Colored sheet excellent in discoloration preventing property

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a colored sheet having excellent anti-discoloration and fading properties. More specifically, the present invention relates to a colored sheet having a colored outer layer made of a pigment-colored thermoplastic resin composition and a surface layer formed on the colored outer layer and containing a photocatalyst. The colored sheet having excellent anti-fading property of the present invention is suitably used as an industrial material such as a medium-sized and large-sized tent, a building member such as a tent warehouse, a truck hood, and a sign sheet for a signboard. The discoloration and fading phenomenon can be prevented for a long period of time. In the present invention, coloring includes white coloring with a white pigment and coloring with a colored pigment mixture containing a white pigment.

【0002】

[Conventional technology]

Recently, by applying a photocatalyst to the surface of polymer compounds such as paper, textile woven fabric, film, and synthetic resin molded products, foul odors that come into contact with or adhere to the surface of these polymer compounds, harmful substances suspended in the air, and harmful substances in the air A technology for deodorizing and purifying organic compounds such as soot and dust by decomposing and removing them by the strong redox action of photocatalysts has been developed, and it is proposed to apply this to applications such as air conditioner filters, curtains, and wallpaper. Has been done. In the sanitary industry, it has been proposed to utilize the strong redox action of photocatalysts as antibacterial and antifungal function-imparting products without using conventional antibacterial agents or antifungal agents. Clean and effective products have been proposed that kill microorganisms such as molds and bacteria and prevent their growth.

【0003】

By the way, products using these photocatalysts on the surface of polymer compounds have foul odors, organic compounds such as harmful substances suspended in the air and soot, and microorganisms such as fungi, molds, and bacteria due to the strong redox action of the photocatalyst. Not only that, but also the polymer compound that is the base material of the photocatalyst also decomposes and deteriorates at the same time, and for that reason, after the start of use indoors and outdoors. It is pointed out that the photocatalyst falls off from the product together with the weathered product of the deteriorated polymer compound at an early stage, which makes it impossible to maintain the photocatalytic effect for a long period of time, and eventually shortens the life of the product significantly. Has been done.

【0004】

Further, the strong redox action of the photocatalyst not only decomposes and deteriorates the polymer compound forming the base material, but also various treatment agents and additives for paper, fiber woven fabric, film, synthetic resin molded product and the like. , When a compounding agent is used in combination, decomposition and deterioration of these substances also progress and accelerate at the same time. Therefore, even if the product is given characteristics and functionality by these treatment agents, additives and compounding agents, its special effect is achieved. However, there is a problem that it disappears in a short period of time. Among the products to which these photocatalysts are applied, the one with the greatest damage of loss of effect is the problem of discoloration and fading of the product due to decomposition and deterioration of the colorant used for coloring the product, and this phenomenon of discoloration and fading can be easily discriminated visually. As it is recognizable, it has a great influence on product value and reliability.

【0005】

For example, a thermoplastic resin composition laminated sheet obtained by coating a fibrous base cloth with a thermoplastic resin composition, such as a awning tent or a medium-sized tent, requires colorful hues and abundant color variations. , It is necessary to have an assortment of various color specifications. The colorants of these thermoplastic resin compositions are generally selected and used according to the purposes such as hue, design, bucklit effect, cost, and processability. However, in particular, these awning tents and medium- and large-sized tent sheets are provided with photocatalysts to provide air purification functionality, harmful substance removal functionality, or antibacterial, antifungal, and antifouling functions. In the development of the laminated sheet of the thermoplastic resin composition, there has been a great deal of interest in technical improvements and improvements for the decomposition and deterioration prevention of the colored thermoplastic resin composition by the redox action of the photocatalyst. Regarding the harmful effects of decomposition and deterioration of the colorant due to the photocatalytic redox action, and the drawback that the hue of the tent gradually changes or fades as a result, this is simply a problem of the limit of weather resistance of the colorant. The reality is that it is considered and no special consideration is given. Therefore, by applying a photocatalyst to a colorful and hue-durable sheet used for long-term outdoor applications such as medium-sized and large-sized tents and awning tents, it has an air purification function and a harmful substance removal function, or is antibacterial. It was considered impossible to put a colored thermoplastic resin composition sheet having antifungal and antifouling properties into practical use.

【0006】

[Problems to be Solved by the Invention]

The present invention maintains excellent color and anti-fading properties when used outdoors for a long period of time, and is stable and highly durable against the redox action of photocatalysts for a long period of time. It is intended to provide a colored sheet having excellent properties.

【0007】

[Means for solving problems]

As a result of repeated studies and studies in view of the above-mentioned current situation, the present invention independently arranges a surface layer containing a photocatalyst on an outer layer of a pigment-colored thermoplastic resin composition, and is a main component of the coloring pigment. The present invention has been completed by finding that a colored sheet capable of withstanding long-term outdoor use and withstanding the redox action of a photocatalyst can be produced by using an inorganic pigment of 70% by weight or more. ..

【0008】

The colored sheet having excellent anti-discoloration and fading properties of the present invention comprises a base material layer having at least one colored outer layer formed of a thermoplastic (elastomer) resin composition colored with a pigment, and the base material layer. It has a surface layer formed on the colored outer layer and containing a photocatalyst, and the colored pigment contained in the colored outer layer contains 70% by weight or more of an inorganic pigment. In the colored sheet having excellent anti-discoloration and fading properties of the present invention, it is preferable that the colored pigment contained in the colored outer layer is composed only of an inorganic pigment. In the colored sheet having excellent anti-discoloration and fading properties of the present invention, the colored pigment contained in the colored outer layer contains 70 to 99% by weight of an inorganic pigment and 1 to 30% by weight of an organic pigment. You may. In the colored sheet having excellent anti-discoloration and fading properties of the present invention, the colored pigment contained in the colored outer layer contains 85 to 99% by weight of an inorganic pigment and 1 to 15% by weight of an organic pigment. You may. In the colored sheet having excellent anti-fading property of the present invention, the base material layer further includes a base cloth layer made of a fiber cloth, and the colored outer layer is formed on at least one surface thereof, and the photocatalyst is used. The contained surface layer may be formed on the at least one colored outer layer. In the colored sheet having excellent anti-discoloration and fading properties of the present invention, the colored outer layer may be formed of a film or sheet formed from the colored pigment-containing thermoplastic (elastomer) resin composition. In the colored sheet having excellent anti-discoloration and fading properties of the present invention, the colored outer layer may be formed from an ink or a paint containing the colored pigment-containing thermoplastic (elastomer) resin composition. In the coloring sheet having excellent anti-discoloration and fading properties of the present invention, the surface layer containing the photocatalyst may be colored with a colorant containing 70% by weight or more of an inorganic coloring pigment.

【0009】

BEST MODE FOR CARRYING OUT THE INVENTION

In the base material layer of the colored sheet having excellent anti-discoloration and fading properties of the present invention, examples of the thermoplastic resin used for the colored outer layer composed of the pigment-colored thermoplastic (elastomer) resin composition include vinyl chloride resin and chloride. Vinyl-based copolymer resin, olefin resin, olefin-based copolymer resin, urethane resin, urethane-based copolymer resin, acrylic resin, acrylic copolymer resin, vinyl acetate resin, vinyl acetate-based copolymer resin, styrene resin, styrene-based It is configured by using a thermoplastic resin such as a polymer resin, a polyester resin, a polyester-based copolymer resin, and a fluorine-based copolymer resin alone, or by blending two or more kinds. In particular, among these thermoplastic resins, vinyl chloride resin and vinyl chloride-based copolymer resin can be preferably used because of their excellent resin physical properties, resin properties, molding processability, and low cost. However, when a halogen-free resin is required for reasons such as environmental protection, recycling, and incineration, an olefin resin and an olefin copolymer resin are most preferably used.

【0010】

When a vinyl chloride resin is used as the thermoplastic resin for the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention, a polyester-based plasticizer having low plasticity transferability should be used as the plasticizer blended therein. Is preferable. Examples of the above-mentioned vinyl chloride resin and vinyl chloride-based copolymer resin include polyvinyl chloride, vinyl chloride-ethylene copolymer resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl ether copolymer resin, and 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. It is preferable to use one or more resins selected from the above.

【0011】

Examples of the olefin resin and olefin-based copolymer resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methyl acrylate copolymer resin, ethylene-methyl methacrylate copolymer resin, and ethylene. -One or more resins selected from methacrylic acid copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-propylene copolymer resin and the like can be used.

【0012】

In addition, 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 Natural or synthetic rubber such as rubber, acrylic rubber, urethane rubber, silicone rubber, and fluorine rubber, as well as cross-linking between these synthetic rubbers and the above thermoplastic resin, thermoplastic elastomer (TPE), which is a sulfide alloy, are also used. Can do things.

【0013】

In the colored outer layer of the colored sheet having excellent anti-discoloration and fading properties of the present invention, if necessary, a plasticizer, a secondary plasticizer, a stabilizer, a lubricant, a flame retardant, a flame retardant, a foaming agent, and an antistatic agent. , Surfactants, water repellents, oil repellents, crosslinkers, hardeners, conductive fillers, various fillers, fungicides, antibacterial agents, UV absorbers, antioxidants, softeners, thickeners, viscosity reducing agents , Etc., which are usually used additives, may be contained within a range that does not deviate from the effect and purpose of the present invention.

【0014】

It is most preferable that the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention is composed of only an inorganic pigment, and the inorganic pigments that can be used include zinc oxide (zinc flower) and titanium oxide (rutyl type, anatase). Type), Antimon Trioxide, Iron Oxide (Iron Black, Bengara), Yellow Iron Oxide, Iron Sulfide (Navy Blue), Navy Blue and Yellow Lead (Zink Green), Lead Oxide (Lead Tan), Chromium Oxide, Oxidation Zulfide, cobalt oxide and aluminum oxide composite (cobalt blue), cobalt oxide, tin oxide and magnesium oxide composite (Cerulean blue), cobalt oxide, lithium oxide and phosphorus pentoxide composite (cobalt violet), oxidation Metal oxides such as cobalt / zinc oxide / magnesium oxide complex (cobalt green), cobalt phosphate (cobalt violet), manganese phosphate (manganese purple), zinc sulfide / barium sulfate complex (lithopon), sulfide Calcium, Strontium Sulfide, Zinc Sulfide, Cadmium Zinc Sulfide, Cadmium Sulfide (Cadmium Yellow), Cadmium Sulfide and Mercury Sulfide Complex (Cadmium Mercury Red), Mercury Sulfide (Silver Zhu), Cadmium Sulfide and Selenium-Cadmium Complex ( Metal sulfides such as Cadmium Red, Cadmium Orange, Cadmium Yellow), Complex of Antimon Sulfide and Antimon Trioxide (Antimon Zhu), Metal Sulfide such as Barium Sulfide, Calcium Sulfate, Lead Sulfate, Basic Lead Sulfide, Carbonate Barium, calcium carbonate, magnesium carbonate, metal carbon oxides such as lead carbonate and lead hydroxide composite (lead white), aluminum hydroxide (alumina white), aluminum hydroxide and calcium sulfate composite (satin white), water Composite of aluminum oxide and barium sulfate (gloss white), metal hydroxides such as sulphide hydrate (viridian), lead chromate (yellow lead), zinc chromate (zinc yellow), barium sulphate, sulphide Metal sulphate such as lead-lead oxide complex (red-mouthed yellow lead), lead sulphate / lead molybdate / lead sulphate (chrome vermilion), and lead sulphate / lead sulphate complex(Molybdenum red), mixture with dark blue chrome yellow (chrome green), spinel type (XY₂O₄) Structural oxides: [Note, XY = Co-Al, Co-Al-Cr, Co-Mg-Sn, Co-Ni-Ti, Co-Zn-Ni-Ti, Co-Zn-Cr-Ti, Zn- Cr-Ti, Zn-Cr-Fe, Co-Zn-Cr-Fe, Co-Ni-Cr-Fe-Si, Co-Mn-Cr-Fe, Cu-Mn-Cr, Mn-Fe, etc.], rutile type [Ti (XY) O₂] Structural oxides [Note, XY = Pb-Sb, Ni-Sb (titanium yellow), Ni-W, Fe-Mo, Cr-Sb, etc.], carbon black, titanium black, acetylene black, graphite, silica, white carbon , Kayla soil, talc, clay, aluminum powder pigment, bronze powder, nickel powder, stainless powder, pearl pigment, etc., which may be used alone or in combination of two or more, depending on the purpose. Can be done. In addition, these inorganic pigments are blended and filled in thermosetting resins such as melamine resin, benzoguanamine resin, urea resin, phenol resin, and epoxy resin, and then finely powdered and crushed to be used as a thermosetting resin-coated inorganic pigment. You may.

【0015】

The amount of these inorganic pigments added can be any amount depending on the desired hue adjustment, and is not particularly limited, but is 0.1 to 50.0% by weight based on 100 parts by weight of the thermoplastic resin. The amount is preferably 1 to 30.0 parts by weight, more preferably 1 to 30.0 parts by weight. When the amount of the inorganic pigment added is 0.1 parts by weight or less, the degree of coloring of the thermoplastic resin is low, and sufficient concealing property may not be obtained as a colored sheet. On the other hand, if it exceeds 50.0 parts by weight, not only the molding processability of the obtained thermoplastic resin composition is deteriorated, but also the mechanical strength and abrasion strength of the obtained colored outer layer may be insufficient.

【0016】

These inorganic pigment products have been treated with a dispersant in order to further improve dispersibility when used in coloring applications such as synthetic resin molded products, films, synthetic fibers, synthetic resin paints, and printing inks. It is preferable to use a processed pigment. As such dispersants for processed pigments, as aqueous dispersants, formalin condensates of sodium lignin sulfonate, sodium alkyl sulfate ester, sodium alkylaryl sulfonate, sodium naphthalene sulfonate, marcel sequen, polyoxyethylene alkyl ether, etc. Examples thereof include polyoxyethylene aryl ether, styrene-maleic acid resin, polyacrylic acid derivative, etc., and examples of the oil dispersant include lecithin, sorbitan fatty acid ester, partial fatty acid ester of polyacrylic acid, alkylamine fatty acid salt, alkyldiamine, and alkyltriamine. Examples include metal naphthenate sheets.

【0017】

Vehicles, press cakes, resins, waxes, plasticizers, water, etc. are further added to the dispersant-treated inorganic pigments in the dispersant-treated composition in order to improve the processing handleability in various applications thereof. Each may be adjusted to a form such as a flushed color, an aqueous liquid color, an oily liquid color, a paste color (vinyl toner color), a dry color, a moisturizing color, a master batch, or a colored pellet. In the colored sheet having excellent anti-discoloration and fading properties of the present invention, the thermoplastic resin is a vinyl chloride resin as a colorant to be blended with the thermoplastic resin of the colored outer layer, and this vinyl chloride resin is a paste vinyl chloride. In the case of, a moisturizing color or a paste color (vinyl toner color) is used, and when straight vinyl chloride is used, it is preferable to use a dry color or a master batch. When the pigment-containing thermoplastic resin composition is subjected to melt-kneading of the thermoplastic resin such as calendar processing, T-die extrusion processing, inflation processing, etc., the processing pigment is dry color or masterbatch. , Or it is preferable to use colored pellets. In particular, for molding of olefin-based resins, the form of colored pellets in which an inorganic pigment is packed in a polyolefin-based resin such as polyethylene or polypropylene together with a dispersant and wax at a high concentration can be more preferably used. When the thermoplastic resin is an aqueous emulsion, an aqueous liquid color can be used. Further, when the thermoplastic resin composition is used as a solvent-based paint or a printing ink, the pigment is preferably a flush color, a paste color, a dry color, an oil-based liquid color or the like.

【0018】

A compound of a thermoplastic resin composition obtained by adding an inorganic pigment to the above-mentioned thermoplastic resin and further blending various additives as necessary can be obtained by a known method, for example, a Banbury mixer, a kneader, a twin-screw kneader or the like. A masterbatch with a high concentration of inorganic pigments is prepared by a method of melt-kneading and then granulating using a tumbler blender, a Banbury mixer, etc., and then dry-blended using a mixer such as a tumbler blender, a tumble mixer, or a Henschel mixer. It can be prepared by adopting a method and a method of melt-kneading and granulating with a single-screw extruder, a twin-screw extruder, or the like after mixing.

【0019】

Gobordeaux, thioindigo magenta, thioindigo brown, etc., examples of perinone pigments include perinone orange, perinone red, etc., and examples of perylene pigments include perylene carlet, perylene Bordeaux, etc., and quinacridone pigments. Examples of the pigment include quinacridone red and quinacridone magenta, examples of the dioxazine pigment include dioxazine violet, and examples of the isoindolinone pigment include isoindolinone yellow 3RLT and isoindolinone orange RLT. Isoindolinone Red 2BLT and the like, examples of the quinophthalone pigment include, for example, quinophthalone yellow, examples of the isoindolin pigment include, for example, isoindrin yellow, and other organic pigments include nitroso pigments, such as nickel. Nitroso Yellow, Pigment Green B and the like can be mentioned, examples of the Alizarin lake pigment include Madder Lake, Alizarin Maroon and the like, examples of the metal complex salt azomethine pigment include copper azomethine yellow, and examples of the aniline pigment include aniline. Black is mentioned. Only one of these organic pigments or two or more of these organic pigments can be used in combination with the inorganic pigment. Further, a thermosetting resin coating pigment prepared by pulverizing and pulverizing a mixture of these organic pigments in a thermosetting resin such as a melamine resin, a benzoguanamine resin, a urea resin, a phenyl resin, or an epoxy resin is used. You may use it. For example, isoindoline yellow 3RLT, isoindoline orange RLT, isoindoline red 2BLT and the like can be mentioned, and examples of the quinophthalone pigment include quinophthalone yellow, and examples of the isoindoline pigment include isoindoline yellow. Examples of other organic pigments include nitroso pigments such as nickel nitroso yellow and pigment green B, and examples of alizarin lake pigments include madder lake and alizarin maroon. Examples of metal complex salt azomethine pigments include, for example. Copper isomethine yellow is mentioned, and examples of the aniline pigment include aniline black. Only one of these organic pigments or two or more of these organic pigments can be used in combination with the inorganic pigment. Further, a thermosetting resin coating pigment prepared by pulverizing and pulverizing a mixture of these organic pigments in a thermosetting resin such as a melamine resin, a benzoguanamine resin, a urea resin, a phenyl resin, or an epoxy resin is used. You may use it. For example, isoindoline yellow 3RLT, isoindoline orange RLT, isoindoline red 2BLT and the like can be mentioned, and examples of the quinophthalone pigment include quinophthalone yellow, and examples of the isoindoline pigment include isoindoline yellow. Examples of other organic pigments include nitroso pigments such as nickel nitroso yellow and pigment green B, and examples of alizarin lake pigments include madder lake and alizarin maroon. Examples of metal complex salt azomethine pigments include, for example. Copper isomethine yellow is mentioned, and examples of the aniline pigment include aniline black. Only one of these organic pigments or two or more of these organic pigments can be used in combination with the inorganic pigment. Further, a thermosetting resin coating pigment prepared by pulverizing and pulverizing a mixture of these organic pigments in a thermosetting resin such as a melamine resin, a benzoguanamine resin, a urea resin, a phenyl resin, or an epoxy resin is used. You may use it.

【0020】

In addition, these organic pigment products are treated with a dispersant in order to further improve dispersibility when used in coloring applications such as synthetic resin molded products, films, synthetic fibers, synthetic resin paints, and printing inks. It is preferable to use it as a processed pigment. Dispersants for processing pigments include aqueous dispersants such as sodium lignin sulfonate, sodium alkyl sulfate ester, sodium alkylaryl sulfonate, formalin condensate of sodium naphthalene sulfonate, marcel sequen, polyoxyethylene alkyl ether, and pooxyethylene. Aryl ether, styrene-maleic acid resin, polyacrylic acid derivative, etc. are mentioned, and examples of the oil dispersant include lecithin, sorbitan fatty acid ester, partial fatty acid ester of polyacrylic acid, alkylamine fatty acid salt, alkyldiamine, alkyltriamine, and metal naphthenate. Esters and the like can be mentioned.

【0021】

These dispersant-treated organic pigments are flushed with vehicles, press cakes, resins, waxes, plasticizers, water, etc., in order to improve processing handleability in various applications. It is preferably used as a processing pigment prepared in the form of color, water-based liquid color, oil-based liquid color, paste color (vinyl toner color), dry color, moisturizing color, master batch, colored pellets and the like.

【0022】

When the thermoplastic resin is a vinyl chloride resin and the vinyl chloride resin is a paste vinyl chloride, the thermoplastic resin of the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention is a colorant. , Moisture color or paste color (vinyl toner color) is preferably used, and in the case of straight vinyl chloride, dry color or master batch is preferably used. When the pigment-containing thermoplastic resin composition is subjected to melt-kneading of the thermoplastic resin such as calendar processing, T-die extrusion processing, and inflation processing, the processed pigments are dry color, masterbatch, and colored pellets. Is preferable. In particular, for molding of olefin resins, the form of colored pellets in which an organic pigment is packed in a polyolefin resin such as polyethylene or polypropylene together with a dispersant and wax at a high concentration can be more preferably used. When the thermoplastic resin is an aqueous emulsion, an aqueous liquid color can be preferably used, and when it is a solvent-based paint or a printing ink, a flushed color, a paste color, a dry color, an oil-based liquid color or the like is preferably used. it can.

【0023】

As the colorant used for the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention, an inorganic pigment and an organic pigment can be used in combination. When an inorganic pigment and an organic pigment are added to the thermoplastic resin in combination, the content of the inorganic pigment is preferably 70 wt% to 99 wt%: the organic pigment is preferably 1 wt% to 30 wt%, and the inorganic pigment is also added. 85 to 99 wt%: More preferably, the organic pigment is 1 to 15 wt%. The amount of the combined pigment added between these inorganic pigments and the organic pigments can be any amount depending on the desired hue, but is 0.1 to 50.0% by weight based on 100 parts by weight of the thermoplastic resin. It is preferably parts, and more preferably 1 to 30.0 parts by weight. If the amount of the pigment added is 0.1 parts by weight or less, the degree of coloring of the thermoplastic resin becomes insufficient, and the desired hiding property may not be obtained. On the other hand, if it exceeds 50.0 parts by weight, not only the molding processability of the thermoplastic resin composition is deteriorated, but also the mechanical strength and abrasion strength of the colored outer layer may be lowered.

【0024】

Further, a method of granulating a compound of a thermoplastic resin composition for a colored outer layer containing various additives, if necessary, after melt-kneading using a known method, for example, a Banbury mixer, a kneader, a twin-screw kneader or the like. Alternatively, a masterbatch with a high concentration of inorganic pigments and organic pigments having the above ratio is prepared with a Banbury mixer or the like, and then dry-blended using a mixer such as a tumbler blender, a tumble mixer, or a Henschel mixer. Further, a method of melt-kneading and granulating with a single-screw extruder, a twin-screw extruder or the like can be adopted.

【0025】

The film or sheet forming the outer layer of the colored thermoplastic resin composition of the colored sheet having excellent discoloration prevention property of the present invention can be obtained by a known film or sheet processing technique such as a T-die method, an inflation method, or a calendar method. Can be manufactured. In the production of the film or sheet, it is desirable from the viewpoint of production efficiency to perform the molding process of the thermoplastic resin composition film or sheet in the temperature range of 100 to 250 ° C by the calendar method.

【0026】

The thickness of the film or sheet used for the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention is preferably 80 to 1000 μm, and more preferably 130 to 500 μm. If the thickness is thinner than this range, molding is difficult, and when the fiber fabric is thermocompression-bonded and laminated, the unevenness of the fiber fabric surface causes the film to break, which impairs waterproofness. It may not be usable for awning tents, medium and large tents, and tent warehouse applications. The thickness is the thickness than the above range if not, not only calendering becomes difficult, heavy and inflexible, it may handleability becomes poor.

【0027】

Further, in order to form the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention on at least one surface of the fiber cloth, vinyl chloride resin emulsion, polyolefin resin emulsion, acrylic resin emulsion, urethane type A known coating method, for example, a doctor knife coat, is applied to a thermoplastic resin composition paint prepared by blending an aqueous liquid pigment with the above-mentioned thermoplastic resin emulsion such as a resin emulsion and an aqueous dispersion, or a printing ink. It can be formed by coating with a method, a gravure coating method, a rotary screen coating method, a dip coating method, etc., and drying. As a method of forming the prepared outer layer using this thermoplastic resin emulsion composition paint or printing ink, the thermoplastic resin emulsion composition paint or printing ink is directly coated on at least one surface of the fiber cloth and dried. The method may be used, or the release paper or release film is coated with a thermoplastic resin emulsion composition paint or printing ink, and the dried product is transferred and laminated on at least one surface of the fiber cloth and laminated. You may.

【0028】

Further, as another method for forming the colored outer layer on at least one surface of the fiber cloth of the colored sheet having excellent discoloration prevention property of the present invention, a polyolefin resin, an acrylic resin, a urethane resin, a polyester resin or the like can be used. A dry color pigment, a paste color pigment, or a flushed color pigment is blended with a resin composition solution prepared by dissolving the above-mentioned thermoplastic resin in an organic solvent to obtain a thermoplastic resin composition paint or a printing ink. It can be formed by preparing it, coating it with a known coating method, for example, a doctor knife coating method, a gravure coating method, a rotary screen coating method, a dip coating method, or the like, and drying it. As a method for forming the colored outer layer using this thermoplastic resin composition paint or printing ink, the thermoplastic resin composition paint or printing ink may be directly coated and dried on the fiber cloth, or may be dried. , This may be coated and dried on a release paper or a release film with a thermoplastic resin composition paint or a printing ink, and the obtained film may be transferred and laminated on a fiber cloth.

【0029】

The fiber cloth base cloth that can be used as the core layer for the base material layer having the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention may be a woven cloth, a knitted cloth, or a non-woven fabric. The woven fabric is not particularly limited in woven structure, but a plain weave woven fabric is preferably used because it has an excellent balance of vertical and weft physical properties of the obtained sheet. As the knitting fabric, a Russell-knitted weft-inserted tricot is preferable, and as the non-woven fabric, a non-woven fabric using long fibers is preferable, and a spunbonded non-woven fabric or the like is particularly preferable. Further, the fiber fabric may be composed of any of synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these, but in consideration of processability and versatility, polypropylene fibers and polyethylene fibers may be used. , Polyvinyl alcohol fiber, polyester fiber, polyamide fiber, acrylic fiber, polyurethane fiber, or synthetic fiber such as a mixed fiber thereof is preferably used, and these synthetic fibers are long fiber yarn and short fiber spun fiber. , Split yarn, tape yarn and the like. Among them, a multifilament plain weave fabric base fabric or a spun plain weave fabric base fabric formed from polyester fibers, polyamide fibers, mixed fibers thereof, composite fibers, etc., which are excellent in tensile strength, tear strength, heat-resistant creep characteristics, etc. are used. Is preferable.

【0030】

The laminated fabric of these fiber fabrics and the film or sheet forming the colored outer layer may be laminated on one side of the fiber fabric or on both sides. Considering the durability for outdoor use, the fiber fabric may be laminated. It is preferable to laminate a film or a sheet that forms a colored outer layer on both sides of the above. Further, as a laminating method, an adhesive layer may be provided between the film or sheet and the fiber fabric, or laminating and fusing may be performed without an adhesive.

【0031】

In the production of the colored sheet having excellent anti-discoloration and fading properties of the present invention, the method of laminating the fiber cloth and the colored outer layer film or the sheet follows the molding step of the film or the sheet, and heat-laminates the fiber cloth on the fiber cloth. When the method, that is, the calendar topping method, the T-die laminating method, or the calendar method, the T-die method, the inflation method, etc. is used, the film or sheet is molded and then heat-bonded to the fiber fabric by a laminator. Laminate on. In order to produce a colored sheet having excellent discoloration prevention property according to the present invention, a method of laminating the film or sheet molded by the calendar method and a polyester fiber plain weave fabric by thermocompression bonding is efficient and economical. It is preferable. At this time, the woven structure of the fiber plain weave fabric is preferably a clear plain weave. In this case, a laminated sheet can be manufactured without the need for an adhesive, and the physical characteristics in the vertical and horizontal directions are The balance is also excellent. Further, the method for forming the colored outer layer forming film or sheet of the colored sheet having excellent discoloration prevention property of the present invention is a pigment blending using the thermoplastic resin emulsion, an aqueous dispersion, or a soft vinyl chloride paste. In the case of a method of coating and drying the coating composition, the woven structure of the fiber plain weave fabric is preferably a non-perforated plain weave with a high thread density, and more preferably a spun fiber plain weave fabric or the like.

【0032】

When the colored outer layer of the colored sheet having excellent discoloration prevention property of the present invention is formed of a vinyl chloride resin, when the vinyl chloride resin is a paste vinyl chloride resin composition, vinyl chloride is applied by coating. After forming the resin paste layer, a step of heating and gelling it at a temperature of 120 to 200 ° C. and solidifying it is particularly necessary.

【0033】

The thickness of the colored sheet having excellent anti-discoloration and fading properties of the present invention is not particularly limited, and is appropriately selected depending on the intended use. For example, 80 to 1000 μm when the surface layer containing the photocatalyst is provided on one side or both sides of the colored film or sheet, and 120 to 120 when the surface layer containing the photocatalyst and the colored outer layer are provided on one side of the fiber cloth. 1600 μm, when the surface layer containing a photocatalyst and the colored outer layer are provided on both sides of the fiber fabric, it is about 160 to 2000 μm.

【0034】

In the colored sheet having excellent anti-discoloration and fading properties of the present invention, a coating layer containing a photocatalyst and a coating layer containing a thermoplastic resin composition as a main component, which is stable against photocatalytic action, is formed on the surface of the colored outer layer. It is formed as a surface layer. Depending on the application, the surface layer containing the photocatalyst can be formed on both sides of the colored sheet having excellent anti-discoloration and fading properties of the present invention. The coating agent containing a photocatalyst used for the colored sheet having excellent anti-discoloration and fading properties of the present invention has an adhesive and protective layer made of an acrylic-silicone resin containing polysiloxane interposed therein on the surface of the colored outer layer. Alternatively, it is applied without intervention, thereby forming a surface layer containing a photocatalyst containing a photocatalytic particle composite containing a metal oxide sol. Specifically, the surface layer containing a photocatalyst contains 1 to 10% by weight of silica sol, 1 to 10% by weight of monoalkyltrimethoxysilane or its hydrolysis product, and 1 to 10% by weight of titanium oxide sol. A surface layer coating agent containing a photocatalyst composed of a compounding solution is applied to the surface of the adhesive / protective layer or the surface of a colored outer layer and dried. In this case, the surface layer containing the photocatalyst may be colored with a colorant containing 70% by weight or more of an inorganic coloring pigment.

【0035】

As the monoalkyltrimethoxysilane, for example, methyltrimethoxysilane, methyltriethoxysilane and the like can be particularly preferably used. The mixing ratio of the silica sol to the monoalkyltrimethoxysilane or its hydrolysis product is preferably 100% / 0% to 60% / 40% by weight, and the ratio of the titanium oxide sol to the silane compound is , The weight ratio of the titanium oxide / silane compound is preferably 5% / 95% to 75% / 25%. If the ratio of the silane compound is 95% or more, the photocatalytic action may be insufficient, and if it is 25% or less, the adhesion and the adhesiveness to the protective layer may be insufficient, which is not preferable. As a photocatalyst, TiO₂, ZnO, SrTiO₃, CdS, GaP, InP, GaAs, BaTiO₃, K₂NbO₃, Fe₂O₃, Ta₂O₅, WO₃, SnO₂, Bi₂O₃, NiO, Cu₂O, SiC, SiO₂, MoS₂, InPb, RuO₂, CeO₂Etc. can be exemplified, and Pt, Rh, RuO can be used for these photocatalysts.₂, Nb, Cu, Sn, NiO and other known metals or metal oxides added can all be used in the present invention. The content of the photocatalyst in the surface layer containing the photocatalyst increases as the photocatalyst action increases, but in order to sufficiently adhere to the surface layer containing the photocatalyst and the protective layer, the weight is 75. It is preferably less than or equal to%.

【0036】

The method of applying the surface layer coating agent containing a photocatalyst, adhering the photocatalyst, and applying the protective layer is not particularly limited, but these photocatalyst coating agents, photocatalyst adhesion, and coating liquid for the protective layer are applied to the colored outer layer. It is preferable to use a coating method that allows uniform and uniform coating on the surface, for example, gravure coating method, micro gravure coating method, comma coating method, roll coating method, reverse roll coating method, bar coating method, kiss coating. The method, the flow coat method and the like are preferable.

【0037】

As the thermoplastic resin used for photocatalyst adhesion and formation of a protective layer of the colored sheet having excellent discoloration prevention property of the present invention, a thermoplastic resin having a stable photocatalytic action is used, for example, acrylic-silicone copolymer. Resins, acrylic-fluorine-based copolymer resins, urethane-silicone-fluorine-based copolymer resins and other copolymer-based resins, silicone-based resins and acrylic-based resin blends, fluorine-based resins and acrylic resins. A blend system or the like is used. Such a resin has high stability to a photocatalyst and can improve the adhesiveness with a colored outer layer. Further, as a thermoplastic resin that can be used for photocatalytic adhesion of a colored sheet having excellent discoloration prevention property and formation of a protective layer of the present invention, an acrylic-silicone copolymer resin can be preferably used. The thickness of the photocatalytic adhesion and protective layer is preferably 1.0 μm or more, and more preferably 1.0 to 10 μm.

【0038】

[Example]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to the scope of these examples.

【0039】

(I) Exam In the following Examples and Comparative Examples, the discoloration prevention performance of the colored sheet was evaluated by the following test method.

【0040】

(A) Outdoor exposure test A test sheet with a width of 20 cm and a length of 2 m is continuously spread by 1 m each on an exposure table installed vertically with an inclination angle of 30 degrees facing south with the surface layer forming surface containing the photocatalyst facing up. An outdoor exposure test was conducted. After 6 months, 12 months, and 18 months, the discoloration and fading state of the sheet is observed, and the degree of discoloration and fading of the surface of the sample is quantified by the color difference ΔE (JIS-Z-8729) and displayed. The discoloration and fading was evaluated. ΔE = 0 ~ 2.9: = Excellent: No discoloration and the initial state is maintained. ΔE = 3 ~ 5.9: = Good: There is some discoloration, but there is no problem in practical use. ΔE = 6 ~ 11.9: = Slightly defective: Discoloration is noticeable. ΔE = 12 ~: × = Defective: Discoloration is severe and not suitable for practical use.

【0041】

(B) Light resistance promotion test The test sheet was subjected to a light resistance acceleration test (JIS-L-0842) with a sunshine carbon weather meter for 1000 hours, 2000 hours, and 3000 hours with the photocatalyst-containing surface layer forming surface facing up, and the sample before the test was used as a reference. The degree of discoloration and fading of the surface of the test sample was quantified by the color difference ΔE (JIS-Z-8729) and displayed, and the discoloration was evaluated according to the following criteria. ΔE = 0 ~ 2.9: = Excellent: No discoloration and the initial state is maintained. ΔE = 3 ~ 5.9: = Good: There is some discoloration, but there is no problem in practical use. ΔE = 6 ~ 11.9: = Slightly defective: Discoloration is noticeable. ΔE = 12 ~: × = Defective: Discoloration is remarkable and not suitable for practical use.

【0042】

(II) Blending materials The compounding materials used in Examples and Comparative Examples are as follows, and for materials not particularly described, general-purpose materials were used as usual. (1) Vinyl chloride resin: Trademark: S-1003 (Kanegabuchi Chemical Industry Co., Ltd.) (2) DOP: Trademark: Sun Sizar DOP (New Japan Chemical Co., Ltd.) (3) Polyester adipic acid: Trademark: Adeka Sizar PN-446 (Asahi Denka Kogyo Co., Ltd.) (4) Epoxy soybean oil: Trademark: Adeka Sizar O-130P (Asahi Denka Kogyo Co., Ltd.) (5) Calcium carbonate: Trademark: Ryton BS (Bikita Powder Industry Co., Ltd.) (6) Ba-Zn stabilizer: Trademark: KV-400B (Kyodo Yakuhin Co., Ltd.) (7) UV absorber: Trademark: Biosorb 510 (Kyodo Yakuhin Co., Ltd.) (8) Inorganic pigment (I): Trademark: Titanium oxide CR: (Ishihara Sangyo Co., Ltd.) (9) Inorganic pigment (II): Trademark: Cobalt blue No.1101 (Co-Al) (Asahi Sangyo Co., Ltd.) (10) Inorganic pigment (III): Trademark: Yellow No.5100 (Pb-Sb-Ti) (Asahi Sangyo Co., Ltd.) (11) Organic Pigment (I): Trademark: HSM9142 Red (Hihiro Bitx Co., Ltd.), *) Quinacridone Red 25wt% conc masterbatch (12) Organic Pigment (II): Trademark: HSM9371 Yellow (Hihiro Bitx Co., Ltd.), *) Isoindolinone Yellow 25wt% conc Masterbatch (13) Organic Pigment (III): Trademark: HSM9611 Blue (Hihiro Bitx Co., Ltd.), *) Phthalocyanine Blue 25wt% conc Masterbatch (14) Organic Pigment (IV): Trademark: HCM1129 Red (Dainichiseika Kogyo Co., Ltd.), *) Quinacridone Red 20wt% conc Colored pellets (15) Organic Pigment (V): Trademark: HCM1434 Yellow, *) Monoazo Yellow 20wt% conc Colored Pellet (16) Organic Pigment (VI): Trademark: HCM1617 Blue, *) Phthalocyanine Blue 20wt% conc Colored pellets (17) Ethylene-vinyl acetate copolymer resin: Trademark: Evertate K-2010 (Sumitomo Chemical Co., Ltd.) (18) Ethylene-methacrylic acid copolymer resin: Trademark: Aklift WH-202 (Sumitomo Chemical Co., Ltd.) (19) Low Density Polyethylene: Trademark: J-Lex LLBF1350 (Japan Polyolefins Co., Ltd.) (20) Lubricants: Trademark: LE-5 (Kawaken Fine Chemicals Co., Ltd.) [0043]

Example 1 (1) Treatment process of textile fabric with thermoplastic resin Polyester filament plain fabric with 1000 denier warp and 1000 denier weft (thread density: 22 vertical / 2.54 cm, 25 horizontal / 2.54 cm: weight 215 g / m)²) As the base cloth, this base cloth is immersed in an organosol obtained by diluting the following paste vinyl chloride resin compounding composition with a solvent, the base cloth is impregnated with the paste vinyl chloride resin compounding composition, and then a roller is used. Aperture, 145g / m²The paste vinyl chloride resin compounding composition was evenly adhered to the entire surface of the base cloth, then dried in a heat treatment furnace at 150 ° C for 1 minute, and then heat-treated in a heat treatment furnace at 185 ° C for 1 minute to perform a paste vinyl chloride resin. The compounding composition was gelled. <Composite composition of paste vinyl chloride resin> 100 parts by weight of paste vinyl chloride resin 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 Solvent (toluene) 20 parts by weight 0.16 mm thick chloride from a straight vinyl chloride resin compound composition colored white by blending 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR) shown in Table 1. A vinyl resin composition film was produced by a calendar molding method under gel kneading conditions at 170 ° C, and this film was set at 165 ° C by a thermal laminating method on both sides of the above-mentioned paste vinyl chloride resin composition impregnated base cloth. Attached using a plastic laminator, thickness 0.5 mm, weight 550 g / m²A white colored base sheet was prepared. This white colored base sheet had a pigment-colored vinyl chloride resin outer layer on both sides thereof.

【0044】

(2) Step of forming a surface layer containing a photocatalyst (a) On one surface of the outer layer of vinyl chloride resin colored with white pigment of the colored base sheet, 15 g of a photocatalytic adhesive and protective layer forming treatment liquid having the following composition composition was applied using an 80 mesh gravure roll coater. / m²The coating was applied and dried in a heat treatment furnace at 100 ° C. for 1 minute to form a photocatalytic adhesive protective layer. <Photocatalyst adhesion, protective layer formation treatment liquid formulation> Acrylic-silicone resin with a silicone content of 3 mol% Ethanol-Ethyl Acetate Containing 8% by Weight (Solid Content) (50/50 weight ratio) 100 parts by weight of solution Methyl silicate MS51 as polysiloxane (col 20 parts by weight of 20% by weight ethanol solution of Coat Co., Ltd. 8 parts by weight γ-glycidoxypropyltrimethoxysilane (silane) Coupling agent) 1 part by weight (b) 12 g / m of a surface layer forming treatment liquid containing the following photocatalyst on the surface of this photocatalyst adhesive and protective layer using a 100 mesh gravure roll coater.²It was applied and dried in a heat treatment furnace at 100 ° C. for 1 minute to form a surface layer containing a photocatalyst, and a colored sheet having a surface layer containing a photocatalyst was prepared. <Formation of photocatalyst forming treatment liquid> Nitric acid acid oxidation corresponding to titanium oxide content of 10% by weight Water-ethanol with titanium sol dispersed (50/50) Weight ratio) 100 parts by weight of solution Nitric acid acidic siri corresponding to silicon oxide content of 10% by weight Water with Casol Dispersed-Ethanol (50/50 Weight) Ratio) 100 parts by weight of solution [0045]

(3) Exam The obtained sheet was subjected to the above-mentioned outdoor exposure test and light resistance promotion test to evaluate the effect of preventing discoloration and fading. The test results are shown in Table 1. The obtained colored sheet maintained the same hue and appearance as at the start of exposure even after 18 months of outdoor exposure, and was extremely excellent in preventing discoloration and fading.

【0046】

Base material used in Examples 2 to 8 In each of Examples 2 to 8, as in Example 1, polyester filament plain fabric with 1000 denier warp and 1000 denier weft (thread density: 22 vertical / 22.54 cm, 25 horizontal / 22.54 cm: weight). 215g / m²) As the base cloth, the same base cloth as in Example 1 was immersed in an organosol diluted with a solvent, and the base cloth was impregnated with the paste vinyl chloride resin compound composition. Squeeze with a roller, 145g / m against the base cloth²The paste vinyl chloride resin compounding composition was evenly adhered to the entire surface of the base cloth, then dried in a heat treatment furnace at 150 ° C for 1 minute, and then heat-treated in a heat treatment furnace at 185 ° C for 1 minute to perform a paste vinyl chloride resin. The compounding composition was gelled. The polyester filament plain weave cloth impregnated with this vinyl chloride resin composition was used as a base material for producing a colored sheet having excellent anti-discoloration and fading properties of the present invention.

【0047】

Example 2 Except that the amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) in the vinyl chloride resin composition used in Example 1 was increased from 10 parts by weight to 20 parts by weight, the others A white-colored sheet was prepared from the base material in the same procedure as in Example 1, and the sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The test results are shown in Table 1. The discoloration prevention property of the obtained colored sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0048】

Example 3 Using the base material, the amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) in the vinyl chloride resin composition used in Example 1 was reduced from 10 parts by weight to 5 parts by weight. However, except that 15 parts by weight of inorganic pigment (II) (blending material (9), cobalt blue No.1101) was newly added, the other parts were colored light blue by the same procedure as in Example 1. , A sheet was prepared and subjected to the outdoor exposure test and the light resistance acceleration test. The test results are shown in Table 1. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0049】

Example 4 Using the base material, the amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) in the vinyl chloride resin composition used in Example 1 was reduced from 10 parts by weight to 5 parts by weight. Then, 3 parts by weight of inorganic pigment (II) (blending material (9), cobalt blue No.1101) and 2 parts by weight of inorganic pigment (III) (blending material (10), yellow No.5100) are newly added. A colored sheet colored yellowish green was prepared in the same procedure as in Example 1 except that the above was added, and the colored sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The test results are shown in Table 1. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0050】

Example 5 Using the base material, the vinyl chloride resin composition used in Example 1 was newly added with 2 parts by weight of an inorganic pigment (II) (blending material (9), cobalt blue No. 1101) and an organic pigment. (I) Except for the addition of 1 part by weight (4 parts by weight of compounding material (11) and HSM9142 red (25 wt% conc)), the sheet colored in light reddish purple was used in the same procedure as in Example 1. It was prepared and subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 92: 8 (weight ratio)). The test results are shown in Table 1. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0051】

Example 6 Using the base material, the amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) in the vinyl chloride resin composition used in Example 1 was reduced from 10 parts by weight to 5 parts by weight. Then, 10 parts by weight of inorganic pigment (III) (blending material (10), yellow No.5100) and 1 part by weight of organic pigment (I) (blending material (11), HSM9371 yellow (25wt% conc) ), 0.5 parts by weight of organic pigment (III) (blending material (12), 2 parts by weight as HSM9611 blue (25 wt% conc)), otherwise the same as in Example 1. A sheet colored in olive color was prepared by the procedure and subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 86: 14 (weight ratio)). The test results are shown in Table 1. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0052】

Example 7 Using the base material, 2 parts by weight of an inorganic pigment (II) (blending material (9), cobalt blue No. 1101) and an organic pigment were newly added to the vinyl chloride resin composition used in Example 1. Except for the addition of 3 parts by weight of pigment (I) (blending material (11), 12 parts by weight as HSM9142 red (25 wt% conc)), the sheet colored reddish purple by the same procedure as in Example 1 was used. It was prepared and subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 80:20 (weight ratio)). The test results are shown in Table 1. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0053】

Example 8 Using the base material, the amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) in the vinyl chloride resin composition used in Example 1 was reduced from 10 parts by weight to 5 parts by weight. Then, 10 parts by weight of inorganic pigment (III) (blending material (10), yellow No.5100) and 2 parts by weight of organic pigment (I) (blending material (11), HS9142 red (25wt% conc) ) As 8 parts by weight), Organic pigment (II) 2 parts by weight (blending material (12), HSM9371 yellow (25wt% conc) as 8 parts by weight), Organic pigment (III) 2 parts by weight (blending material (13) ), 8 parts by weight) as HSM9611 blue (25 wt% conc)), and other than that, a sheet colored in olive color was prepared by the same procedure as in Example 1, and this was subjected to the outdoor exposure test and light resistance. Used for accelerated test (* Inorganic pigment: Organic pigment = 71:29 (weight ratio)). The test results are shown in Table 1. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0054】

Examples 9-12 In each of Examples 9 to 12, a polyester filament plain woven fabric with 1000 denier warp threads and 1000 denier weft threads (thread density: 22 vertical threads / 2.54 cm, 25 horizontal threads / 2.54 cm: grain weight 215 g / m).²) As the base cloth, and the following paste vinyl chloride resin compounding composition (the type and amount of the pigment were changed as described below) was immersed in an organosol diluted with a solvent, and the paste vinyl chloride resin compounded. After impregnating the base cloth with the composition, squeeze it with a roller and 145 g / m with respect to the base cloth.²The vinyl chloride resin-blended composition was evenly adhered to the entire surface of the base cloth, dried in a heat treatment furnace at 150 ° C for 1 minute, and then heat-treated in a heat treatment furnace at 185 ° C for 1 minute to obtain pigment-colored paste chloride. The vinyl resin-blended composition was gelled. Next, the same paste vinyl chloride resin compound composition organosol as above was used on the polyester filament plain woven fabric to which the paste vinyl chloride resin compound composition was gelled and adhered, and this time, the single-sided adhesion weight was 85 g / m.²The set knife coating treatment was applied to both sides, dried in a heat treatment furnace at 150 ° C for 1 minute, and then heat-treated in a heat treatment furnace at 185 ° C for 1 minute to gel a pigment-colored paste vinyl chloride resin compounding composition. 0.5mm thick, 530g / m weight²The base material layer of was prepared. This colored base material layer had a pigment-colored vinyl chloride resin outer layer on both sides thereof, as in Examples 9 to 12, respectively.

【0055】

<Paste vinyl chloride resin compounding composition> 100 parts by weight of paste vinyl chloride resin 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 Pigment (Vinyl Toner) X parts by weight (as described below) Solvent (toluene) 20 parts by weight [0056]

On one side of the base material layer having the pigment-colored vinyl chloride resin composition outer layer, a photocatalytic adhesive and protective layer forming treatment liquid having the same composition as in Example 1 was applied in the same procedure as in Example 1. A surface containing the photocatalyst is formed, and then a surface layer forming treatment liquid containing the same photocatalyst as in Example 1 is applied and formed on the surface of the photocatalyst adhesive and protective layer in the same procedure as in Example 1. A layer was formed to prepare a colored sheet (excellent in preventing discoloration and fading).

【0057】

However, in Example 9, as the pigment (vinyl toner) in the paste vinyl chloride resin composition, 15 parts by weight of the vinyl toner having the following composition was added, and the obtained colored vinyl chloride resin compound composition organosol was used. .. Titanium oxide (rutile) (inorganic pigment) 30 parts by weight Yellow iron oxide (inorganic pigment) 15 parts by weight Carbon black (inorganic pigment) 2 parts by weight Bengara (inorganic pigment) 2 parts by weight Cyanine Green (organic pigment) 1 part by weight DOP (Plasticizer) 48 parts by weight Dispersant 2 parts by weight (* Inorganic pigment: Organic pigment = 99: 1 (weight ratio)) The obtained olive drab-colored sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The discoloration and fading resistance of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained, and the discoloration and fading after 3000 hours of the light resistance promotion test were maintained. The color difference ΔE, which is the criterion for determining the preventability, was 2.8.

【0058】

In Example 10, as a pigment (vinyl toner) in the paste vinyl chloride resin composition, 15 parts by weight of a vinyl toner having the following composition was added, and the obtained colored vinyl chloride resin compound composition organosol was used. Yellow iron oxide (inorganic pigment) 50 parts by weight Polyazo red (organic pigment) 2 parts by weight Cyanine Blue (organic pigment) 3 parts by weight DOP (Plasticizer) 43 parts by weight Dispersant 2 parts by weight (* Inorganic pigment: Organic pigment = 91: 9 (weight ratio)) The obtained gray-colored sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The discoloration and fading resistance of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained, and the discoloration and fading after 3000 hours of the light resistance promotion test were maintained. The value of the color difference ΔE, which is the criterion for determining the preventability, was 3.1.

【0059】

In Example 11, as the pigment (vinyl toner) in the paste vinyl chloride resin composition, 15 parts by weight of the vinyl toner having the following composition was added, and the obtained colored vinyl chloride resin compound composition organosol was used. Titanium oxide (rutile) (inorganic pigment) 30 parts by weight Yellow iron oxide (inorganic pigment) 15 parts by weight Carbon black (inorganic pigment) 7 parts by weight Cyanine Green (organic pigment) 8 parts by weight (* Inorganic pigment: Organic pigment = 87:13 (weight ratio)) The obtained dark green color sheet was subjected to the outdoor exposure test and the light resistance promotion test. The discoloration and fading resistance of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained, and the discoloration and fading after 3000 hours of the light resistance promotion test were maintained. The color difference ΔE, which is the criterion for determining the preventability, was 3.4.

【0060】

In Example 12, as the pigment (vinyl toner) in the paste vinyl chloride resin composition, 15 parts by weight of the vinyl toner having the following composition was added, and the obtained colored vinyl chloride resin compound composition organosol was used. Titanium oxide (rutile) (inorganic pigment) 40 parts by weight Yellow iron oxide (inorganic pigment) 3 parts by weight Isoindrinone Yellow (organic pigment) 13 parts by weight Polyazo red (organic pigment) 1 part by weight DOP (Plasticizer) 41 parts by weight Dispersant 2 parts by weight (* Inorganic pigment: Organic pigment = 76:24 (weight ratio)) The obtained orange sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The discoloration and fading resistance of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained, and the discoloration and fading after 3000 hours of the light resistance promotion test were maintained. The color difference ΔE, which is the criterion for determining the preventability, was 4.4.

【0061】

Example 13 (1) Treatment process of textile fabric with thermoplastic resin Polyester filament plain fabric with 1000 denier warp and 1000 denier weft (thread density: 22 vertical / 2.54 cm, 25 horizontal / 2.54 cm: weight 215 g / m)²) As the base cloth, this base cloth is dipped in the following ethylene-vinyl acetate copolymer resin-based olefin resin emulsion composition, the base cloth is impregnated with this olefin resin emulsion composition, and then a roller. Squeeze with, 95g / m for the base cloth²The olefin resin emulsion composition of No. 1 was evenly adhered to the entire surface of the base cloth, 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 obtain the olefin resin composition. I fixed the object.

【0062】

<Olefin resin emulsion compounding composition> Ethylene-vinyl acetate copolymer resin emulsion 100 parts by weight Calcium carbonate 10 parts by weight * Ethylene-vinyl acetate copolymer resin emulsion = Trademark: Aquatex EC -1700 (resin solid content 50% by weight: Chuo Rika Kogyo Co., Ltd.) [0063]

Next, a 0.16 mm thick film made of an ethylene-vinyl acetate copolymer resin composition containing 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR) shown in Table 2 was formed on a calendar. It was produced under melt-kneading conditions of 140 ° C by a molding method, and the above-mentioned ethylene-vinyl acetate copolymer resin emulsion composition was impregnated and fixed to this film, and set to 150 ° C by a thermal laminating method on both sides of the base cloth. Attached using a plastic laminator, thickness 0.5 mm, weight 480 g / m²A base material layer having an outer layer of a thermoplastic resin composition made of an ethylene-vinyl acetate copolymer resin colored in white was prepared.

【0064】

(2) Step of forming a surface layer containing a photocatalyst (a) 80 mesh gravure of a photocatalytic adhesive and protective layer forming treatment liquid having the following composition composition on one surface of a base material layer having an outer layer of a thermoplastic resin composition made of the above-mentioned colored ethylene-vinyl acetate copolymer resin. 15g / m with roll coater²The coating was applied and dried in a heat treatment furnace at 100 ° C. for 1 minute to bond with a photocatalyst and form a protective layer. <Photocatalyst adhesion, protective layer formation treatment liquid formulation> Acrylic-silicone resin with a silicone content of 3 mol% Ethanol-Ethyl Acetate Containing 8% by Weight (Solid Content) (50/50 weight ratio) 100 parts by weight of solution Methyl silicate MS51 as polysiloxane (col 20 parts by weight of 20% by weight ethanol solution of Coat Co., Ltd. 8 parts by weight γ-glycidoxypropyltrimethoxysilane (silane) Coupling agent) 1 part by weight [0065]

(b) 12 g / m of a surface layer forming treatment liquid containing the following photocatalyst on the surface of the photocatalyst and protective layer using a 100 mesh gravure roll coater.²Was applied and dried in a heat treatment furnace at 100 ° C. for 1 minute to form a surface layer containing a photocatalyst to prepare a colored sheet (excellent in preventing discoloration and fading). <Formation of photocatalyst forming treatment liquid> Nitric acid acid oxidation corresponding to titanium oxide content of 10% by weight Water-ethanol with titanium sol dispersed (50/50) Weight ratio) 100 parts by weight of solution Nitric acid acidic siri corresponding to silicon oxide content of 10% by weight Water with Casol Dispersed-Ethanol (50/50 Weight) Ratio) 100 parts by weight of solution [0066]

The obtained colored sheet was subjected to the outdoor exposure test and the light resistance promotion test. The test results are shown in Table 2. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0067】

Example 14 In the ethylene-vinyl acetate copolymer resin composition used in Example 13, the blending amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) was reduced from 10 parts by weight to 5 parts by weight. Except for the addition of 10 parts by weight of the inorganic pigment (II) (blending material (9), cobalt blue No. 1101), a light blue colored sheet was prepared in the same procedure as in Example 13. , This was subjected to the outdoor exposure test and the light resistance promotion test. The test results are shown in Table 2. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0068】

Example 15 In the ethylene-vinyl acetate copolymer resin composition used in Example 13, 100 parts by weight of the ethylene-vinyl acetate copolymer resin (blending material (17)) was added to the ethylene-methacrylic acid copolymer resin (blending material (18)). ) Replaced with 100 parts by weight, and made cream-colored by the same procedure as in Example 13 except that 5 parts by weight of inorganic pigment (III) (blending material (10), yellow No. 5100) was added. A colored sheet was prepared and subjected to the outdoor exposure test and the light resistance acceleration test. The test results are shown in Table 2. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0069】

Example 16 50 parts by weight of 100 parts by weight of the ethylene-vinyl acetate copolymer resin (blending material (17)) in the ethylene-vinyl acetate copolymer resin composition used in Example 13 is made of an ethylene-methacrylic acid copolymer resin. (Mixed material (18)) Replaced with 50 parts by weight, and added 5 parts by weight of inorganic pigment (III) (blended material (10), yellow No. 5100), otherwise the same as in Example 13. A cream-colored sheet was prepared according to the above procedure, and the sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The test results are shown in Table 2. The discoloration prevention property of the obtained sheet was extremely good, and even after 18 months of outdoor exposure, the appearance and hue similar to those at the start of exposure were maintained.

【0070】

Example 17 The amount of the inorganic pigment (I) (blending material (8)) in the ethylene-vinyl acetate copolymer resin composition used in Example 13 was reduced from 10 parts by weight to 2 parts by weight, and a new inorganic pigment was added. Pigment (II) (blending material (9), cobalt blue No.1101) 10 parts by weight and organic pigment (IV) 1 part by weight (blending material (10), HCM1129 red (20 wt% concentration) 5 parts by weight) Except for the addition of, a bluish-purple colored sheet was prepared in the same procedure as in Example 13 and subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment). = 92: 8 (weight ratio). The test results are shown in Table 2. The obtained sheet has extremely good anti-discoloration and fading properties, and even after 18 months of outdoor exposure, the appearance and hue are the same as those at the start of exposure. I was keeping it.

【0071】

Example 18 The blending amount of the inorganic pigment (I) (blending material (8)) in the ethylene-vinyl acetate copolymer resin composition used in Example 13 was reduced from 10 parts by weight to 5 parts by weight, and a new inorganic pigment was added. Pigment (III) (blending material (10), yellow No.5100) 10 parts by weight and organic pigment (IV) 1 part by weight (blending material (14), HCM1129 red (20wt% conc) 5 parts by weight), Organic pigment (V) 1 part by weight (blending material (15), HCM1434 yellow (20wt% conc) 5 parts by weight), organic pigment (VI) 0.5 part by weight (blending material (16), HCM1617 blue (20wt%) Except for the addition of 2.5 parts by weight) as the concentration), an olive-colored sheet was prepared in the same procedure as in Example 13 and subjected to the outdoor exposure test and the light resistance acceleration test (*). Inorganic pigment: Organic pigment = 86: 14 (weight ratio). The test results are shown in Table 2. The discoloration prevention property of the obtained sheet is extremely good, and even after 18 months of outdoor exposure, at the start of exposure. It maintained the same appearance and hue as.

【0072】

Example 19 The amount of the inorganic pigment (I) (blending material (8)) in the ethylene-vinyl acetate copolymer resin composition used in Example 13 was reduced from 10 parts by weight to 2 parts by weight, and a new inorganic pigment was added. Pigment (II) (blending material (9), cobalt blue No.1101) 10 parts by weight and organic pigment (IV) 3 parts by weight (blending material (14), HCM1129 red (20 wt% concentration) 15 parts by weight) Except for the addition of, a bluish-purple colored sheet was prepared in the same procedure as in Example 13 and subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment). = 80: 20 (weight ratio). The test results are shown in Table 2. The obtained sheet has extremely good anti-discoloration and fading properties, and even after 18 months of outdoor exposure, the appearance and hue are the same as those at the start of exposure. I was keeping it.

【0073】

Example 20 The blending amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) in the ethylene-vinyl acetate copolymer resin composition used in Example 13 was reduced from 10 parts by weight to 5 parts by weight, and newly added. In addition, 10 parts by weight of inorganic pigment (III) (blending material (11), yellow No.5100) and 2 parts by weight of organic pigment (IV) (blending material (14), HCM1129 red (20 wt% concentration)) By weight, 2 parts by weight of organic pigment (V) (blending material (15), 10 parts by weight as HCM1434 yellow (20wt% concentration)), 2 parts by weight of organic pigment (VI) (blending material (16), HCM1617 blue) Except for the addition of (10 parts by weight) as (20 wt% concentration), an olive-colored sheet was prepared in the same procedure as in Example 13 except that the sheet was subjected to the outdoor exposure test and the light resistance acceleration test. (* Inorganic pigment: Organic pigment = 71:29 (weight ratio). The test results are shown in Table 2. The obtained sheet has extremely good anti-discoloration and fading properties, and even after 18 months of outdoor exposure, It maintained the same appearance and hue as at the start of exposure.

【0074】

Comparative Examples 1 to 6 In each of Comparative Examples 1 to 6, a polyester filament plain woven fabric having 1000 denier warp threads and 1000 denier weft threads (thread density: 22 vertical threads / 2.54 cm, 25 horizontal threads / 2.54 cm: weight) is the same as in Example 1. 215g / m²) As the base cloth, the paste vinyl chloride resin composition of Example 1 is immersed in an organosol diluted with a solvent, and the base cloth is impregnated with the paste vinyl chloride resin compounding composition, and then the base cloth is impregnated. Squeeze with a roller, 145g / m against the base cloth²The paste vinyl chloride resin compounding composition of No. 1 was evenly adhered to the entire surface of the base cloth, dried in a heat treatment furnace at 150 ° C for 1 minute, and then heat-treated in a heat treatment furnace at 185 ° C for 1 minute. The compounding composition was gelled. The obtained vinyl chloride resin composition-impregnated polyester filament plain woven fabric was used as a base material. Next, a vinyl chloride resin composition film having a thickness of 0.16 mm composed of straight vinyl chloride resin compositions (Comparative Examples 1 to 6) prepared by the method described below and having the compositions shown in Table 3 was formed by a calendar molding method 170. It was prepared under gelling kneading conditions at ° C, and this film was attached to both sides of the above-mentioned vinyl chloride resin composition-impregnated plain fabric (base material) using a laminator set at 165 ° C by the thermal laminating method. , Thickness 0.5mm, weight 550g / m²A sheet having the colored vinyl chloride resin film as an outer layer was prepared.

【0075】

In Comparative Example 1, in the vinyl chloride resin composition film used in Example 1, the addition of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR) was omitted, and instead, it was organic. A colored sheet was prepared in the same procedure as in Example 1 except that 4 parts by weight of the system pigment (I) (blending material (14) and 16 parts by weight as HSM9142 red (25 wt% concentration)) was used. This was subjected to the outdoor exposure test and the light resistance promotion test. The test results are shown in Table 3. In the obtained colored sheet, the discoloration and fading of the organic pigment became remarkable 12 months after the outdoor exposure, and the red color faded after 18 months. The color difference ΔE after 3000 hours of the light resistance acceleration test was 21.3. It was confirmed that the sheet of Comparative Example 1 is not suitable for long-term outdoor use as a awning tent sheet or a medium-sized or large-sized tent sheet.

【0076】

In Comparative Example 2, in the vinyl chloride resin composition film used in Example 1, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the organic pigment (II) was used. Except for the fact that 4 parts by weight (blending material (12), 16 parts by weight as HSM9371 yellow (25 wt% concentration)) was used, a sheet was prepared in the same procedure as in Example 1, and this was subjected to the outdoor exposure test. , And the light resistance promotion test. The test results are shown in Table 3. In the obtained colored sheet, the discoloration and fading of the organic pigment began to be noticeable 12 months after the outdoor exposure, and the yellow color faded 18 months later. The color difference ΔE after 3000 hours of the light resistance acceleration test was 16.6. The sheet of Comparative Example 2 was unsuitable for long-term outdoor use as a awning tent sheet or a medium- or large-sized tent sheet.

【0077】

In Comparative Example 3, in the vinyl chloride resin composition film used in Example 1, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the organic pigment (II) was used. 2 parts by weight (blending material (12), 8 parts by weight as HSM9371 yellow (25wt% concentration)) and 2 parts by weight of organic pigment (III) (blending material (13), 8 parts by weight as HSM9611 blue (25wt% concentration)) A sheet was prepared in the same procedure as in Example 1 except that the part) was used, and the sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The test results are shown in Table 3. In the obtained sheet, the discoloration and fading of the organic pigment began to be noticeable 12 months after the outdoor exposure, and the yellowish green color faded after 18 months. The color difference ΔE after 3000 hours of the light resistance acceleration test was 19.7. The colored sheet of Comparative Example 3 was unsuitable for long-term outdoor use as a awning tent sheet or a medium-sized or large-sized tent sheet.

【0078】

In Comparative Example 4, in the vinyl chloride resin composition film used in Example 1, the blending amount of the inorganic pigment (I) (blending material (8), titanium oxide CR) was reduced from 10 parts by weight to 5 parts by weight. However, except that 3 parts by weight of the organic pigment (I) (12 parts by weight as compounding material (11), HSM9142 red) (25 wt% concentration) was added, the sheet was formed in the same procedure as in Example 1. Was used for the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 63: 37 (weight ratio)). The test results are shown in Table 3. In the obtained sheet, the discoloration and fading of the organic pigment was not noticeable until 6 months after the outdoor exposure, but the pink color faded 18 months after the outdoor exposure. The color difference ΔE after 3000 hours of the light resistance acceleration test was 12.4. The colored sheet of Comparative Example 4 was not a material that could be used outdoors for a long period of time as a awning tent sheet or a medium-sized or large-sized tent sheet.

【0079】

In Comparative Example 5, in the vinyl chloride resin composition film used in Example 1, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the inorganic pigment (II) was used. (Compounding material (9), cobalt blue No.1101) 5 parts by weight, organic pigment (II) 3 parts by weight (blending material (12), HSM9371 yellow (25wt% concentration) 12 parts by weight), organic Except for the use of pigment (III) (blending material (12), 8 parts by weight as HSM9611 blue (25 wt% concentration)), a sheet was prepared in the same procedure as in Example 1 except that the sheet was exposed to the outdoors. It was used for the test and the light resistance acceleration test (* Inorganic pigment: Organic pigment = 50:50 (weight ratio)). The test results are shown in Table 3. In the obtained sheet, the discoloration and fading of the organic pigment was not noticeable until 6 months after the outdoor exposure, but the yellowish green color faded 18 months after the outdoor exposure, and the light resistance promotion test 3000 The color difference ΔE after time was 15.3. The colored sheet of Comparative Example 5 was not a material that could be used outdoors for a long period of time as a awning tent sheet or a medium-sized or large-sized tent sheet.

【0080】

In Comparative Example 6, in the vinyl chloride resin composition film used in Example 1, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the inorganic pigment (III) was used. 3 parts by weight of (blending material (10), yellow No. 5100), 5 parts by weight of organic pigment (I) (blending material (11), HSM9142 red (20 parts by weight as 25 wt% concentration), and organic A sheet was prepared in the same procedure as in Example 1 except that 5 parts by weight of pigment (II) (blending material (12), 20 parts by weight as HSM9371 yellow (25 wt% concentration)) was used. It was subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 23: 77 (weight ratio)). The test results are shown in Table 3. The obtained sheet is 6 months after outdoor exposure. Until then, the discoloration and fading of the organic pigment was not noticeable, but the olive color faded 18 months after outdoor exposure, and the color difference ΔE after 3000 hours of the light resistance acceleration test was 20.4. The colored sheet of Comparative Example 6 was not a material that could be used outdoors for a long period of time as a sunshade tent sheet or a medium- or large-sized tent sheet.

【0081】

Comparative Examples 7 to 12 In each of Comparative Examples 7 to 12, a polyester filament plain woven fabric having 1000 denier warp yarns and 1000 denier weft yarns (yarn density: 22 vertical yarns / 2.54 cm, 25 horizontal yarns /), as in Example 1. 2.54cm: Eye weight 215g / m²) As the base cloth, and this base cloth is immersed in the same olefin resin composition processing liquid as the ethylene-vinyl acetate copolymer resin-based olefin resin emulsion composition of Example 1 to form an olefin resin emulsion composition. After impregnating the base cloth with an object, squeeze it with a roller and apply 95 g / m to the base cloth.²The olefin-based resin emulsion composition of No. 1 was evenly adhered to the entire surface of the base cloth, 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. An object was fixed to prepare a base material. Next, a 0.16 mm thick film prepared by the method described below and composed of an ethylene-vinyl acetate copolymer resin composition having the composition shown in Table 4 was subjected to melt-kneading conditions at 140 ° C. by a calendar molding method. This film was prepared and attached to both sides of the above-mentioned base material 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.²A base material layer having a colored thermoplastic resin composition outer layer made of an ethylene-vinyl acetate copolymer resin was prepared. A photocatalyst-adhering and protective layer forming treatment liquid having the same composition as in Example 1 was applied and dried on one surface of this base material layer in the same procedure as in Example 1 to form a photocatalyst-adhering and protective layer. A surface layer forming treatment liquid containing the same photocatalyst as in Example 1 was applied to the surface of the photocatalyst-bonded and protective layer in the same procedure as in Example 1 to form a surface layer containing a photocatalyst and colored. A colored sheet having an outer layer of the thermoplastic resin composition was prepared.

【0082】

In Comparative Example 7, in the ethylene-vinyl acetate copolymer resin composition film used in Example 13, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the organic pigment was used. A colored sheet was prepared in the same procedure as in Example 13 except that 4 parts by weight of the pigment (IV) (blending material (14), 20 parts by weight as HCM1129 red (20 wt% concentration)) was used. Was subjected to the outdoor exposure test and the light resistance promotion test. The test results are shown in Table 4. In the obtained sheet, the discoloration and fading of the organic pigment began to be noticeable 12 months after outdoor exposure, the red color faded after 18 months, and the color difference ΔE after 3000 hours of the light resistance promotion test was 25.1. It was. The colored sheet of Comparative Example 7 was not a material that could be used outdoors for a long period of time as a awning tent sheet or a medium-sized or large-sized tent sheet.

【0083】

In Comparative Example 8, in the ethylene-vinyl acetate copolymer resin composition film used in Example 13, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the organic pigment was used. A sheet was prepared in the same procedure as in Example 13 except that 4 parts by weight of pigment (IV) (blending material (15), 20 parts by weight as HCM1434 yellow (20 wt% concentration)) was used. It was subjected to the outdoor exposure test and the light resistance promotion test. The test results are shown in Table 4. In the obtained sheet, discoloration and fading of organic pigments began to be noticeable 12 months after outdoor exposure, yellow color faded after 18 months, and the color difference ΔE after 3000 hours of the light resistance promotion test was 19.8. It was. The colored sheet of Comparative Example 8 was not a material that could be used outdoors for a long period of time as a awning tent sheet or a medium-sized or large-sized tent sheet.

【0084】

In Comparative Example 9, in the ethylene-vinyl acetate copolymer resin composition film used in Example 13, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the organic pigment was used. Pigment (v) 2 parts by weight (blending material (15), HCM1434 yellow (20wt% concentration) 10 parts by weight) and organic pigment (VI) 2 parts by weight (blending material (16), HCM1617 blue (20wt% concentration) A sheet was prepared in the same procedure as in Example 13 except that 10 parts by weight) was used as the), and the sheet was subjected to the outdoor exposure test and the light resistance acceleration test. The test results are shown in Table 4. In the obtained sheet, discoloration and fading of organic pigments began to be noticeable 12 months after outdoor exposure, yellowish green color faded after 18 months, and the color difference ΔE after 3000 hours of the light resistance promotion test was 23.5. there were. The colored sheet of Comparative Example 9 was not a material that could be used outdoors for a long period of time as a awning tent sheet or a medium- or large-sized tent sheet.

【0085】

In Comparative Example 10, in the ethylene-vinyl acetate copolymer resin composition film used in Example 13, 100 parts by weight of the ethylene-vinyl acetate copolymer resin (blending material (17)) was subjected to ethylene-methacrylic acid copolymerization. Replaced with 100 parts by weight of resin (blending material (18)), and further reduced the blending amount of inorganic pigment (I) (blending material (8), titanium oxide CR) from 10 parts by weight to 5 parts by weight to make it organic. A sheet was prepared in the same procedure as in Example 13 except that 3 parts by weight of the system pigment (IV) (blending material (14) and 15 parts by weight as HCM1129 red (20 wt% concentration)) was added. Was subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 63: 37 (weight ratio)). The test results are shown in Table 4. In the obtained sheet, the discoloration and fading of the organic pigment was not noticeable until 6 months after outdoor exposure, but the pink color faded 18 months after outdoor exposure, and the light resistance promotion test 3000 The color difference ΔE after time was 11.9. The colored sheet of Comparative Example 10 was not a material that could be used outdoors for a long period of time as a awning tent sheet or a medium- or large-sized tent sheet.

【0086】

In Comparative Example 11, in the ethylene-vinyl acetate resin composition film used in Example 13, 50 parts by weight of the ethylene-vinyl acetate copolymer resin was replaced with 50 parts by weight of the ultra-low density polyethylene resin. Furthermore, instead of 10 parts by weight of inorganic pigment (I) (blending material (8), titanium oxide CR), 5 parts by weight of inorganic pigment (II) (blending material (9), cobalt blue No.1101) As organic pigment (V) 3 parts by weight (blending material 15), HCM1434 yellow (20 wt% concentration) as 15 parts by weight) and organic pigment (VI) (blended material (16), HCM1617 blue (20 wt% concentration) A sheet was prepared in the same procedure as in Example 13 except that 10 was used, and the sheet was subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 50:). 50 (weight ratio)). The test results are shown in Table 4. The obtained sheet showed inconspicuous discoloration and fading of organic pigments until 6 months after outdoor exposure, but 18 months after outdoor exposure. The yellowish green color faded, and the color difference ΔE after 3000 hours of the light resistance acceleration test was 15.3. The colored sheet of Comparative Example 4 is used outdoors for a long period of time as a sunshade tent sheet or a medium-sized tent sheet. It was not something that could be used for any purpose.

【0087】

In Comparative Example 12, in the ethylene-vinyl acetate copolymer resin composition film used in Example 13, instead of 10 parts by weight of the inorganic pigment (I) (blending material (8), titanium oxide CR), the inorganic pigment was used. Pigment (III) (blending material (10), yellow No. 5100) 3 parts by weight, organic pigment (IV) 5 parts by weight (blending material 14), HCM1129 red (20 wt% concentration) 25 parts by weight) A sheet was prepared in the same procedure as in Example 13 except that 5 parts by weight of the organic pigment (V) (blending material (15) and 25 parts by weight as HCM1434 yellow (20 wt% concentration)) was used. This was subjected to the outdoor exposure test and the light resistance acceleration test (* inorganic pigment: organic pigment = 23:77 (weight ratio)). The test results are shown in Table 4. In the obtained sheet, the discoloration and fading of the organic pigment was not noticeable until 6 months after outdoor exposure, but the olive color faded 18 months after outdoor exposure, and the light resistance promotion test 3000 The color difference ΔE after time was 24.4. The colored sheet of Comparative Example 12 was not a material that could be used outdoors for a long period of time as a awning tent sheet or a medium-sized or large-sized tent sheet.

【0088】

[table 1]

<img file="JP2001105535A_D0001.tif" />【0089】

[Table 2]

<img file="JP2001105535A_D0002.tif" />【0090】

[Table 3]

<img file="JP2001105535A_D0003.tif" />【0091】

[Table 4]

<img file="JP2001105535A_D0004.tif" />【0092】

[Effect of the invention]

The colored sheet having excellent anti-fading property according to the present invention is used as a colorant for a thermoplastic resin, in particular, an inorganic pigment is selected and used, or an inorganic pigment and an organic pigment are used in a specific ratio. As a result, it is possible to solve the drawback that the colorant is decomposed and deteriorated by the redox action of the photocatalyst, and as a result, the hue and appearance of the product are changed. Therefore, the present invention is extremely useful, and the colored sheet having excellent anti-discoloration and fading properties of the present invention is used as a sheet for industrial materials, especially for applications requiring colorful hue and abundant color variations. For example, it can be suitably used for applications such as awning tents and medium and large tents.