a soft vinyl chloride resin composition with a photocatalyst, soot and pollutant organic substances, which are the causative substances of stains adhering to the surface of the sheet over time, are treated as photocatalysts. A technique has been proposed in which the aesthetics of a sheet is maintained for a long period of time by being decomposed and removed by a photocatalytic action. However, since this photocatalyst simultaneously deteriorates and decomposes the soft vinyl chloride resin composition itself which is the base material, the photocatalyst drops out together with the deterioration product of the soft vinyl chloride resin composition at an early stage after the start of use outdoors. On the contrary, it has the drawbacks of promoting dirt and significantly shortening the outdoor durability of the sheet.

Therefore, even when the photocatalyst is widely applied to synthetic resin compositions, one method of preventing the synthetic resin composition from deteriorating or decomposing is, for example, that the surface of the synthetic resin composition base material is stable to the photocatalytic action. It has been proposed to form a protective layer of resin and utilize this protective layer as a support for a photocatalyst and as a carrier, and it is said that this proposed method is the most effective and practical. However, a resin that is stable to photocatalysis is
Since it is limited to either a silicone resin or a fluorine resin, the resulting adhesive / protective layer does not necessarily have excellent adhesiveness and adhesiveness with the synthetic resin composition of the base material, but in reality it is a synthetic resin. It has the drawback of poor adhesion to the composition. Therefore, in order to solve the above problems, an acrylic / silicone copolymer resin, an acrylic-fluorine copolymer resin, and a urethane-silicone-fluorine resin are used as an adhesive / protective layer provided on the surface of a synthetic resin composition substrate. Using a copolymer resin such as a copolymer resin, a resin blend of a silicone resin and an acrylic resin, a resin blend of a fluorine resin and an acrylic resin, and the like,
A method having a certain degree of resistance to decomposition (stability) with respect to a photocatalyst and improving the adhesion to a synthetic resin composition substrate to some extent has gradually come into practical use. By forming a protective layer of these acrylic-silicone-based or acrylic-fluorine-based copolymer resin or blend resin on the surface of the synthetic resin composition base material, the antifouling effect by the photocatalytic action is certainly relatively long. It will be possible to maintain it for a period of time. However, since the acrylic component in these copolymer resins or blended resins is decomposed and deteriorated over time due to photocatalytic action, the synthetic resin composition of the underlying base material layer is gradually decomposed and deteriorated, and eventually. This results in deterioration and loss of the photocatalyst coating layer.

Although the adhesiveness between the protective layer of these silicone-based or fluorine-based copolymer resin or blend resin and the base material layer is improved to some extent, however, it is outdoors for a long period of time. When it is used as a building member such as medium and large-sized tents, sunshade tents, and tent warehouses that are used throughout, it cannot sufficiently withstand severe fluttering due to wind and rain, shock, and abrasion. Therefore,
When the photocatalyst is applied to the synthetic resin composition base material, the copolymer resin and the blend resin are not practically satisfactory for the above-mentioned tent use. In addition, as the colorant for these synthetic resin base materials, a wide variety of organic pigments and inorganic pigments are selected and used according to the desired hue, design, and cost, but especially the colorant. When an organic pigment is used as a pigment, not only the synthetic resin is decomposed and deteriorated by photocatalytic action, but also these organic pigments are decomposed.Therefore, such as medium and large tents, shade tents, tent warehouses, etc. In use, the decomposition and deterioration of the synthetic resin are accompanied by the decomposition and deterioration of the organic pigment, which causes a problem that the tent gradually discolors or fades.

[0007]

DISCLOSURE OF THE INVENTION The present invention is capable of maintaining excellent antifouling property outdoors for a long period of time and, when colored, maintaining its color, and has a photocatalytic effect. The present invention intends to provide an antifouling sheet that is stable for a long period of time and has excellent durability.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted research and studies on the antifouling sheet in view of the above-mentioned situation, and as a result, a thermoplastic resin composition for a base material layer carrying a photocatalyst-containing surface layer has been obtained. The present invention has been completed by discovering that the above problems can be solved by incorporating and containing a specific amount of an antioxidant in a layer.

The antifouling sheet of the present invention has a base material layer containing at least one thermoplastic resin composition layer, and a surface layer formed on at least one surface thereof and containing a photocatalyst. The thermoplastic resin composition layer closest to the surface layer containing at least the photocatalyst of the base material layer is 0.01 to 5.0.
At least one layer of the thermoplastic resin composition layer and the surface layer containing a photocatalyst, which contains an antioxidant in a weight percentage, is colored with a colorant containing an inorganic pigment. It is a thing. In the antifouling sheet of the present invention, a photocatalyst adhesive containing a thermoplastic resin containing 0.01 to 5.0% by weight of an antioxidant between the substrate layer and the surface layer containing the photocatalyst. It is preferable that a protective layer is formed. In the antifouling sheet of the present invention, it is preferable that the antioxidant is at least one selected from phenolic compounds, phosphite compounds, sulfur compounds, and vitamin E compounds. In the antifouling sheet of the present invention, the base material layer may have a base fabric made of a fiber cloth and the thermoplastic resin composition layer laminated on at least one surface thereof. . In the antifouling sheet of the present invention, the surface layer containing the photocatalyst may contain 0.01 to 5.0% by weight of an antioxidant. In the antifouling sheet of the present invention, the photocatalyst adhesion / protection layer may be further colored with a colorant containing an inorganic pigment.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The antifouling sheet of the present invention comprises a base material layer and a surface layer formed on at least one surface thereof and containing a photocatalyst. , At least one thermoplastic resin composition layer is included, and the thermoplastic (elastomer) resin composition layer contains 0.01
˜5.0 wt% antioxidant is included. The photocatalyst-containing surface layer is formed on the thermoplastic resin composition layer of the base material layer.

As the thermoplastic resin (including thermoplastic elastomer) used in the present invention, vinyl chloride resin,
Vinyl chloride copolymer resin, olefin resin, olefin copolymer resin, urethane resin, urethane copolymer resin,
Acrylic resin, acrylic copolymer resin, vinyl acetate resin, vinyl acetate copolymer resin, styrene resin, styrene copolymer resin, polyester resin, and thermoplastic resin such as polyester copolymer resin and fluorine copolymer resin ( A thermoplastic elastomer (including a thermoplastic elastomer) or a blend of two or more thereof is preferably used. Among these thermoplastic resins, vinyl chloride resins and vinyl chloride copolymer resins are particularly preferably used because they are excellent in resin physical properties, resin characteristics, molding processability, cost efficiency and the like. However, when halogen-free resins are desired for environmental reasons, especially olefin resins,
And olefinic copolymer resins are most preferably used.

When a vinyl chloride resin is used as a resin (including an elastomer) for the thermoplastic resin composition layer of the antifouling sheet of the present invention, the plasticizer is
It is preferable to use a polyester-based plasticizer, which has the advantage of being less stain resistant. Examples of the above vinyl chloride resin and vinyl chloride copolymer resin include polyvinyl chloride, vinyl chloride-ethylene copolymer resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl ether copolymer resin, vinyl chloride-vinylidene chloride. Copolymer resin, vinyl chloride-maleic acid ester copolymer resin, vinyl chloride-
Acrylic acid copolymer resin, vinyl chloride-methacrylic acid copolymer resin, vinyl chloride-methacrylic acid ester copolymer resin, vinyl chloride-urethane copolymer resin, etc. can be used. Further, as the above-mentioned olefin resin and olefin-based copolymer resin, polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methyl acrylate copolymer resin, ethylene-methyl methacrylate copolymer resin, Ethylene-methacrylic acid copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-propylene copolymer resin, etc. can be used. Further, instead of the above thermoplastic resin, for example, natural rubber, isoprene rubber, butadiene rubber, styrene rubber, butyl rubber, ethylene-propylene rubber, ethylene-vinyl acetate rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin. Synthetic rubber such as rubber, acrylic rubber, urethane rubber, silicone rubber, and fluorine rubber,
And a thermoplastic elastomer (TPE) which is a cross-linked and vulcanized alloy of these synthetic rubbers and the above-mentioned thermoplastic resin
Can also be used.

In the present invention, the antioxidant contained in the thermoplastic resin composition layer in the base material layer is at least selected from phenol-based, phosphite-based, sulfur-based, and vitamin E-based antioxidants. The thing containing 1 or more types can be used.

Examples of the above-mentioned phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6
-Diphenyl-4-octadecyloxyphenol, stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate,
Thiodiethylenebis [3- (3,5-di-tert-butyl-4]
-Hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl) -4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-)
3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2- Tert-Butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-) Tert-butylbenzyl) isocyanurate,
1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, pentaerythritol tetrakis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate],
2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-
Tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [(3-tert-butyl-4] -Hydroxy-5
-Methylphenyl) propionate] and the like.

Examples of the above-mentioned phosphite antioxidants include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-). Tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritol diphosphite , Di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Fight, bis (2,4,6-tri-tert-butylphenyl) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2- Tert-Butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-)
4-hydroxy-5-tert-butylphenyl) butane triphosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) -2-ethylhexylphosphite, 2,2'-methylenebis (4,6-) Di-tert-butylphenyl) octadecyl phosphite, 2,2'-ethylidene bis (4,6-di-tert-butylphenyl) fluorophosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9 , 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl) oxy] ethyl) amine, 2 -Ethyl-2-butyl propylene glycol and phosphite ester of 2,4,6-tri-tert-butylphenol.

Further, as the sulfur-based antioxidant,
Examples thereof include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and β-alkylmercaptopropionate esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples of the vitamin E-based antioxidant include, for example,
3,4-dihydro-2,5,7,8-tetramethyl-2
A typical example thereof is-(4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol.

In the thermoplastic resin composition layer of the antifouling sheet of the present invention, one of the above-mentioned antioxidants is used according to the type and characteristics of the thermoplastic resin (including thermoplastic elastomer) used and the molding conditions. Or a mixture of two or more
It is contained in an amount of 0.01 to 5.0% by weight based on the thermoplastic resin composition. The content of the antioxidant is preferably 0.1 to 3.0% by weight. When the addition amount of the antioxidant contained in the thermoplastic resin composition layer is less than 0.01% by weight, the resulting antifouling sheet has an effect of sustaining the antifouling property for a long period in outdoor use. Is insufficient, which causes the inconvenience that dirt is attached within a short period of time. Further, when the amount of the antioxidant added exceeds 5.0% by weight, during the molding of the thermoplastic resin composition, the antioxidant plate outs on the heat roll, deteriorating its processability,
Further, the surface of the antifouling sheet is whitened by causing an antioxidant to bloom out from the thermoplastic resin composition layer after molding,
And / or inconvenience such as stickiness occurs. In the thermoplastic resin composition layer of the antifouling sheet of the present invention, if necessary, a plasticizer, a secondary plasticizer, a stabilizer, a lubricant, a flameproofing agent, a flame retardant, a foaming agent, an antistatic agent, an interface Activator, water repellent, oil repellent, cross-linking agent, curing agent, organic pigment colorant, conductive filler, various fillers, fungicide, antibacterial agent, ultraviolet absorber, softener, thickener, viscosity reducing agent Ordinarily used additives such as, may be added within a range not deviating from the intended effects of the present invention. Inclusion of an antioxidant in the surface layer containing the photocatalyst gives more favorable results.

In the antifouling sheet of the present invention, the thermoplastic
At least a resin composition layer and a surface layer containing a photocatalyst
One layer, and if necessary, the photocatalyst adhesion / protection layer is an inorganic type
It is colored by a colorant containing a pigment. This wear
Inorganic pigments for color include zinc oxide and zinc oxide.
Tan (rutile type, anatase type), antimony trioxide,
Iron oxide (iron black, red iron oxide), lead oxide (red lead), black oxide
Aluminum, zirconium oxide, cobalt oxide and aluminum oxide
Complex of cobalt (cobalt blue), cobalt oxide and lithium oxide
Compound of cobalt and phosphorus pentoxide (cobalt violet
G), a composite of cobalt oxide and zinc oxide (cobalt green)
Oxide), such as zinc oxide and barium sulfate.
Compound (lithopone), zinc sulfide, cadmium sulfide (cadmium
Umm yellow), mercury sulfide (silver vermilion), cadmium sulfide
Selenium-cadmium complex (cadmium red,
Cadmium orange, cadmium yellow), Anne sulfide
A compound of antimony trioxide and antimony (antimon vermilion)
Which metal sulfide, barium sulfate, calcium sulfate, sulfuric acid
Metal sulfides such as lead, barium carbonate, calcium carbonate,
Magnesium carbonate, a compound of lead carbonate and lead hydroxide (lead white)
Metal carbonates such as aluminum hydroxide (alumina
Wite), a composite of aluminum hydroxide and calcium sulfate
Metal hydroxides such as things (satin white), lead chromate (yellow)
Lead), zinc chromate (zinc yellow), barium chromate, etc.
Chromate metal salt, a composite of lead molybdate and lead sulfate
(Molybdenum red), Spinel type (XY₂ O_Four )Construction
Oxide: XY = Co-Al, Co-Al-Cr, Co
-Mg-Sn, Co-Ni-Ti, Co-Zn-Ni-
Ti, Co-Zn-Cr-Ti, Zn-Cr-Ti, Z
n-Cr-Fe, Co-Zn-Cr-Fe, Co-Ni
-Cr-FE-Si, Co-Mn-Cr-Fe, Cu-
Rutile type such as Mn-Cr and Mn-Fe [Ti (XY)
O ₂ ] Structural oxide: XY = Pb-Sb, Ni-Sb, N
i-W, Fe-Mo, Cr-Sb, and other carbon
Black, titanium black, aluminum pigment, and powder
And pigments, etc., and one or more of these are mixed.
Suitable for the purpose and purpose of the antifouling sheet of the present invention.
It can be conveniently used. Thermoplastic in the present invention
(Elastomer) containing resin composition layer and photocatalyst
At least one surface layer and, if necessary, photocatalytic adhesion
The protective layer preferably contains 70% by weight or more of an inorganic pigment
It is colored with a coloring agent. Discoloration
A color-preventing sheet having excellent preventive properties can be obtained.

In order to form the thermoplastic resin composition layer of the antifouling sheet of the present invention, an antioxidant is added to the above thermoplastic resin, or an antioxidant is further required in the above thermoplastic resin. Depending on the compounding of various additives, the resulting compound of the thermoplastic resin composition, a known kneading method, for example, a method of melt kneading and granulating using a Banbury mixer, kneader, biaxial kneader, etc. Alternatively, a high concentration masterbatch of the antioxidant is prepared with a Banbury mixer or the like, and is dry blended using a mixer such as a tumbler blender, a tumble mixer, a Henschel mixer, and after mixing the above components, simply A method such as melt-kneading and granulating with a single-screw extruder or a twin-screw extruder can be adopted. The film or sheet molded from the thermoplastic resin composition for forming the thermoplastic resin composition layer of the antifouling sheet of the present invention is a T-
It can be manufactured by a known film or sheet processing technique such as a die method, an inflation method, or a calendar method. The method for producing the film or sheet,
A method of molding in a temperature range of 100 to 250 ° C. using a calender is excellent in production efficiency and is a preferable method.

The thickness of the film or sheet used for forming the thermoplastic resin composition layer of the antifouling sheet of the present invention is
It is preferably 80 to 1000 μm, particularly 130
It is preferably about 500 μm. If the thickness is less than 80 μm, molding processing becomes difficult, and when laminating it on a base fabric made of fiber cloth by thermocompression bonding, unevenness on the surface of the fiber cloth causes film breakage and impairs waterproofness. In this case, the antifouling sheet may not be used for outdoor sunshades, medium and large tents, and tent warehouses. Also, the thickness is 10
If it is thicker than 00 μm, not only the calendering process becomes difficult, but also it is heavy and lacks flexibility, and the handleability may be poor.

To form the thermoplastic resin composition film, a vinyl chloride resin emulsion, a polyolefin resin emulsion, an acrylic resin emulsion, an urethane resin emulsion, or another such thermoplastic resin emulsion and an aqueous dispersion are oxidized. Incorporating an inhibitor, a known coating method of the resulting thermoplastic resin composition, for example, a doctor knife coating method, a gravure coating method, a rotary screen coating method, or a dip coating method or the like, a method of drying, Can be used.
When this thermoplastic resin emulsion composition is used, the thermoplastic resin emulsion composition of the present invention may be directly applied to the fiber cloth and dried, or release paper,
The thermoplastic resin composition emulsion may be applied and dried on a release film, and the resin layer may be transferred and laminated on a fiber cloth. Further, when a soft vinyl chloride resin is used as the thermoplastic resin composition, the soft vinyl chloride resin may be a paste vinyl chloride resin composition, and in this case, a soft vinyl chloride layer is formed by coating the soft vinyl chloride resin composition. A step of forming and heat-gelling this at 120 to 200 ° C. is required.

The fiber cloth for the base cloth which can be used for the antifouling sheet of the present invention may be any cloth such as woven cloth, knitted cloth and non-woven cloth, and the woven cloth is not particularly limited to the woven structure. The use of the plain woven fabric is particularly preferable because the resulting antifouling sheet has an excellent balance of physical properties in the longitudinal and weft directions. Russell knitted weft insertion tricots are preferable as the knitted fabric, and non-woven fabrics using long fibers are preferable as the non-woven fabric, and spunbonded non-woven fabric and the like can be particularly used. Further, the fibers constituting the fiber cloth may be any of synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these, and polypropylene fibers in view of processability and versatility, Polyethylene fiber,
Polyvinyl alcohol fiber, polyester fiber, polyamide fiber, acrylic fiber, polyurethane fiber, or
It is preferable to use these mixed fibers, and these fibers may have any shape such as a long fiber yarn, a short fiber spun yarn, a split yarn and a tape yarn.
Among these, multifilament plain woven fibers or spun plain woven fibers formed from polyester fibers, polyamide fibers, or mixed fibers or composite fibers thereof, which have excellent tensile strength, tear strength, heat-resistant creep properties, etc. It is preferable to use a product.

The thermoplastic resin composition layer may be formed on one side of the base cloth made of a fiber cloth, or may be formed on both sides thereof. Generally, in consideration of durability for outdoor use,
It is preferable to form a thermoplastic resin composition layer on both sides of the base fabric. As a method for laminating it, an adhesive layer may be provided between the thermoplastic resin composition and the base cloth, or laminating and heat bonding may be performed without an adhesive. The method of laminating the base fabric and the thermoplastic resin composition film or sheet used in the production of the antifouling sheet of the present invention is a calender topping method in which a base fabric and a heat laminate are simultaneously laminated at the time of molding processing of the film or sheet. , A T-die laminating method, or a calendering method, a T-die method, an inflation method, etc.
This may be attached to the base fabric by thermocompression bonding using a laminator. In the production of the antifouling sheet according to the present invention, a method of thermocompression bonding the film or sheet molded by a calendering method and a base fabric made of a polyester fiber plain woven fabric is efficient and economically excellent in practical use. It is preferable. At this time, since the plain weave base fabric has a hollow plain weave structure, it is possible to manufacture a laminated sheet without using an adhesive. Further, this method is more preferably used in order to obtain an antifouling sheet having a well-balanced physical property in the longitudinal and transverse directions. Further, when the thermoplastic resin composition film or sheet is formed by using the antioxidant-containing thermoplastic resin emulsion or water dispersion, or a soft vinyl chloride paste, it is a plain woven base fabric. The woven structure is preferably a non-blank plain weave with a high yarn density, and more preferably a spun fiber plain woven base fabric or the like is used.

The surface of the thermoplastic (elastomer) resin composition layer of the antifouling sheet of the present invention contains a photocatalyst and a binder whose main component is a thermoplastic resin composition stable against photocatalysis. Layers have been formed. The surface layer containing these photocatalysts can be formed on one side or both sides of the antifouling sheet of the present invention, depending on the application.
The photocatalyst-containing surface layer of the antifouling sheet of the present invention is formed on the surface of the thermoplastic resin composition layer via an adhesive / protective layer made of an acrylic-silicone resin containing an antioxidant and polysiloxane. Good. The photocatalyst-containing surface layer is
It includes a photocatalyst particle composite containing a metal oxide sol. The photocatalyst-containing surface layer is composed of, for example, 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. The photocatalyst coating agent can be formed by directly coating the surface of the above-mentioned antioxidant-containing adhesive / protective layer or the surface of the thermoplastic resin composition layer and drying. As the monoalkyltrimethoxysilane, for example, methyltrimethoxysilane and methyltriethoxysilane can be particularly preferably used.

The mixing weight ratio of silica sol and monoalkyltrimethoxysilane or its hydrolysis product is 1
It is preferably from 00% / 0% to 60% / 40%,
The weight mixing ratio of the titanium oxide sol and the silane compound is preferably 5% / 95% to 75% / 25%. If the ratio of the silane compound exceeds 95%, the photocatalytic action may be insufficient, and if it is less than 25%, the adhesiveness with the thermoplastic resin composition layer or the adhesive / protective layer may be insufficient. Sometimes.

As the photocatalyst, TiO ₂ , ZnO, Sr
TiO ₃ , CdS, GaP, InP, GaAs, BaT
iO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO
₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O, Si
C, SiO ₂ , MoS ₂ , InPb, RuO ₂ , CeO
_{2 and the} like, and these photocatalysts have P
It is possible to use those to which metals such as t, Rh, RuO ₂ , Nb, Cu, Sn and NiO and metal oxides are added. The content of the photocatalyst in the photocatalyst-containing surface layer is higher as the photocatalyst becomes higher, but from the viewpoint of adhesiveness with the thermoplastic resin composition layer or the photocatalyst adhesion / protection layer, it is 75% by weight.
The following is preferable.

The thermoplastic resin used for forming the photocatalyst adhesion / protection layer in the antifouling sheet of the present invention includes acrylic-silicone copolymer resin, acrylic-fluorine copolymer resin, and urethane-silicone-fluorine. High stability for photocatalysts such as copolymer resins such as copolymer resins, resin blends of silicone resins and acrylic resins, and resin blends of fluorine resins and acrylic resins, and Those having excellent adhesiveness to the thermoplastic resin composition layer can be preferably used. A photocatalyst adhesion / protection layer is formed on the surface of the thermoplastic resin composition layer by using these silicone-based or fluorine-based copolymerization thermoplastic resins or blends thereof. In order to maintain the antifouling effect due to the photocatalytic action in outdoor use for a long period of time, it is preferable to prevent the decomposition and deterioration of the acrylic resin component due to the photocatalytic action. Add inhibitor. The antioxidant that can be used in the photocatalyst adhesion / protection layer can be appropriately combined and used from the above-mentioned antioxidants, and the addition amount of the antioxidant is 0.01 with respect to the solid weight of the photocatalyst adhesion and protection layer. It is preferably ˜5.0 wt%, and more preferably 0.1 to 3.0 wt%. Further, as the thermoplastic resin for forming the photocatalyst adhesion / protection layer of the antifouling sheet of the present invention, it is preferable to use an acrylic-silicone copolymer resin. The thickness of this photocatalytic adhesion and protective layer can be adjusted by any of the above coating methods.
It is preferably formed to a thickness of 1.0 μm or more.

Coating a surface layer coating liquid containing a photocatalyst,
The method for coating the photocatalyst adhesion / protection layer is not particularly limited, but these photocatalyst-containing coating liquids and the photocatalyst adhesion / protection layer coating liquids are uniformly applied to the surface of the thermoplastic resin composition layer, and A coating method or coating method that can be applied uniformly is desirable. For example, a gravure coating method, a micro gravure coating method, a comma coating method, a roll coating method, a reverse roll coating method, a bar coating method,
A kiss coat method, a flow coat method and the like are preferably used.

The thickness of the antifouling sheet of the present invention is not particularly limited, and is appropriately set according to its application and constitution.
For example, the thickness of the antifouling sheet when the base cloth is not included is 8
It is preferably 0 to 1000 μm, and in the case of a sheet in which the thermoplastic resin composition layer and the photocatalyst-containing surface layer are arranged on one side of the base fabric, it is preferably 120 to 1600 μm, and on both sides of the base fabric, 1 in the case of a sheet provided with a thermoplastic resin composition layer and a photocatalyst-containing surface layer, respectively.
It is preferably about 60 to 2000 μm.

[0030]

EXAMPLES The present invention will be further explained by the following examples, but the scope of the present invention is not limited by these examples.

In the following Examples and Comparative Examples, the test method used for evaluating the antifouling performance of the sheet is as follows. Test (I) Outdoor exposure test A test sheet having a width of 20 cm and a length of 2 m was installed with the surface layer forming surface containing the photocatalyst on the front side, and the tilt angle was set to face south 3
1 on each of the 0 ° exposure table and the vertical exposure table
The samples were continuously spread by m and subjected to an outdoor exposure test. After 6 months, 12 months, and 18 months of exposure, the test sheets were observed for stains and rain streaks. (B) With respect to the installed sample having the antifouling property at an inclination angle of 30 °, 18 months after exposure, 12 months after exposure, based on the color of the sample at the start of exposure.
Color difference ΔE (JIS-Z-872
9) was measured and the antifouling property was evaluated according to the following criteria. ΔE = 0 to 2.9: ⊚ = No stain and good. The initial state is maintained. ΔE = 3 to 5.9: ◯ = Some dirt, but no problem in practical use. ΔE = 6 to 11.9: Δ = dirt becomes noticeable. Practical is difficult. ΔE = 12 or more: × = Staining is severe and cannot be put to practical use.

(B) Rain streak dirt Vertically streaked rain due to the rainfall of the sample placed 6 months, 12 months, and 18 months after the exposure, with reference to the surface condition of the sample at the start of the exposure. The generation state of streak stains was visually observed and the rain streak preventive property was evaluated according to the following criteria. ⊚ = good with no rain streaks. The initial state is maintained. ○ = Slightly streak stains occur, but there is no practical problem. △ = Rain line stains are noticeable. Practical is difficult. × = Rain streaks are too dirty to be used practically.

(II) Light fastness test (a) Discoloration and fading The surface layer forming surface containing the photocatalyst of the test sample was measured for 1000 hours with a sunshine carbon weather meter, and
000 hours and 3000 hours light fastness test (JIS
-L-0842) is applied and the color of the original sample is used as a reference, and the degree of discoloration on the surface of the sample under test is determined by the color difference ΔE (JIS-Z-
8729) was measured and digitized, and the discolorability was evaluated according to the following criteria. ΔE = 0 to 2.9: A = No discoloration and good. The initial state is maintained. ΔE = 3 to 5.9: ◯ = Slightly discolored, but practically no problem. ΔE = 6 to 11.9: Δ = Discoloration is noticeable. Practical is difficult. ΔE = 12-: × = Severe discoloration, which is not practical.

The following ingredients were used in the following examples and comparative examples. Compounding materials General-purpose materials were used in the usual manner unless otherwise specified . (1) Vinyl chloride resin: Trademark: S-1003 (Kanegafuchi Chemical Industry Co., Ltd.) (2) DOP: Trademark: Sanso Sizer DOP (New Japan Rika Co., Ltd.) (3) Adipic polyester: Trademark: ADEKA Sizer PN-446 (Asahi Denka Co., Ltd.) (4) Epoxidized soybean oil: Trademark: ADEKA Sizer O-1
30P (Asahi Denka Co., Ltd.) (5) Calcium carbonate: Trademark: Ryton BS (Bihoku Powder Industry Co., Ltd.) (6) Ba-Zn stabilizer: Trademark: KV-400B (Kyodo Pharmaceutical Co., Ltd.) (7) Antioxidant (I): Trademark: Irganox 101
0 (phenolic), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (8) Antioxidant (II): Trademark: Irganox 103
5 (phenol-sulfur system), thiodiethylene bis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate] (9) Antioxidant (III): Trademark: Irgafos 168
(Phosphite type), tris (2,4-di-tert-butylphenyl) phosphite [Note: (7) to (9):
Ciba. Specialty. Chemicals Co., Ltd.] (10) Ultraviolet absorber: Trademark: Biosorb 510 (Kyodo Pharmaceutical Co., Ltd.) (11) Inorganic pigment (I): Trademark: Titanium oxide CR (Ishihara Sangyo Co., Ltd.) (12) Inorganic Pigment (II): Trademark: Yellow No. 55
50 (Asahi Sangyo Co., Ltd.) (13) Organic pigment (I): Trademark: HSM9361 Yellow (Hirohiro Bix Co., Ltd.) * Condensation Azo Yellow 25 wt% conc Masterbatch (14) Organic pigment (II): Trademark : HSM9142 Red (Hihiro Vix Co., Ltd.) * Quinacridone Red 25 wt% conc masterbatch (15) Ethylene-vinyl acetate copolymer resin: Trademark: EvaTate K-2010 (Sumitomo Chemical Co., Ltd.) (16) Ethylene-meta Acrylic acid copolymer resin: Trademark:
Acryft WH-202 (Sumitomo Chemical Co., Ltd.) (17) Low-density polyethylene: Trademark: J-LEX LL
BF1350 (Japan Polyolefin Co., Ltd.) (18) Lubricant: Trademark: LE-5 (Kawaken Fine Chemicals Co., Ltd.) (19) Organic pigment (III): Trademark: HCM1429 Yellow (Dainichi Seika Kogyo Co., Ltd.) * Isoindolinone Yellow 20 wt% conc colored pellets (20) Organic pigment (IV): Trademark: HCM1170 Red (Dainichi Seika Chemicals Co., Ltd.) * Condensed Azo Red 20 wt% conc colored pellets

Example 1 (1) Process of Treating Base Fabric Made of Fiber Cloth with Thermoplastic Resin Polyester filament plain woven fabric of 1000 denier vertical yarn × 1000 denier horizontal yarn (yarn density: 22 vertical /
2.54 cm, 25 horizontal pieces / 2.54 cm: 21 basis weight
5 g / m ² ) was used as a base cloth, and the base cloth was immersed in an organosol prepared by diluting the following paste vinyl chloride resin composition with a solvent to impregnate the base vinyl chloride resin composition into the base cloth and then using a roller. 145g for squeezing and base cloth
/ M ² of the paste vinyl chloride resin composition is evenly attached to the entire surface of the base fabric, dried for 1 minute in a heat treatment furnace at 150 ° C, and then heat-treated for 1 minute in a heat treatment furnace at 185 ° C,
The paste vinyl chloride resin composition was gelled. A base substrate made of a polyester filament plain woven fabric impregnated with a vinyl chloride resin composition was obtained. <Composition composition of paste vinyl chloride resin> Paste vinyl chloride resin 100 parts by weight DOP (plasticizer) 70 parts by weight Epoxidized soybean oil (ESBO) 4 parts by weight Calcium carbonate 10 parts by weight Ba-Zn stabilizer 2 parts by weight Phenol-based oxidation Inhibitor ⁽⁷⁾ 1 part by weight Pigment (TiO ₂ ) 5 parts by weight Solvent (toluene) 20 parts by weight [Note] (7) ... Phenolic antioxidant (compounding material (7)) = pentaerythritol tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], trademark: Irganox 1010 (Ciba Specialty Chemicals Co., Ltd.) A straight vinyl chloride resin composition having the composition described in Table 1 (implemented A soft vinyl chloride resin composition film having a thickness of 0.16 mm consisting of Example 1) was prepared by a calender molding method at 170 ° C. under gelling and kneading conditions, and this film was prepared by impregnating the paste vinyl chloride resin composition impregnated group described above. Laminated on both sides of the cloth using a laminator set at 165 ° C. by a thermal laminating method, thickness 0.5 mm, weight 550 g /
A base material layer including a thermoplastic resin composition layer made of a soft yellow vinyl chloride resin of m ² was prepared.

(2) Photocatalyst Layer Forming Process A coating liquid for forming a photocatalyst adhesion / protection layer having the following composition is formed on one surface of the base material layer containing the thermoplastic resin composition layer made of the above soft vinyl chloride resin. Was coated at a coating amount of 15 g / m ² using an 80 mesh gravure roll coater, and this was dried in a heat treatment furnace at 100 ° C. for 1 minute. <Photocatalyst Adhesion / Protection Layer Forming Coating Liquid Blend> (a) 100 parts by weight of an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight (solid content) of an acrylic-silicone resin having a silicone content of 3 mol%. (b) 20 wt% ethanol solution of methyl silicate MS51 (Colcoat Co., Ltd.) as polysiloxane 8 parts by weight (c) γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by weight (d) octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (phenolic antioxidant) 0.02 parts by weight: Trademark: Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.)

A coating solution for forming a photocatalyst layer having the following composition was coated on the surface of the photocatalyst adhesion / protection layer at a coating amount of 12 g / m ² using a 100 mesh gravure roll coater, and this was heat treated at 100 ° C. It was dried in an oven for 1 minute to form a photocatalyst-containing surface layer to prepare an antifouling sheet. <Blending of photocatalyst forming coating solution> (a) 100 parts by weight of water-ethanol (50/50 weight ratio) solution in which nitric acid acidic titanium oxide sol corresponding to titanium oxide content of 10% by weight is dispersed (b) Silicon oxide content of 10 100 parts by weight of a water-ethanol (50/50 weight ratio) solution in which a nitric acid-acidic silica sol corresponding to the weight% is dispersed.

The obtained antifouling sheet was subjected to the outdoor exposure test and the light fastness test to specifically evaluate the antifouling property, the rain streak stain prevention and the discoloration prevention effect. Table 1 shows the test results
This is shown in (Example 1). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was observed. I couldn't do it.

[0039] In each of Examples 2-8 Examples 2-8, in the same manner as in Example 1,
1000 denier warp yarn x 1000 denier weft yarn polyester filament plain weave (yarn density: 22 warp /
2.54 cm, 25 horizontal / 2.54 cm: weight per unit area: 2
15 g / m ² ) was used as the base fabric, and this base fabric was used in Example 1
The same paste vinyl chloride resin composition as described above is immersed in an organosol diluted with a solvent to impregnate the base vinyl cloth with the paste vinyl chloride resin composition, which is then squeezed with a roller to give 145 g / m ² to the base cloth. The paste vinyl chloride resin composition of 1 is evenly adhered to the entire surface of the base fabric, dried for 1 minute in a heat treatment furnace at 150 ° C., and further heat treated for 1 minute in a heat treatment furnace at 185 ° C. The product gelled. This vinyl chloride resin composition-impregnated polyester filament plain woven fabric was used as a base substrate for laminating a soft vinyl chloride resin composition film. Using this base material, except for the following matters, Example 1
A vinyl chloride resin composition film was laminated, a photocatalyst adhesion / protection layer was formed, and a photocatalyst-containing surface layer was formed in the same manner as in.

In Example 2, an antifouling sheet was produced in the same manner as in Example 1 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, instead of 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010), another antioxidant (II) ( Compounding material (8), Irganox 103
5) 3 parts by weight was used. The results of the outdoor exposure test and the light fastness test are shown in Table 1 (Example 2). The antifouling property of the obtained antifouling sheet was extremely good, and the outdoor exposure 1
After 8 months, the same hue and appearance as at the start of exposure were maintained, and no rain streaks were observed.

In Example 3, an antifouling sheet was prepared in the same manner as in Example 1, using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was replaced with another antioxidant (III) (compounding). 3 parts by weight of the material (8), Irgafos 168) were used. The results of the outdoor exposure test and the light fastness test are shown in Table 1 (Example 3). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was observed. I couldn't do it.

In Example 4, an antifouling sheet was prepared in the same manner as in Example 1 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, the compounding amount of the antioxidant (I) (compounding material (7), Irganox 1010) was changed from 3 parts by weight to 5 parts by weight. The results of the outdoor exposure test and the light fastness test are shown in Table 1 (Example 4). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was observed. I couldn't do it.

In Example 5, an antifouling sheet was prepared in the same manner as in Example 1 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, in place of 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010), another antioxidant (II) (compounding) Material (8), Irganox 1035)
5 parts by weight was used. The results of the outdoor exposure test and the light fastness test are shown in Table 1 (Example 5). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained,
Moreover, the generation of dirt on the rain streak was not observed.

In Example 6, an antifouling sheet was prepared in the same manner as in Example 1, using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, instead of 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010), another antioxidant (III) (compounding) 5 parts by weight of material (9), Irgafos 168) were used. The results of the outdoor exposure test and the light fastness test are shown in Table 1 (Example 6). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

In Example 7, an antifouling sheet was prepared in the same manner as in Example 1, using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was replaced with 2 parts by weight of the other parts. 1 part by weight of antioxidant (II) (compounding material (8), Irganox 1035) and antioxidant (III)
(Compounding material (9), Irgafos 168) 1 part by weight was used. The results of the outdoor exposure test and the light fastness test are shown in Table 1 (Example 7). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was observed. I couldn't do it.

In Example 8, an antifouling sheet was prepared in the same manner as in Example 1, using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, out of 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010), 2 parts by weight thereof was replaced with another oxidation product. 1 part by weight of an inhibitor (II) (compounding material (8), Irganox 1035) and 1 part by weight of an antioxidant (III) (compounding material (9), Irgafos 168), and further an inorganic pigment (I) (Compounding material (11), titanium oxide CR) was not added, and the compounding amount of inorganic pigment (II) (compounding material (12), yellow No. 5550) was changed from 2 parts by weight to 7 parts by weight, and yellow Colored. The results of the outdoor exposure test and the light fastness test are shown in Table 1 (Example 8). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

Comparative Examples 1 to 8 As in Example 1, 1000 denier warp × weft 1
000 denier polyester filament plain weave (thread density: vertical 22 / 2.54 cm, horizontal 25 / 2.54
(cm: basis weight 215 g / m ² ) was used as a base fabric to prepare a base fabric, and this base fabric was used to prepare an antifouling sheet in the same manner as in Example 1. However, as the paste vinyl chloride composition, the paste vinyl chloride resin composition of Example 1 from which 1 part by weight of the antioxidant (compounding material (7), (Irganox 1010)) was removed was used.
The plain fabric is dipped in an organosol obtained by diluting this composition with a solvent, and the paste vinyl chloride resin composition is impregnated into a base cloth, which is then squeezed with a roller to give 145 g of the base cloth.
/ M ² paste The vinyl chloride resin composition is evenly attached to the entire surface of the base cloth, dried for 1 minute in a heat treatment furnace at 150 ° C, and then heat-treated for 1 minute in a heat treatment furnace at 185 ° C to obtain a paste. The vinyl chloride resin compounded composition was gelled. This paste vinyl chloride resin composition-impregnated polyester filament plain weave was used as a base substrate for laminating a soft vinyl chloride resin composition film.
Using this base substrate, a soft vinyl chloride resin composition film was laminated, a photocatalyst adhesion / protection layer was formed, and a photocatalyst-containing surface layer was formed in the same manner as in Example 1 except for the following matters. <Paste vinyl chloride resin composition> Paste vinyl chloride resin 100 parts by weight DOP (plasticizer) 70 parts by weight Epoxidized soybean oil (ESBO) 4 parts by weight Calcium carbonate 10 parts by weight Ba-Zn-based stabilizer 2 parts by weight Pigment (TiO2) ₂ ) 5 parts by weight solvent (toluene) 20 parts by weight

In Comparative Examples 1 to 6, the photocatalyst layer forming step was performed in the same manner as in Example 1. However, photocatalyst adhesion
As the protective layer-forming coating liquid, the following composition was used except that the antioxidant octadecyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate (Irganox 1076) was used from that used in Example 1. The one which has was used. This photocatalyst adhesion / protection layer forming coating liquid was applied to the surface of the base material layer with a coating amount of 15 g / m ² using an 80 mesh gravure roll coater and dried in a heat treatment furnace at 100 ° C. for 1 minute. <Photocatalyst Adhesion / Protection Layer Forming Coating Liquid> (a) 100 parts by weight of an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight (solid content) of an acrylic-silicone resin having a silicone content of 3 mol% ( b) 20 wt% ethanol solution of methyl silicate MS51 (Colcoat Co., Ltd.) as polysiloxane 8 parts by weight (c) γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by weight

In Comparative Example 1, a sheet was prepared in the same manner as in Example 1 using the above base material. However, the soft vinyl chloride resin composition film used in Example 1 from which 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was omitted was used. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 1). Outdoor exposure 12 in the obtained sheet exposure test
Staining began to stand out after a month, and rain streak stains were also observed. Further, after 18 months of outdoor exposure, the soft vinyl chloride resin composition layer in the base material layer deteriorated due to the photocatalyst, and the photocatalyst surface layer was dropped off. Progressed. For this reason, the sheet of the comparative example was unsuitable for long-term outdoor use.

In Comparative Example 2, a sheet was prepared in the same manner as in Example 2 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 2, 3 parts by weight of the antioxidant (II) (compounding material (8), Irganox 1035) was omitted, and the inorganic pigment (I
I) (Compounding material (12), Yellow No. 5550) 2
Instead of parts by weight, organic pigment (I) (compounding material (13),
2 parts by weight of condensed azo yellow (8 parts by weight as a HSM 9361 yellow (25 wt% conc) masterbatch) were used. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 2). In the outdoor exposure test of the obtained sheet colored in pale yellow, stains became noticeable 12 months after outdoor exposure, and discoloration and fading of the organic pigment also began to be noticeable. In addition, the occurrence of stains on the rain streak was also observed. Further, after 18 months of outdoor exposure, the thermoplastic resin of the base material layer deteriorated due to the photocatalyst, and the photocatalyst surface layer fell off, so that the adhesion of dirt and the occurrence of rain streaks rapidly progressed. Therefore, the sheet of Comparative Example was unsuitable for long-term outdoor use.

In Comparative Example 3, a sheet was prepared in the same manner as in Example 3 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 3, 3 parts by weight of the antioxidant (III) (compounding material (7), Irgafos 168) was omitted, and the inorganic pigment (I) was added.
(Compounding material (11), 5 parts by weight of titanium oxide CR), organic pigment (II) (compounding material (14), 1 part by weight of quinacridone red (4 parts by weight as HSM9142 (25 wt% conc) masterbatch)) Inorganic pigment (I
I) (Compounding material (12), Yellow No. 5550) 2
Instead of parts by weight, organic pigment (I) (compounding material (13),
2 parts by weight of condensed azo yellow (8 parts by weight as a HSM 9361 yellow (25 wt% conc) masterbatch) were used. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 3). In the above-mentioned exposure test of the obtained orange-colored sheet, stains became noticeable 12 months after outdoor exposure, and at the same time discoloration and fading of the organic pigments became noticeable. In addition, the occurrence of stains on the rain streak was also observed. Further, after 18 months of outdoor exposure, the thermoplastic resin composition layer of the soft vinyl chloride resin composition of the base material layer deteriorated due to the photocatalyst, and the photocatalyst surface layer fell off. The fouling occurred rapidly. Therefore, the sheet of Comparative Example 3 was unsuitable for long-term outdoor use.

In Comparative Example 4, a sheet was prepared in the same manner as in Example 1 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, the compounding amount of the antioxidant (I) (compounding material (7), Irganox 1010) was changed to 0.01 part by weight. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 4). In the exposure test of the obtained sheet, stains began to stand out after 18 months of outdoor exposure,
In addition, the occurrence of dirt on the rain streak was also observed. Furthermore, the thermoplastic resin composition layer made of the soft vinyl chloride resin composition of the base material layer gradually causes resin deterioration due to the photocatalyst, and the photocatalyst surface layer is dropped off, so that the adhesion of dirt and the occurrence of rain streaks stains, Progressed. Therefore, the sheet of Comparative Example 4 was unsuitable for long-term outdoor use.

In Comparative Example 5, a sheet was prepared in the same manner as in Example 2 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 2, the compounding amount of the antioxidant (II) (compounding material (8), Irganox 1035) was changed to 0.01 part by weight. In addition, inorganic pigment (II) (compounding material (1
2)) Instead of 2 parts by weight, 2 parts by weight of organic pigment (I) (compounding material (13)) condensed azo yellow (HSM 9361)
Yellow (25 wt% conc) 8 parts by weight as a masterbatch was used. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 5). In the exposure test of the obtained sheet colored in pale yellow, stains became conspicuous after 18 months of outdoor exposure, and generation of rain streaks was also observed. Furthermore, the thermoplastic resin composition layer made of the soft vinyl chloride resin composition of the base material layer gradually causes resin deterioration due to the photocatalyst, and the photocatalyst surface layer is dropped,
Adhesion of dirt and dirt on rain streaks progressed. Therefore, the sheet of Comparative Example 5 was unsuitable for long-term outdoor use.

In Comparative Example 6, a sheet was prepared in the same manner as in Example 3 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 3, the compounding amount 3 parts by weight of the antioxidant (III) (compounding material (9), Irgafos 168) was changed to 0.01 parts by weight, Further, instead of 5 parts by weight of the inorganic pigment (I) (blending material (11), titanium oxide CR), organic pigment (II) (blending material (14), 1 part by weight of quinacridone red (HSM
9142 (4 wt parts as a 25 wt% conc masterbatch)) and changed to inorganic pigment (II) (compounding material (1
2), yellow No. 5550) 2 parts by weight of organic pigment (I) (compounding material (13), condensed azo yellow 2)
Parts by weight (8 parts by weight as a HSM 9361 yellow (25 wt% conc) masterbatch) were used. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 6). In the exposure test of the obtained orange-colored sheet, stains began to stand out after 18 months of outdoor exposure, and at the same time discoloration and fading of the organic pigments started to stand out considerably. In addition, the occurrence of stains on the rain streak was also observed. Further, the thermoplastic resin composition layer made of the soft vinyl chloride resin composition of the base material layer caused resin deterioration due to the photocatalyst, and the photocatalyst surface layer was dropped off, so that the adhesion of dirt and the occurrence of rain streaks were promoted. . Therefore, the sheet of Comparative Example 6 was unsuitable for long-term outdoor use.

In Comparative Example 7 and Comparative Example 8, antifouling sheets were prepared in the same manner as in Example 1 using the above-mentioned base material. However, as a photocatalyst adhesion / protection layer forming coating solution, an antioxidant (Irganox 1076) was used as in Example 1.
Was used in an amount of 0.02 part by weight. <Photocatalyst Adhesion / Protection Layer Forming Coating Liquid> (a) 100 parts by weight of an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight (solid content) of an acrylic-silicone resin having a silicone content of 3 mol% ( b) 20 wt% ethanol solution of methyl silicate MS51 (Colcoat Co., Ltd.) as polysiloxane 8 parts by weight (c) γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by weight (d) stearyl-β -(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate (phenolic antioxidant) 0.02 parts by weight: trade name: Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.)

In Comparative Example 7, a sheet was prepared in the same manner as in Example 1 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was omitted, and the inorganic pigment (I) (compounding) In place of 5 parts by weight of the material (11) and titanium oxide CR, an organic pigment (II) (compounding material (14), 1 part by weight of quinacridone red (HSM9142 (25 wt% co
nc) 4 parts by weight as a masterbatch), and an inorganic pigment (II) (compounding material (12), yellow No. 555)
0) Organic pigment (I) (compounding material (1
3), 2 parts by weight of condensed azo yellow (8 parts by weight as a HSM 9361 yellow (25 wt% conc) master batch) were used. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 7). In the obtained orange-colored sheet exposure test, stains began to be noticeable after 18 months of outdoor exposure, and at the same time discoloration and fading of the organic pigments became noticeable. In addition, the occurrence of stains on the rain streak was also observed. Furthermore, the thermoplastic resin composition layer made of the soft vinyl chloride resin composition of the base material layer causes resin deterioration due to the photocatalyst, and the photocatalyst surface layer is dropped,
Adhesion of dirt and dirt on rain streaks progressed. Therefore, the sheet of Comparative Example 7 was not suitable for long-term outdoor use.

In Comparative Example 8, a sheet was prepared in the same manner as in Example 1 using the above-mentioned base material. However, in the soft vinyl chloride resin composition film used in Example 1, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was changed to 0.01% by weight. In addition, inorganic pigment (I) (compounding material (1
1), the organic pigment (II) (compounding material (14), 1 part by weight of quinacridone red (4 parts by weight as a HSM9142 (25 wt% conc) masterbatch)) was used instead of 5 parts by weight of titanium oxide CR) Organic pigment (I) (compounding material (13), condensed azo yellow 2 parts by weight (HSM9361 yellow (25 wt% conc)) instead of 2 parts by weight of pigment (II) (compounding material (12), yellow No. 5550)
8 parts by weight) was used as a masterbatch. The results of the outdoor exposure test and the light fastness test are shown in Table 2 (Comparative Example 8).
Shown in. In the obtained orange-colored sheet exposure test, stains began to be noticeable after 18 months of outdoor exposure, and at the same time discoloration and fading of the organic pigments became noticeable. In addition, the occurrence of stains on the rain streak was also observed. Further, the thermoplastic resin composition layer made of the soft vinyl chloride resin composition of the base material layer caused resin deterioration due to the photocatalyst, and the photocatalyst surface layer was dropped off, so that the adhesion of dirt and the occurrence of rain streaks were promoted. . Therefore, the sheet of Comparative Example 8 was unsuitable for long-term outdoor use.

Example 9 An antifouling sheet was produced by the following steps. (1) Process of treating base fabric made of fiber cloth with thermoplastic resin Polyester filament plain woven fabric having 1000 denier vertical yarn × 1000 denier horizontal yarn (yarn density: 22 vertical /
2.54 cm, 25 horizontal pieces / 2.54 cm: 21 basis weight
5 g / m ² ) is used as a base cloth, and the base cloth is dipped in an ethylene-vinyl acetate copolymer resin-based olefin resin emulsion composition having the following composition to impregnate the base cloth with the olefin resin emulsion composition. After squeezing with a roller, the olefin resin emulsion composition of 95 g / m ² is evenly adhered to the entire surface of the base cloth with respect to the base cloth, and this is dried in a heat treatment furnace at 100 ° C. for 1 minute. 130
A heat treatment was performed in a heat treatment furnace at a temperature of 1 ° C. for 1 minute to impregnate and fix the olefin resin composition onto the base cloth. <Olefin-based resin emulsion composition> Ethylene-vinyl acetate copolymer resin emulsion 100 parts by weight Calcium carbonate 10 parts by weight Phenolic antioxidant 1 part by weight Pigment (TiO ₂ ) 5 parts by weight [Note] Ethylene-vinyl acetate copolymer resin Emulsion =
Trademark: Aquatex EC-1700 (resin solid content 50
% By weight: Chuo Rika Kogyo Co., Ltd., phenolic antioxidant = 2,4-dimethyl-6- (1-methylpentadecyl) phenol (trademark: Irganox 1076) and octadecyl-3- (3,5-) A blended product of di-tert-butyl-4-hydroxyphenyl) propionate (trademark: Irganox 1141 (Ciba Specialty Chemicals Co., Ltd.) in a 50/50 weight ratio.

A film having a thickness of 0.16 mm and made of the ethylene-vinyl acetate copolymer resin composition shown in Table 3 (Example 9) was formed by a calender molding method at 140 ° C. under melt-kneading conditions. The above-mentioned ethylene-vinyl acetate copolymer resin emulsion composition impregnated base cloth was pasted on both sides by a thermal laminating method using a laminator set at 150 ° C., and the thickness was 0.5 mm and the weight was 480 g / m ^2.
A base material layer having a thermoplastic resin composition composed of the light yellow colored ethylene-vinyl acetate copolymer resin and front and back double-sided layers was prepared.

(2) Photocatalyst layer forming step A photocatalyst adhesive / protection layer forming treatment liquid having the following composition was applied to one surface of the base material layer using an 80 mesh gravure roll coater at a coating amount of 15 g / m ² . Apply and 100
It was dried for 1 minute in a heat treatment furnace at ℃. <Photocatalyst Adhesion / Protection Layer Forming Treatment Mixture> (a) 100 parts by weight of an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight (solid content) of an acrylic-silicone resin having a silicone content of 3 mol%. (b) 20 wt% ethanol solution of methyl silicate MS51 (Colcoat Co., Ltd.) as polysiloxane 8 parts by weight (c) γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by weight (d) octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (phenolic antioxidant) 0.02 parts by weight: Trademark: Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.)

A photocatalyst layer forming treatment liquid having the following composition was applied to the surface of the photocatalyst adhesion / protection layer formed on one surface of the base material layer using a 100-mesh gravure roll coater.
Apply at a coating amount of g / m ² , and in a heat treatment furnace at 100 ° C,
A photocatalyst surface layer was formed by drying for 1 minute to prepare an antifouling sheet. <Photocatalyst forming coating solution> (a) 100 parts by weight of water-ethanol (50/50 weight ratio) solution in which nitric acid acidic titanium oxide sol corresponding to titanium oxide content of 10% by weight is dispersed (b) Silicon oxide content of 10 weight % Water-ethanol (50/50 weight ratio) solution in which nitric acid acidic silica sol equivalent to 100% is 100 weight parts

The obtained antifouling sheet was subjected to the outdoor exposure test and the light resistance accelerated test, and its antifouling property, rain streak stain prevention and discoloration prevention effects were specifically evaluated. The test results are shown in Table 3 (Example 9). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

[0063] In each of Examples 10 to 16 Example 10 to 16 were prepared antifouling sheet by the following steps. As in Example 9, warp yarn 10
00 denier x 1000 denier polyester filament plain weave (yarn density: 22 warp / 2.54c
m, horizontal 25 / 2.54 cm: basis weight 215 g / m ²
) Is used as a base cloth, and the base cloth is immersed in the same ethylene-vinyl acetate copolymer resin-based olefin resin emulsion composition as in Example 9 to impregnate the base cloth with the olefin resin emulsion compounding composition. After squeezing with a roller, 95 g / m ² of the olefin resin emulsion composition is evenly adhered to the entire surface of the base cloth, and then dried in a heat treatment furnace at 100 ° C. for 1 minute, and then at 130 ° C.
Heat treatment was carried out for 1 minute in the heat treatment furnace, and the base fabric was impregnated and fixed with the olefin resin compound composition to prepare a base substrate.

On this base substrate, a thermoplastic resin composition was attached, a photocatalyst adhesion / protection layer was formed, and a photocatalyst surface layer was formed in the same manner as in Example 9 except for the following matters.

In Example 10, in the ethylene-vinyl acetate copolymer resin composition film used in Example 9, 3 parts by weight of antioxidant (I) (compounding material (7), Irganox 1010) was used. An antifouling sheet was produced in the same procedure as in Example 9 using 3 parts by weight of the antioxidant (II) (compounding material (8), Irganox 1035).
The results of the outdoor exposure test and the light fastness test are shown in Table 3 (Example 10). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

In Example 11, the ethylene-vinyl acetate copolymer resin composition film used in Example 9 was replaced by 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010). Using 3 parts by weight of antioxidant (III) (compounding material (9), Irgafos 168),
An antifouling sheet was produced in the same procedure as in Example 9. The results of the outdoor exposure test and the light fastness test are shown in Table 3 (Example 11). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

In Example 12, in the olefinic thermoplastic resin composition film used in Example 9,
An antifouling sheet was produced in the same procedure as in Example 9 using 100 parts by weight of the ethylene-methacrylic acid copolymer resin instead of 100 parts by weight of the ethylene-vinyl acetate copolymer resin. Table 3 shows the results of the outdoor exposure test and the light fastness test.
This is shown in (Example 12). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

In Example 13, in the olefinic thermoplastic resin composition film used in Example 9,
Instead of 100 parts by weight of the ethylene-vinyl acetate copolymer resin, 100 parts by weight of the ethylene-methacrylic acid copolymer resin was used, and 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was used. Instead, antioxidant (II) (compounding material (8), Irganox 1035)
An antifouling sheet was prepared by the same procedure as in Example 9 using a blend of 1.5 parts by weight and 1.5 parts by weight of antioxidant (III) (compounding material (9), Irgafos 168). .
The results of the outdoor exposure test and the light fastness test are shown in Table 3 (Example 13). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

In Example 14, in the olefinic thermoplastic resin composition film used in Example 9,
An antifouling sheet was produced in the same procedure as in Example 9 except that 100 parts by weight of the low-density polyethylene resin was used instead of 100 parts by weight of the ethylene-vinyl acetate copolymer resin. The results of the outdoor exposure test and the light fastness test are shown in Table 3 (Example 1).
4). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

In Example 15, in the olefinic thermoplastic resin composition film used in Example 9,
100 parts by weight of a low-density polyethylene resin was used in place of 100 parts by weight of the ethylene-vinyl acetate copolymer resin, and the antioxidant (I) (compounding material (7), Irganox 1
010) Antioxidant (II) (compounding material (8), Irganox 1035) 1.5 parts by weight and antioxidant (III) (compounding material (9), Irgafos 168) instead of 3 parts by weight
An antifouling sheet was produced by the same procedure as in Example 9 using the two-blended with 1.5 parts by weight. The outdoor exposure test,
And the results of the light fastness test are shown in Table 3 (Example 15).
The antifouling property of the obtained antifouling sheet is extremely good,
Even after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and no generation of rain streaks was observed.

In Example 16, in the olefinic thermoplastic resin composition film used in Example 9,
50 parts by weight of 100 parts by weight of the ethylene-vinyl acetate copolymer resin was replaced by 50 parts by weight of the low-density polyethylene resin, and the antioxidant (I) (compounding material (7),
2 parts by weight out of 3 parts by weight of Irganox 1010), 1 part by weight of antioxidant (II) (compounding material (8), Irganox 1035) and antioxidant (III) (compounding material (9), Irgafoss 168) A three blend of antioxidants was used, replacing the two blend with 1 part by weight.
An antifouling sheet was produced in the same procedure as in Example 9. The results of the outdoor exposure test and the light fastness test are shown in Table 3 (Example 16). The antifouling property of the obtained antifouling sheet was extremely good, and after 18 months of outdoor exposure, the same hue and appearance as at the start of exposure were maintained, and the occurrence of rain streaks was also observed. There wasn't.

[0072] In each of Comparative Examples 9 to 16 Comparative Examples 9 to 16 were prepared antifouling sheet by the following process. Processing of base fabric made of fiber cloth with thermoplastic resin Warp yarn 1000 denier x weft yarn 10
00 denier polyester filament plain weave (thread density: vertical 22 / 2.54 cm, horizontal 25 / 2.54c
m: basis weight of 215 g / m ² ) was used as a base fabric, and the base fabric was prepared from the ethylene-vinyl acetate copolymer resin-based olefin resin emulsion composition of Example 9 with an antioxidant (2,4-dimethyl- A 50/50 weight ratio blend compound of 6- (1-methylpentadecyl) phenol and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trademark: Irganox 1076). Immersion in an olefin resin emulsion composition from which the entire amount of Irganox 1141)) has been removed, the base cloth is impregnated with the olefin resin emulsion composition, and then squeezed with a roller to obtain 95 g of the base cloth.
/ M ² of the olefin-based resin emulsion blended composition is evenly attached to the entire surface of the base fabric, then dried in a heat treatment furnace at 100 ° C. for 1 minute, and then heat-treated in a heat treatment furnace at 130 ° C. for 1 minute to give an olefin. The resin-based composition was fixed. A base material comprising an olefin resin composition-impregnated base fabric was obtained. <Olefin-based resin emulsion compounding composition> Ethylene-vinyl acetate copolymer resin emulsion 100 parts by weight Calcium carbonate 10 parts by weight Pigment (TiO ₂ ) 5 parts by weight [Note] Ethylene-vinyl acetate copolymer resin emulsion =
Trademark: Aquatex EC-1700 (resin solid content 50
Weight%: Chuo Rika Kogyo Co., Ltd.

Adhesion of a thermoplastic resin film to the base substrate was carried out in the same manner as in Example 9 except for the following matters.
A photocatalyst adhesion / protection layer and a photocatalyst surface layer were formed to prepare an antifouling sheet.

Comparative Examples 9 to 11 and Comparative Examples 13 and 14
Then, in the step of forming the photocatalyst adhesion / protection layer, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (from the photocatalyst adhesion / protection layer forming treatment liquid used in Example 9 was used. Irganox 107
The composition having the following composition obtained by removing the entire amount of 6) was used as a photocatalyst adhesion / protection layer forming treatment liquid, and this was used on the surface of the thermoplastic resin composition film layer of the base material layer using an 80 mesh gravure roll coater. To a coating amount of 15 g / m ² and dried in a heat treatment furnace at 100 ° C. for 1 minute to form a photocatalyst adhesion / protection layer. <Photocatalyst Adhesion / Protection Layer Forming Treatment Mixture> (a) 100 parts by weight of an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight (solid content) of an acrylic-silicone resin having a silicone content of 3 mol%. (b) 20 wt% ethanol solution of methyl silicate MS51 (Colcoat Co., Ltd.) as polysiloxane 8 parts by weight (c) 1 part by weight of γ-glycidoxypropyltrimethoxysilane (silane coupling agent)

In Comparative Example 9, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was not used in the ethylene-vinyl acetate copolymer resin composition film used in Example 9. A sheet was produced in the same procedure as in Example 9. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 9). In the obtained sheet, dirt began to stand out after 12 months of outdoor exposure,
In addition, the occurrence of dirt on the rain streak was also observed. Further outdoor exposure 18
After a month, the ethylene-vinyl acetate copolymer resin composition layer in the base material layer deteriorates the resin due to the photocatalyst, and the photocatalyst layer falls off. Proceeded to. Therefore, the sheet of Comparative Example 9 was unsuitable for long-term outdoor use.

In Comparative Example 10, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was not used in the ethylene-vinyl acetate copolymer resin composition film used in Example 9, Furthermore, inorganic pigments (II)
(Compounding material (12), yellow No. 5550) 2 parts by weight of organic pigment (III) (compounding material (19), isoindolinone yellow 1 part by weight (HCM1429 yellow (20 wt% conc)) as colored pellets 5 Parts by weight) were used to prepare an orange-colored sheet by the same procedure as in Example 9. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 9). In the obtained sheet, stains began to stand out after 12 months of outdoor exposure, and rain streak generation was also observed. Further, after 18 months of outdoor exposure, the ethylene-vinyl acetate copolymer resin composition layer of the base material layer deteriorates the resin due to the photocatalyst, and the photocatalyst surface layer falls off, which causes the adhesion of dirt and the generation of rain streaks. , Progressed rapidly. Therefore, the sheet of Comparative Example 10 was unsuitable for long-term outdoor use.

In Comparative Example 11, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was not added to the ethylene-vinyl acetate copolymer resin composition film used in Example 9. Further, instead of 5 parts by weight of the inorganic pigment (I) (compounding material (11), titanium oxide CR), organic pigment (IV) (compounding material (20), 1 part by weight of condensed azo red (HCM1170 red (20 wt%
conc) 5 parts by weight as colored pellets), and inorganic pigment (II) (compounding material (12), yellow N)
o. 5550) Organic pigment (III) instead of 2 parts by weight
(Compounding material (19), 1 part by weight of isoindolinone yellow (5 parts by weight as HCM1429 yellow (20 wt% conc) colored pellets) were used. A sheet colored orange was prepared by the same procedure as in Example 9. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 1).
It is shown in 1). In the obtained sheet, stains began to stand out after 12 months of outdoor exposure, and rain streak generation was also observed. Further, after 18 months of outdoor exposure, the ethylene-vinyl acetate copolymer resin composition layer in the base material layer deteriorated due to the photocatalyst, and the photocatalyst surface layer was dropped off, resulting in adhesion of dirt and generation of rain streaks. , Progressed rapidly. Therefore, the sheet of Comparative Example 11 was unsuitable for long-term outdoor use.

In Comparative Example 13, in the ethylene-vinyl acetate copolymer resin composition film used in Example 9, 3 parts by weight of 0.01 parts by weight of antioxidant (I) (compounding material (7), Irganox 1010) was used. Inorganic pigment (I) (compounding material (11), titanium oxide C)
R) In place of 5 parts by weight, an organic pigment (IV) (compounding material (20), 1 part by weight of condensed azo red (5 parts by weight as HCM1170 red (20 wt% conc) colored pellets)), and an inorganic pigment ( II) (Compounding material (12),
Yellow No. 5550) 2 parts by weight of organic pigment (III) (compounding material (19), 1 part by weight of isoindolinone yellow (HCM1429 yellow (20 wt% conc))
5 parts by weight) were used as colored pellets. By the same procedure as in Example 9, a sheet colored orange was prepared. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 13). In the obtained sheet, stains began to stand out after 12 months of outdoor exposure, and rain streak generation was also observed. After 18 months of outdoor exposure,
The ethylene-vinyl acetate copolymer resin composition layer in the base material layer deteriorated due to a photocatalyst, and the photocatalyst surface layer fell off, so that the adhesion of dirt and the occurrence of rain streaks rapidly progressed. Therefore, the sheet of Comparative Example 13 was unsuitable for long-term outdoor use.

In Comparative Example 14, in the ethylene-vinyl acetate copolymer resin composition film used in Example 9, 3 parts by weight of antioxidant (I) (compounding material (7), Irganox 1010) was used. 0.01 parts by weight of antioxidant (II) (compounding material (8), Irganox 1035) was used, and inorganic pigment (I) (compounding material (11),
Titanium oxide CR) Organic pigment (IV) instead of 5 parts by weight
(Compounding material (20), 1 part by weight of condensed azo red (HCM
1170 red (20 wt% conc) (5 parts by weight as colored pellets)) and used in place of 2 parts by weight of inorganic pigment (II) (compounding material (12), yellow No. 5550), organic pigment (III) (compounding) Material (19), 1 part by weight of isoindolinone yellow (HCM1429 yellow (20 wt
% Conc) 5 parts by weight) were used as colored pellets. By the same procedure as in Example 9, a sheet colored orange was prepared. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 14). In the obtained sheet, stains began to stand out after 12 months of outdoor exposure, and rain streak generation was also observed. Furthermore, after 18 months of outdoor exposure, the ethylene-methacrylic acid copolymer resin composition layer in the base material layer deteriorated due to a photocatalyst, and the photocatalyst surface layer fell off, resulting in adhesion of dirt and generation of rain streaks. But it progressed rapidly. Therefore, the sheet of Comparative Example 14 was unsuitable for long-term outdoor use.

In Comparative Example 12 and Comparative Examples 15 and 16
Is a photocatalyst adhesion / protection layer forming treatment solution containing 0.02 of the same antioxidant (Irganox 1076) as in Example 9 below.
A mixture of parts by weight was used. <Photocatalyst Adhesion / Protection Layer Forming Treatment Mixture> (a) 100 parts by weight of an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight (solid content) of an acrylic-silicone resin having a silicone content of 3 mol%. (b) 20 wt% ethanol solution of methyl silicate MS51 (Colcoat Co., Ltd.) as polysiloxane 8 parts by weight (c) γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by weight (d) octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (phenolic antioxidant) 0.02 parts by weight: Trademark: Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.)

In Comparative Example 12, 3 parts by weight of the antioxidant (I) (compounding material (7), Irganox 1010) was added to the ethylene-vinyl acetate copolymer resin composition film used in Example 9. In addition, instead of 5 parts by weight of the inorganic pigment (I) (compounding material (11), titanium oxide CR), an organic pigment (IV) (compounding material (20), 1 part by weight of condensed azo red (HCM1170 red (20 wt. % Co
nc) 5 parts by weight as colored pellets)), and inorganic pigment (II) (compounding material (12), yellow No. 55)
50) 2 parts by weight of organic pigment (III) (compounding material (19), 1 part by weight of isoindolinone yellow (HCM
1429 yellow (5 wt parts as 20 wt% conc colored pellets)) was used. By the same procedure as in Example 9, a sheet colored orange was prepared. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 12). In the obtained sheet, stains began to stand out after 12 months of outdoor exposure, and rain streak generation was also observed. Furthermore, after 18 months of outdoor exposure, ethylene-
The vinyl acetate copolymer resin composition layer deteriorated due to the photocatalyst, and the photocatalyst surface layer fell off, so that the adhesion of dirt and the generation of rain streaks rapidly progressed. Therefore, the sheet of Comparative Example 12 was unsuitable for long-term outdoor use.

In Comparative Example 15, in the ethylene-vinyl acetate copolymer resin composition film used in Example 9, 3 parts by weight of antioxidant (I) (compounding material (7), Irganox 1010) was used. 0.01 parts by weight of the antioxidant (III) (compounding material (9), Irgafos 168) were used, and further, instead of 5 parts by weight of the inorganic pigment (I) (compounding material (11), titanium oxide CR), Organic pigment (IV)
(Compounding material (20), 1 part by weight of condensed azo red (HCM
1170 red (20 wt% conc) (5 parts by weight as colored pellets)) and used in place of 2 parts by weight of inorganic pigment (II) (compounding material (12), yellow No. 5550), organic pigment (III) (compounding) Material (19), 1 part by weight of isoindolinone yellow (HCM1429 yellow (20 wt
% Conc) 5 parts by weight) were used as colored pellets. By the same procedure as in Example 9, a sheet colored orange was prepared. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 15). In the obtained sheet, stains began to stand out after 12 months of outdoor exposure, and rain streak generation was also observed. Furthermore, after 18 months of outdoor exposure, the ethylene-methacrylic acid copolymer resin composition layer in the base material layer deteriorated due to a photocatalyst, and the photocatalyst surface layer fell off, resulting in adhesion of dirt and generation of rain streaks. But it progressed rapidly. Therefore, the sheet of Comparative Example 15 was unsuitable for long-term outdoor use.

In Comparative Example 16, in the olefinic thermoplastic resin composition film used in Example 9,
50 parts by weight of 100 parts by weight of ethylene-vinyl acetate copolymer resin was replaced by 50 parts by weight of low-density polyethylene resin, and 3 parts by weight of antioxidant (I) (compounding material (7), Irganox 1010) was added. In addition, inorganic pigment (I) (compounding material (11), titanium oxide CR) 5
Instead of parts by weight, organic pigment (IV) (compounding material (20),
1 part by weight of condensed azo red (HCM1170 (20 wt% co
nc) 5 parts by weight as colored pellets)), and inorganic pigment (II) (compounding material (12), yellow No. 55)
50) 2 parts by weight of organic pigment (III) (compounding material (19), 1 part by weight of isoindolinone yellow (HCM
1429 yellow (5 wt parts as 20 wt% conc colored pellets)) was used. A sheet colored in orange was prepared by the same procedure as in Example 9. The results of the outdoor exposure test and the light fastness test are shown in Table 4 (Comparative Example 16). In the obtained sheet, stains began to stand out after 12 months of outdoor exposure, and rain streak generation was also observed. Further, after 18 months of outdoor exposure, the thermoplastic resin composition layer composed of the ethylene-vinyl acetate copolymer resin and the low-density polyethylene resin composition in the base material layer deteriorated due to the photocatalyst, and the photocatalyst surface layer fell off. As a result, the adhesion of dirt and the generation of dirt on the rain streak progressed rapidly. Therefore,
The sheet of Comparative Example 16 was unsuitable for long-term outdoor use.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

As is apparent from the above Examples and Comparative Examples, the antifouling sheet according to the present invention is obtained by adding an antioxidant to the thermoplastic resin composition layer in the base material layer. ,
The antioxidant supplements the active oxygen that affects the thermoplastic resin composition layer among the active oxygen generated by the photocatalytic action, so that the effect of decomposing and degrading the photocatalyst with respect to the thermoplastic resin composition can be obtained. Since the photocatalyst surface layer does not come off due to the decomposition and deterioration of the thermoplastic resin during long-term outdoor use, it is possible to maintain the stable antifouling effect due to the stable photocatalytic action over a long period of time. Is extremely useful as Further, in the antifouling sheet of the present invention, at least one layer of a thermoplastic resin composition layer and a surface layer containing a photocatalyst and optionally a photocatalyst adhesion / protection layer is colored with a colorant containing an inorganic pigment. As a result, the appearance and design of the sheet can be maintained for a long period of time. Therefore, the antifouling sheet of the present invention is extremely useful as a tent sheet.

Claims (6)

[Claims] 1. A substrate layer comprising at least one thermoplastic resin composition layer, and a surface layer formed on at least one surface thereof and containing a photocatalyst, wherein at least the photocatalyst of the substrate layer. The thermoplastic resin composition layer closest to the surface layer containing contains 0.01 to 5.0% by weight of an antioxidant, and the thermoplastic resin composition layer and the surface layer containing a photocatalyst. An antifouling sheet, wherein at least one layer is colored with a colorant containing an inorganic pigment. 2. A photocatalyst adhesion / protection layer containing a thermoplastic resin containing 0.01 to 5.0% by weight of an antioxidant is formed between the base material layer and the surface layer containing the photocatalyst. The antifouling sheet according to claim 1, which is contained. 3. The antifouling sheet according to claim 1, wherein the antioxidant is at least one selected from phenolic compounds, phosphite compounds, sulfur compounds and vitamin E compounds. .. 4. The antifouling agent according to claim 1, wherein the base material layer has a base cloth made of a fiber cloth, and the thermoplastic resin composition layer laminated on at least one surface thereof. Sex sheet. 5. The surface layer containing the photocatalyst is 0.01
~ 5.0 wt% antioxidant is contained.
The antifouling sheet according to any one of 4 above. 6. The photocatalyst / protection layer is further colored with a colorant containing an inorganic pigment.
Antifouling sheet as described in.