JP2003182001A - Anti-staining waterproof sheet excellent in rain streak anti-staining effect - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-staining waterproof sheet excellent in anti-staining properties, especially rain streak anti-staining effect though the sheet has a polyvinyl chloride resin-containing waterproof resin layer. <P>SOLUTION: The polyvinyl chloride resin-containing waterproof resin layer is formed on at least one surface of base cloth and an anti-staining layer containing a fluoroplastic and silica fine particles is formed thereon and, if necessary, an additive transfer preventing layer is formed (on a surface side and/or a back surface side) and/or an adhesive layer is formed between the waterproof resin layer and the anti-staining layer or the additive transfer preventing layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling waterproof sheet having an excellent effect of preventing rain streak stains. More specifically, the present invention is extremely useful for industrial material applications such as medium and large-sized tents, tent warehouses, eaves tents, truck hoods, and backlit signboards, and has an excellent rain line stain prevention effect. The present invention relates to a dirty waterproof sheet.

[0002]

2. Description of the Related Art Conventionally, as sheets used for industrial materials such as medium and large tents, tent warehouses, eaves tents, hoods for trucks and backlits for signboards, for example,
BACKGROUND ART One in which a waterproof resin layer made of synthetic rubber or synthetic resin is laminated on one side or both sides of a fibrous base cloth is widely used. In particular, the one using a polyvinyl chloride resin as the waterproof resin layer has a good balance of processability, economic efficiency, flameproofness, flexibility and the like, and is the most popular. Such a conventional seat is
Most of the time, it is used outdoors, but as the usage period increases, the surface of the sheet may be polluted by smoke and soot emitted from factories and automobiles, pollen, sap, or bird and insect feces. It has been pointed out that it is contaminated and impairs the initial aesthetics. In particular, a sheet with a polyvinyl chloride resin as a waterproof resin layer contains a large amount of plasticizers, stabilizers, etc. in the composition, so even if the composition is carefully examined, if it is used outdoors for a long time, The resin is gradually decomposed due to the influence of ultraviolet rays and rain (acid rain), and the plasticizer migrates to the surface to gradually make the surface sticky, so dust and dirt easily adhere and the sheet surface becomes dirty. There are drawbacks. In a membrane structure such as a tent warehouse constructed by using such a sheet, a part of the dirt attached to the ceiling sheet flows down to the side sheet due to rainfall, and the streak-like remarkable dirt ( (Rain streaks stains) occur. In applications such as medium- and large-sized tents and tent warehouses where the spread area is extremely large, it is difficult to clean even if the pollution becomes severe. Or, you have to switch to a new sheet within a short period of time. Therefore, in the industry, there is a demand for the development of a sheet in which the surface of the sheet does not easily become dirty over a long period of time.

As a method for improving the antifouling property, for example, a method of coating the surface of a polyvinyl chloride resin with an acrylic resin solution dissolved in an organic solvent and drying it is generally used. The effect is not sufficient because the plasticizer in the polyvinyl chloride resin dissolves in the solvent and the liquid plasticizer and liquid stabilizer compounded in the polyvinyl chloride resin migrate to the coating resin layer. The method of coating fluorine-containing resin on the surface instead of acrylic resin is more effective in suppressing migration of plasticizers compared to the case of coating acrylic resin, and also has a high barrier property against ultraviolet rays and rain. However, since its surface is lipophilic and hydrophobic, it is easily contaminated by pollutants containing organic components such as oil, and its antifouling property, particularly rain line antifouling property is not sufficient.

[0004]

The object of the present invention is to solve the above-mentioned problems, that is, an antifouling sheet which is excellent in antifouling property of a sheet having a waterproof resin layer containing a polyvinyl chloride resin, particularly excellent in rain streak antifouling property. To provide.

[0005]

Means for Solving the Problems As a result of diligent studies on the above problems, the present inventors have found that in a sheet having a polyvinyl chloride resin layer, silica fine particles are contained in an antifouling layer containing a fluorine-containing resin. The present inventors have found that the compounding of the composition significantly improves the rain line stain prevention property, and have completed the present invention.

The antifouling waterproof sheet of the present invention, which is excellent in the effect of preventing rain stains, has a base cloth containing at least one layer of fiber cloth and a polyvinyl chloride resin formed on at least one surface of the base cloth. A waterproof resin layer containing, and an antifouling layer containing a resin component containing a fluorine-containing resin and a dispersed particle component containing silica fine particles is further formed on at least one layer of the waterproof resin layer. It is a feature. In the antifouling waterproof sheet of the present invention which is excellent in the rain line stain prevention effect, it is preferable that the resin component in the antifouling layer further contains at least one acrylic resin together with the fluorine-containing resin. In the antifouling waterproof sheet having excellent rain line stain prevention effect of the present invention, the content of the fluorine-containing resin in the resin component of the antifouling layer is 30% by mass or more based on the total mass of the resin components. It is preferable. The antifouling waterproof sheet excellent in the rain line stain prevention effect of the present invention further comprises an adhesive layer and / or an additive migration prevention layer formed between the waterproof resin layer and the antifouling layer. Is preferred. In the antifouling waterproof sheet having excellent rain line stain prevention effect of the present invention, the adhesive layer comprises at least one selected from acrylic resin, polyurethane resin, and cyanoethylated ethylene-vinyl alcohol copolymer resin. It is preferable to include. In the antifouling waterproof sheet of the present invention which is excellent in the effect of preventing rain streaks, it is preferable that an additive migration preventing layer is formed on the outermost back surface of the antifouling waterproof sheet. In the antifouling waterproof sheet excellent in the rain line stain prevention effect of the present invention, the additive migration prevention layer,
It is preferable to include at least one selected from fluorine-containing resin, acrylic resin, polyurethane resin, and cyanoethylated ethylene-vinyl alcohol copolymer resin. The antifouling waterproof sheet of the present invention, which has an excellent effect of preventing rain streak stains, may be a roll-up body.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION An antifouling waterproof sheet of the present invention which is excellent in the effect of preventing stains on rain lines (hereinafter referred to as an antifouling sheet).
The fiber cloth used for the base fabric is a natural fiber such as cotton or hemp, an inorganic fiber such as glass fiber, carbon fiber,
Regenerated fibers such as metal fibers, such as viscose rayon,
Cupra and the like, semi-synthetic fibers, such as di- and triacetate fibers, and synthetic fibers, such as nylon 6,
Nylon 66, polyester (polyethylene terephthalate, etc.) fiber, polylactic acid fiber, aromatic polyamide fiber,
It is composed of at least one selected from acrylic fiber, polyolefin fiber, polyvinyl chloride fiber, and the like.

The fibers forming the fiber cloth in the base cloth may be any shape such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn and the like. The structure of the fiber cloth for the base cloth may be a woven fabric, a knitted fabric, a non-woven fabric, or a composite thereof. There is no particular limitation on the knitting or weaving structure of the fiber cloth for the base cloth, for example, at least a coarse knitted woven fabric composed of yarns including warps and wefts arranged in parallel with a gap between the yarns, and Non-coarse knitted fabrics (knitted fabrics having substantially no gaps formed between yarns) are included. The coarse fabric preferably has a basis weight of 30 to 700 g / m ² , and the through area ratio of the coarse knit fabric is preferably about 10 to 95% with respect to the total surface area of the coarse knit fabric. When the fibrous base fabric is a non-coarse knitted fabric, there are no restrictions on its structure, basis weight, thickness, etc., but knitted fabrics such as plain weave, twill weave, circular knit, weft knit, and warp knit according to the purpose of use. Can be selected, and the basis weight is 50-100
It is preferably about 0 g / m ² . There is no particular limitation on the strength of the base cloth, but for use as a stretchable membrane material that is fixed under tension, 392 N /
It is preferable to have a tensile strength of 3 cm (40 kgf / 3 cm) or more. Fiber for base cloth The base cloth may be previously water-repellent using a water repellent such as a fluorine compound or a silicone compound, or may be softened using a softening agent such as an amino-modified silicone compound. Good.

In the antifouling waterproof sheet of the present invention, the polyvinyl chloride resin that can be used for the polyvinyl chloride resin-containing waterproof resin layer formed on the front surface or both front and back surfaces of the base cloth is a vinyl chloride homopolymer. , And one or more polyvinyl chloride resins selected from copolymers of vinyl chloride and other monomers. As the monomer copolymerizable with vinyl chloride, vinylidene chloride, vinyl acetate, ethylene, acrylonitrile, (meth) acrylic acid esters and the like can be used. The polyvinyl chloride resin-containing waterproof resin layer is a plasticizer, stabilizer, filler, colorant, flameproofing agent, ultraviolet absorber, light stabilizer, antifungal agent, antistatic agent for these vinyl chloride resins. Alternatively, a mixture of one or more additives such as a crosslinking agent may be used.

Examples of plasticizers that can be used in the polyvinyl chloride resin-containing waterproof resin layer used in the antifouling waterproof sheet of the present invention include phthalate ester plasticizers, adipate ester plasticizers, and fumarate ester plasticizers. Agent, maleic acid ester plasticizer, azelaic acid ester plasticizer, sebacic acid ester plasticizer, citric acid ester plasticizer, trimellitic acid ester plasticizer, pyromellitic acid ester plasticizer, phosphoric acid ester plasticizer A plasticizer such as a plasticizer or an epoxy plasticizer can be used. Particularly, general-purpose plasticizers such as phthalic acid ester-based plasticizers and adipic acid ester-based plasticizers are advantageous in terms of cost and can be preferably used. Examples of the phthalate ester-based plasticizer include dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, and phthalate. Butylbenzyl acid salt and the like can be used. As the adipic acid ester plasticizer, di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate, or the like can be used. In addition to the above plasticizer, ethylene-vinyl acetate-carbon monoxide terpolymer, ethylene- (meth) acrylic acid ester-carbon monoxide terpolymer, ester-based urethane polymer, polyester-based plasticizer You may use polymeric plasticizers, such as. You may use these plasticizers individually or in mixture of 2 or more types.

In the antifouling waterproof sheet of the present invention, the thickness of the polyvinyl chloride resin-containing waterproof resin layer can be appropriately set according to the basis weight of the base cloth and the application.
This thickness is a sufficient thickness to give desired antifouling property and mechanical strength to the resulting antifouling waterproof sheet, for example, 0.0
It is preferable to adjust to 1 to 2.0 mm, and 0.05 to
It is more preferable to adjust to 1.5 mm. In addition, the polyvinyl chloride resin-containing waterproof resin layer may be composed of one or more layers having the same composition or two or more layers having different compositions on the base fabric, and different compositions may be provided on the front and back sides of the base fabric. The polyvinyl chloride resin-containing waterproof resin layer may be formed.

In the antifouling waterproof sheet of the present invention, the waterproof resin layer is formed of a film containing the above polyvinyl chloride resin, a solution, an emulsion, a paste sol, etc., by a known method such as topping, calendering, It can be formed on the base fabric by a method such as coating or dipping.

In the antifouling waterproof sheet of the present invention, the fluorine-containing resin used in the antifouling layer formed on the waterproof resin layer is, for example, a tetrafluoroethylene polymer or a tetrafluoroethylene-perfluoroolefin copolymer. (For example, tetrafluoroethylene-hexafluoropropylene copolymer), tetrafluoroethylene-perfluoroalkylvinylether copolymer, tetrafluoroethylene-perfluoroalkylvinylethylene copolymer, chlorotrifluoroethylene polymer, vinylidene fluoride copolymer At least one selected from coalesce, chlorotrifluoroethylene-ethylene copolymer and the like can be used. Particularly, as vinylidene fluoride-based polymer, a monomer copolymerizable with vinylidene fluoride, for example, tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, fluoroethylene, and (meth) acrylic acid ester 1 selected from compounds, vinyl ethers, vinyl esters, etc.
A copolymer obtained by copolymerizing one or more kinds of monomers is preferably used. These copolymers are not limited to random copolymers, and may be graft copolymers. The fluorine-containing resin used in the antifouling layer of the antifouling waterproof sheet of the present invention is preferably contained in an amount of 30% by mass or more based on the total mass of the resin components in the antifouling layer. If it is 30% by mass or less, sufficient antifouling property cannot be exhibited.

The fine silica particles used in the antifouling layer of the antifouling waterproof sheet of the present invention are selected from crystalline silica (natural silica), fused silica (amorphous silica) and synthetic silica (synthetic amorphous silica). One or more types of fine particles of silica can be used. As a synthetic silica, a dry method,
It may be obtained by either a wet method or an airgel method. By adding silica fine particles to the antifouling layer, the surface of the silica fine particles is exposed on the surface of the antifouling layer, which imparts hydrophilicity to the antifouling layer and improves the antifouling property and the rain streak antifouling property of the sheet. . In the antifouling waterproof sheet of the present invention, the silica fine particles preferably have an average particle diameter of 30 μm or less as a powder. When the average particle diameter of the silica fine particles exceeds 30 μm, the coating strength of the antifouling layer is lowered, or when the antifouling layer is formed using a solution, the silica fine particles are likely to settle. In the antifouling waterproof sheet of the present invention, the silica fine particles are
Preferably T specific surface area of 40~500m ² / g, and more preferably 40 to 400 ² / g.
Particularly, it is preferable to use silica fine particles having the BET specific surface area range and manufactured by a dry method or a wet method. The silica fine particles having a BET specific surface area of less than 40 m ² / g or the silica fine particles of more than 500 m ² / g have a low effect of imparting hydrophilicity to the antifouling layer. The amount of silica fine particles used in the antifouling layer is 5% of the total mass of the antifouling layer.
Is preferably 70% by mass, 10% by mass to 60% by mass
Is more preferable. If it is less than 5% by mass, sufficient antifouling property cannot be obtained, and if it exceeds 70% by mass, the film strength of the antifouling layer is remarkably reduced and the antifouling layer may be easily damaged.

In the antifouling waterproof sheet of the present invention, the antifouling layer may contain another resin which is compatible with the fluorine-containing resin. For example, as the resin having good compatibility with the vinylidene fluoride polymer, acrylic resin, urethane resin, cyanoethylated ethylene-
A vinyl alcohol copolymer or the like can be used.
Addition of these resins improves the adhesion between the antifouling layer and the polyvinyl chloride resin layer. Acrylic resins are particularly suitable. The acrylic resin that can be used as the mixed resin in the antifouling layer of the antifouling waterproof sheet of the present invention is a polymer or copolymer containing acrylic acid or methacrylic acid C _{1 to} C ₄ alcohol ester as a main constituent monomer. It is preferable that the resin is selected from the resins whose main component is coalescence.
As a main constituent monomer of such an acrylic resin,
Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate can be used, and methyl acrylate and methyl methacrylate are particularly preferable. Examples of the monomer copolymerized with these main constituent monomers include acrylic acid or methacrylic acid, and esters of C _{1 to} C ₁₂ alcohols of acrylic acid or methacrylic acid, 2-hydroxyethyl methacrylate, glycidyl methacrylate, N-. Methylol acrylamide, N, N-dimethylaminoethyl methacrylate, methyl vinyl ether, vinyl ethoxysilane, α-methacryloxypropyltrimethoxysilane, vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, acrylonitrile, methacrylic acid. Mention may be made of monomers such as ronitrile and butadiene. These copolymers are not limited to random copolymers and may be graft copolymers. For example, a polymer obtained by adding vinylidene fluoride to a methyl methacrylate polymer and then graft-polymerizing this may be used. In addition, an acrylic resin containing an ethyleneimine residue, an alkylenediamine residue, or the like can also be used.

In the antifouling layer of the antifouling waterproof sheet of the present invention, the urethane resin which can be used as a mixed resin is obtained by reacting a polymer polyol, a polyisocyanate, and optionally a chain extender. A resin can be used. As the polymer polyol used for such urethane-based resin, it is possible to use a polyester-based polyol having hydroxyl groups at both ends of a molecular chain, a polyether-based polyol, a polycarbonate-based polyol, a polyesteramide polyol, or an acrylate-based polyol. it can. As the polyisocyanate, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylene diisocyanate, 1,6-
Aromatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and aliphatic polyisocyanates and alicyclic polyisocyanates can be used. As the chain extender, low molecular weight polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and diethylene glycol, aliphatic diamines such as ethylenediamine, propylenediamine, butylenediamine and hexamethylenediamine, Aliphatic polyamines such as piperazine, 1,4-diaminopiperazine and 1,3-cyclohexylenediamine, aromatic polyamines such as diphenylmethanediamine, tolylenediamine and phenylenediamine, alkanolamines such as ethanolamine and propanolamine are used. be able to. In particular, a urethane resin using an aliphatic polyisocyanate or an alicyclic polyisocyanate as a polyisocyanate component is preferable because it does not yellow due to exposure to ultraviolet rays and has good weather resistance.

If desired, the antifouling layer may contain additives such as an ultraviolet absorber, a light stabilizer, a mildew proofing agent, a coloring agent and a filler, and an epoxy type curing agent. Various curing agents such as an isocyanate curing agent, a silane coupling agent, an oxazoline crosslinking agent, and an aziridine crosslinking agent may be added. In particular, when an ultraviolet absorber is added, it is preferable to use at least one selected from copolymers containing ultraviolet absorbing monomers such as benzotriazole compounds and benzophenone compounds. As the filler, either an inorganic filler or an organic filler may be used, and as the inorganic filler, for example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, Titanium oxide, zinc oxide, zinc sulfate, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, silica, alumina, magnesium oxide, magnesium hydroxide, etc. can be used. Organic filler For example, porous resin fine particles such as styrene beads, acrylic beads, chitosan beads, cellulose beads, nylon beads, and urea resin beads can be used. You may use these pigments individually or in mixture. As the colorant, either an organic colorant or an inorganic colorant may be used.

In the antifouling waterproof sheet of the present invention, as a method for forming the antifouling layer, a film, a solution, an emulsion or the like containing a fluorine-containing resin and silica fine particles is used, and known methods such as topping and lamination are used. It can be formed on the sheet by a method such as coating or coating. In particular, it is preferably formed by a coating process using a solution containing a fluorine-containing resin and silica fine particles and / or a dispersion. In this case, good antifouling property can be obtained even if the mixing ratio of the silica fine particles in the antifouling layer is small. In forming the antifouling layer on the waterproof resin layer, as a pretreatment, the surface of the polyvinyl chloride resin-containing waterproof resin layer may be subjected to corona discharge treatment or plasma treatment before forming the antifouling layer. . When the antifouling layer is formed into a film, the antifouling layer film may be subjected to corona discharge treatment or plasma treatment, and then the treated surfaces may be bonded together. The thickness of the antifouling layer is 0.
The thickness is preferably 3 to 50 μm, and more preferably 1 to 30 μm. If it is less than 0.3 μm, the antifouling property may be insufficient, and if it exceeds 30 μm, the effect is saturated and the effect is not improved.

In the antifouling waterproof sheet of the present invention, an adhesive layer may be formed between the antifouling layer and the waterproof resin layer. By forming the adhesive layer, the adhesiveness of the antifouling layer to the waterproof resin layer can be improved. As the resin that can be used for the adhesive layer, polyvinyl chloride resin, acrylic resin, polyurethane resin, polyethylene resin, epoxy resin, melamine resin, polypropylene resin, polyamide resin, polyester resin, ethylene -Vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, polyvinyl alcohol resin, cyanoethylated ethylene-vinyl alcohol copolymer resin, polyvinyl butyral resin, silicone resin, fluorine-containing resin, fluorine-modified resin, etc. It is possible to use at least one polymer selected from the above synthetic resins. The adhesive layer may be formed using a composition having ultraviolet curability. The adhesive layer has an epoxy curing agent, an isocyanate curing agent, a silane coupling agent,
Various curing agents such as oxazoline-based cross-linking agents and aziridine-based cross-linking agents may be added. It is preferable that the adhesive layer contains at least one selected from an acrylic resin, a urethane resin, and a cyanoethylated ethylene-vinyl alcohol copolymer resin. Further, the adhesive layer may contain additives such as an ultraviolet absorber, a light stabilizer, a fungicide, a coloring agent and a filler, if necessary.

In the antifouling waterproof sheet of the present invention, as a method for forming an adhesive layer, a film, a solution, an emulsion or the like containing the above-mentioned adhesive layer polymer is used, and a known method such as topping or laminating is used. It can be formed on the sheet by a method such as coating, or the like. The thickness of the adhesive layer is not particularly limited, for example,
It is preferably 0.3 to 200 μm. If the thickness of the adhesive layer is less than 0.3 μm, a special processing machine is required, which may cause manufacturing difficulties. On the other hand, when the adhesive layer having a sufficient thickness is provided, the effect of suppressing the migration of the plasticizer and the like contained in the polyvinyl chloride resin-containing waterproof resin layer is imparted, and the antifouling property of the antifouling waterproof sheet is improved. It may be further improved. However, if the thickness exceeds 200 μm, the texture of the obtained antifouling sheet may become hard, and this may cause adverse effects.

In the antifouling waterproof sheet of the present invention, an additive migration preventing layer may be formed between the waterproof resin layer and the antifouling layer instead of the adhesive layer or together with the adhesive layer. In addition, when a polyvinyl chloride resin-containing waterproof resin layer is formed on both sides of the base fabric and the antifouling layer is formed on only one side (front side) of the base cloth, the additive transfer as the outermost layer on the other side (back side). It is preferable to form a preventive layer. By forming the additive migration prevention layer as the outermost layer on the back surface side, when the sheet is rolled and stored in a roll state, the antifouling layer on the front surface is a plastic contained in the polyvinyl chloride resin layer on the back surface. It is possible to prevent migration components such as agents and stabilizers from adhering. By doing so, the original antifouling property of the antifouling layer can be exhibited when the sheet is actually used. In the case where the antifouling waterproof sheet of the present invention has a hydrophilic antifouling layer, the deterioration of the antifouling property caused by the attachment of additives such as a plasticizer and a stabilizer is a non-hydrophilic antifouling property. Since it is more prominent than the layer, the laminated structure is such that the antifouling layer surface and the polyvinyl chloride resin-containing waterproof resin layer surface do not come into direct contact, or
Blending considerations such as the use of polymer plasticizers in the polyvinyl chloride resin-containing waterproof resin layer are necessary. In making the antifouling waterproof sheet of the present invention into a roll-shaped roll,
There is no particular limitation on the winding method, but for example, when winding an antifouling waterproof sheet having an antifouling layer formed on only one side, it is preferable to wind the antifouling layer inside. With this configuration, the back surface of the sheet is exposed at the outermost periphery of the roll-shaped roll, and it is possible to prevent the stains or scratches from being attached to the antifouling layer due to the movement of the roll-shaped roll or the like.

Resins that can be used in the additive migration prevention layer include polyvinyl chloride resins, acrylic resins, polyurethane resins, polyethylene resins, epoxy resins, melamine resins, polypropylene resins, polyamide resins, polyesters. -Based resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, polyvinyl alcohol-based resin, cyanoethylated ethylene-
At least one polymer selected from synthetic resins such as vinyl alcohol copolymer resin, polyvinyl butyral resin, silicone resin, fluorine-containing resin and fluorine-modified resin can be used. You may form an additive migration prevention layer using the composition which has ultraviolet curability.
Various hardening agents such as epoxy-based hardening agents, isocyanate-based hardening agents, silane coupling agents, oxazoline-based cross-linking agents, and aziridine-based cross-linking agents may be added to the additive migration prevention layer. The additive migration prevention layer preferably contains at least one selected from acrylic resins, urethane resins, and cyanoethylated ethylene-vinyl alcohol copolymer resins in the adhesive layer. The additive migration prevention layer may contain additives such as antifungal agents, colorants, and fillers, if necessary.

In the antifouling waterproof sheet of the present invention, as a method for forming the additive migration preventing layer, a film, solution, emulsion or the like containing the above-mentioned polymer for additive migration preventing layer is used, and a known method is used. For example, it can be formed on the sheet by a method such as topping, laminating and coating. The additive migration prevention layer preferably has a thickness of 0.3 to 200 μm, and a thickness of 1 to 1
More preferably, it is set to 00 μm. Its thickness is 0.3
If it is less than μm, the effect of preventing the migration of the additive from the polyvinyl chloride resin-containing waterproof resin layer may be insufficient, and if it exceeds 200 μm, the effect will not change and the texture will be rather conversely. It may cause problems such as hardening.

[0024]

The present invention will be further described with reference to the following examples.

[Evaluation Method] The performance of the antifouling waterproof sheet of the present invention was measured and evaluated by the following test method. 1. Evaluation of Contamination Property The test sheet was installed facing the south with a tilt angle of 30 degrees and vertically, and an outdoor exposure test was performed to evaluate the antifouling property of the test sheet and the generation state of rain streaks. (B) About the sheet installed at the antifouling inclination angle of 30 degrees, the difference in lightness (Δ of the surface of the sample for one year after the exposure, based on the sample before the exposure)
L) was measured. A color reader CR-10 (measurement diameter: 8 mm) manufactured by Minolta Co., Ltd. was used for measuring the difference in lightness, and the measurement was performed on the day following the day when there was rainfall at the sampling time. The evaluation was performed based on the following criteria. ◯: ΔL = −5 or more (slightly dirty) Δ: ΔL = −10 or more and less than −5 (dirty) ×: ΔL = −10 or less (significantly dirty) (B) Rain line dirt vertically installed With respect to the prepared sheet, the generation state of rain streaks was visually observed and evaluated based on the following criteria. ◯: Almost no stain on the rain streak is observed. Δ: Light rain streaks are observed. X: Heavy rain stains are observed.

2. Adhesion evaluation Regarding the test sheet, JIS L-1096-1984
Adhesion durability between the antifouling layer and the sheet substrate was evaluated by the B method (Scott type) of the abrasion strength test described in 1.
The test was performed 500 times and 1000 times with a rubbing load of 1.0 kgf, and the adhered state of the antifouling layer was visually determined. ◯: No abnormality Δ: Part of the antifouling layer (less than 1/3) has fallen off from the sheet substrate. X: 1/3 or more of the antifouling layer has fallen off from the sheet substrate.

[Example 1] As the base fabric, a non-coarse woven fabric made of polyester long-fiber yarn and having the following woven structure was used. A polyvinyl chloride resin dispersion having the following composition 1 was applied to both sides of this base cloth with a knife coater at 100 g / m ² per side.
Each was subjected to coating processing, and further heat-treated at 180 ° C. for 2 minutes to form a polyvinyl chloride resin layer (1). <Composition 1> Polyvinyl chloride resin for paste processing 100 parts by mass Di-2-ethylhexyl phthalate 70 parts by mass Epoxidized soybean oil 5 parts by mass Ba-Zn-based stabilizer 3 parts by mass Antimony trioxide 5 parts by mass Rutile titanium oxide 5 parts by mass Tetrachloroisophthalonitrile (mildewproofing agent) 0.1 parts by mass Mineral Spirit (diluent) 5 parts by mass On one surface of the polyvinyl chloride resin layer (1), a thickness of 0. A polyvinyl chloride resin film having the following composition 2 formed into 2 mm is thermally laminated to form a polyvinyl chloride resin layer (2), and a polyvinyl chloride resin layer (2) is formed on the surface side.
A waterproof resin layer having a layered structure was formed. <Composition 2> Polyvinyl chloride resin for calendering 100 parts by mass Di-2-ethylhexyl phthalate 70 parts by mass Epoxidized soybean oil 5 parts by mass Ba-Zn-based stabilizer 3 parts by mass Antimony trioxide 5 parts by mass Rutile titanium oxide 5 parts by mass UV absorber 0.1 parts by mass (Trademark: Tinuvin P, manufactured by Ciba Specialty Chemicals) Tetrachloroisophthalonitrile (antifungal agent) 0.1 parts by mass Polyvinyl chloride of the waterproof resin layer of the above sheet On the resin layer (2), an antifouling layer coating solution having the following composition 3 was coated by a gravure coater and dried at 120 ° C. for 2 minutes to form an antifouling layer having a thickness of 2 μm. A dirty tarpaulin was obtained. Table 1 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 3> Vinylidene fluoride polymer resin 80 parts by mass Hexamethylene diisocyanate 5 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

[Example 2] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, instead of the antifouling layer coating solution of the above composition 3, the antifouling layer coating solution of the following composition 4 was used. Table 1 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 4> Vinylidene fluoride-chlorotrifluoroethylene copolymer resin 80 parts by mass Hexamethylene diisocyanate 5 parts by mass Wet method silica fine particles (average particle size: 1.5 μm, BET specific surface area: 135 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

Example 3 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 1. However, instead of the antifouling layer coating solution of the above composition 3, the antifouling layer coating solution of the following composition 5 was used. Table 1 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 5> Chlorotrifluoroethylene-vinyl ether copolymer resin 80 parts by mass Hexamethylene diisocyanate 5 parts by mass Wet method silica fine particles (average particle diameter: 7 μm, BET specific surface area: 200 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

[Example 4] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, instead of the antifouling layer coating solution of the above composition 3, an antifouling layer coating solution of the following composition 6 was used. Table 1 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 6> Vinylidene fluoride polymer resin 56 parts by mass Methyl methacrylate polymer resin 24 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

[Example 5] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, the antifouling layer coating solution of the following composition 7 was used in place of the antifouling layer coating solution of the above composition 3. Table 1 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 7> Vinylidene fluoride-chlorotrifluoroethylene polymer resin 40 parts by mass Methyl methacrylate polymer resin 40 parts by mass Wet method silica fine particles (average particle size: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Part methyl ethyl ketone 900 parts by mass

Example 6 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, the antifouling layer coating solution of the following composition 8 was used in place of the antifouling layer coating solution of the above composition 3. Table 1 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 8> Vinylidene fluoride polymer resin 24 parts by mass Methyl methacrylate polymer resin 56 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

Example 7 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 1. However, the antifouling layer coating solution of the above composition 3 was changed to the antifouling layer coating solution of the following composition 9. Table 1 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 9> Vinylidene fluoride polymer resin 16 parts by mass Methyl methacrylate polymer resin 64 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

Comparative Example 1 A comparative waterproof sheet was produced in the same manner as in Example 1. However, in the coating liquid for antifouling layer containing fine silica particles of the above composition 3, the fine silica particles were not added, and the addition amount of the vinylidene fluoride polymer resin was changed from 80 parts by mass to 100 parts by mass. Table 1 shows the evaluation results of the obtained waterproof sheet.

Comparative Example 2 A comparative waterproof sheet was produced in the same manner as in Example 1. However, 20 parts by mass of silica fine particles (20 parts by mass) contained in the antifouling layer coating solution of the above composition 3 were added to light calcium carbonate fine particles (average particle diameter: 3 μm, BET specific surface area: 12.3 m ² / g). changed. Table 1 shows the evaluation results of the obtained waterproof sheet.

Comparative Example 3 A comparative waterproof sheet was produced in the same manner as in Example 1. However, the vinylidene fluoride copolymer resin (80 parts by mass) contained in the antifouling layer coating solution of the above composition 3 was replaced with a methyl methacrylate polymer resin (80 parts by mass).
Changed to. Table 1 shows the evaluation results of the obtained waterproof sheet.

[Example 8] The same waterproof resin layer-coated sheet as in Example 1 was used, and the polyvinyl chloride resin layer (2) of this sheet was coated with an adhesive layer coating solution having the following composition 10 using a gravure coater. And dried at 100 ° C. for 2 minutes, thereby forming an adhesive layer having a thickness of 4 μm. Then, an antifouling layer coating solution having the following composition 11 was applied onto the adhesive layer by a gravure coater, and the coating was performed at 120 ° C. for 2 hours.
An antifouling layer having a thickness of 2 μm was formed by drying for minutes. Table 2 shows the evaluation results of the obtained waterproof sheet. <Composition 10> Butyl methacrylate polymer resin 200 parts by mass Methyl ethyl ketone 800 parts by mass <Composition 11> Vinylidene fluoride polymer resin 80 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g ) 20 parts by mass Methyl ethyl ketone 900 parts by mass

Example 9 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 8. However, instead of the antifouling layer coating solution of the above composition 11, an antifouling layer coating solution of the following composition 12 was used. Table 2 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 12> Vinylidene fluoride-tetrafluoroethylene copolymer resin 80 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

[Example 10] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 8. However, the composition 11
Instead of the antifouling layer coating solution of No. 3, an antifouling layer coating solution of the following composition 13 was used. Table 2 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 13> Tetrafluoroethylene-vinyl ether copolymer resin 80 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass

Example 11 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 8. However, the composition 11
An antifouling layer coating solution having the following composition 14 was used instead of the antifouling layer coating solution of Table 2 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 14> Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer resin 80 parts by mass Wet method silica fine particles (average particle diameter: 2.7 μm, BET specific surface area: 275 m ² / g) 20 parts by mass Methyl ethyl ketone 900 parts by mass Department

[Example 12] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 8. However, the composition 10
Instead of the adhesive layer coating liquid of No. 3, an adhesive layer coating liquid having the following composition 15 was used. Table 2 shows the evaluation results of the obtained antifouling waterproof sheet. <Composition 15> Polyurethane resin 80 parts by mass Vinylidene fluoride polymer resin 20 parts by mass Methyl ethyl ketone 350 parts by mass Dimethylformamide 50 parts by mass

[Example 13] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 8. However, the composition 10
Instead of using the adhesive layer coating solution of cyanoethylated ethylene-vinyl alcohol copolymer resin film (thickness 5
0 μm), and this was heat laminated to form an adhesive layer. Table 2 shows the evaluation results of the obtained antifouling waterproof sheet.

[0043]

[Table 1]

[0044]

[Table 2]

The antifouling waterproof sheets of Examples 1 to 13 were good in antifouling properties, particularly in the rain line stain prevention properties. Particularly, in the antifouling sheets of Examples 4 to 7, since the acrylic resin was added to the antifouling layer, the adhesion to the waterproof resin layer was also good. The antifouling waterproof sheets of Examples 8 to 13 also
Since the adhesive layer was provided thereon, the adhesion between the antifouling layer and the waterproof resin layer was good. On the other hand, in the waterproof sheets of Comparative Examples 1 and 2, since silica fine particles were not added to the antifouling layer, the antifouling property, particularly the rain streak antifouling property was insufficient. Since the waterproof sheet of Comparative Example 3 did not use the fluorine-containing resin, the antifouling property was deteriorated over time, and the rain line antifouling property was also insufficient.

The antifouling waterproof sheets obtained in Examples 14 to 19 below were subjected to the following tests. 3. Antifouling property of roll-up rolls after production and accelerated test
Evaluation The test sheet was wound around a paper tube having a diameter of 5.08 cm with the antifouling layer inside (sheet length: 40 cm) to prepare a roll-shaped roll of the antifouling waterproof sheet. This roll-shaped roll was left in an oven set at 50 ° C.-90% relative humidity for 2 weeks to perform an acceleration test. Table 3 shows the evaluation results of the antifouling property of the sheet after the acceleration test.

[Example 14] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. Table 3 shows the evaluation results of the roll-shaped roll of the obtained antifouling waterproof sheet. [Example 15] An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 1. However, antifouling layers were formed on both the front and back surfaces of the sheet. Table 3 shows the evaluation results of the roll-shaped roll of the obtained antifouling sheet.

Example 16 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 5. However, antifouling layers were formed on both the front and back surfaces of the sheet. Table 3 shows the evaluation results of the roll-shaped roll of the obtained antifouling waterproof sheet. [Example 17] An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 8. However, the adhesive layer and the antifouling layer were formed on both front and back surfaces of the sheet. Table 3 shows the evaluation results of the roll-shaped roll of the obtained antifouling waterproof sheet.

[Example 18] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, an additive migration preventing layer coating solution having the following composition 16 is coated on the polyvinyl chloride resin layer (1) on the side opposite to the antifouling layer forming surface with a gravure coater and dried at 100 ° C. for 2 minutes. Thus, an additive migration preventing layer having a thickness of 4 μm was formed. Table 3 shows the evaluation results of the roll-shaped roll of the obtained antifouling waterproof sheet. <Composition 16> Methyl methacrylate polymer resin 90 parts by mass Fine particle silica (average particle diameter: 5 μm) 10 parts by mass Methyl ethyl ketone 400 parts by mass

Example 19 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 18. However, the composition 1
Instead of the additive migration preventing layer coating liquid of 6, the following composition 17
The additive migration prevention layer coating liquid of 1. was used. Table 3 shows the evaluation results of the roll-shaped roll of the obtained antifouling waterproof sheet. <Composition 17> Methyl methacrylate polymer resin 70 parts by mass Vinylidene fluoride-chlorotrifluoroethylene copolymer resin 30 parts by mass Methyl ethyl ketone 400 parts by mass

[0051]

[Table 3]

The antifouling waterproof sheet roll-shaped roll of Example 14 exhibited good antifouling properties when the promotion time was short, but exhibited antifouling properties and rain streaks stain resistance when the promotion time was long. A decrease was observed. Since each of the antifouling waterproof sheet roll-shaped rolls of Examples 15 to 17 had the antifouling layer formed on both sides, there was almost no deterioration in the antifouling property and the rain streak antifouling property. In the antifouling waterproof sheet roll-shaped rolls of Examples 18 and 19, the antifouling layer was formed on only one surface as in Example 14, but the additive migration preventing layer was formed. Even when the acceleration time was long, there was almost no deterioration in the antifouling property and the rain line stain prevention property. Example 14
In the roll-shaped wound body of the antifouling waterproof sheet of Examples 18 and 19, the antifouling layer formed on one surface of the sheet-shaped substrate was wound up inside, so that dirt may be attached to the antifouling layer during handling. It wasn't scratched.

The following tests were conducted on the antifouling waterproof sheets of Examples 4, 6, 8 and 17. 4. Regarding the joint part durability evaluation test sheet, the front and back surfaces of the two sheets were overlapped and joined by a high-frequency welding machine, and the width was measured along the thread line in the direction perpendicular to the joint part so that the joint part was located at the center. A creep test was performed on a test piece cut into a strip shape having a length of 3 cm and a length of 30 cm to evaluate the durability of the joint. The lap width of the bonded portion was 3 cm, and the creep test was conducted for 24 hours under an atmosphere temperature of 65 ° C. and an applied load of 196 N / 3 cm (20 kgf / 3 cm). The evaluation was performed based on the following criteria. The evaluation results are shown in Table 4. ○: No abnormality ×: Abnormality (joint peeling)

[0054]

[Table 4]

The antifouling waterproof sheet of the present invention has good durability of the joint portion, and can be sufficiently used for large-area stretchable membrane materials such as medium / large tents and tent warehouses. .

[0056]

The antifouling waterproof sheet of the present invention has an excellent antifouling property by forming an antifouling layer containing a fluorine-containing resin and silica fine particles, and is particularly excellent in rain streak antifouling property. Is. The antifouling waterproof sheet of the present invention includes a medium / large tent, a tent warehouse, an eaves tent, a truck hood,
Even if it is used for industrial materials such as backlit for signs, it can maintain a beautiful appearance without rain streaks for a long time,
It is extremely useful in practice.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 18, 2002 (2002.1.1
8)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

[Title of Invention] Antifouling waterproof sheet excellent in rain line stain prevention effect

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

As a method for improving the antifouling property, for example, a method of coating the surface of a polyvinyl chloride resin with an acrylic resin solution dissolved in an organic solvent and drying it is generally used. The effect is not sufficient because the plasticizer in the polyvinyl chloride resin dissolves in the solvent and the liquid plasticizer and liquid stabilizer compounded in the polyvinyl chloride resin migrate to the coating resin layer. The method of coating fluorine-containing resin on the surface instead of acrylic resin is more effective in suppressing migration of plasticizers compared to the case of coating acrylic resin, and also has a high barrier property against ultraviolet rays and rain. However, the effect of preventing rain stains is not sufficient.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, that is, the antifouling property of a sheet having a polyvinyl chloride resin-containing waterproof resin layer, particularly, the antifouling property of a rain line which is excellent in antifouling property. To provide a seat.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

[0005]

Means for Solving the Problems As a result of diligent studies on the above problems, the present inventors have found that in a sheet having a polyvinyl chloride resin layer, silica fine particles are contained in an antifouling layer containing a fluorine-containing resin. The present inventors have found that the compounding of the composition significantly improves the rain line stain prevention effect, and completed the present invention.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

The antifouling waterproof sheet of the present invention, which is excellent in the effect of preventing rain stains, has a base cloth containing at least one layer of fiber cloth and a polyvinyl chloride resin formed on at least one surface of the base cloth. A waterproof resin layer containing, and an antifouling layer containing a resin component containing a fluorine-containing resin and a dispersed particle component containing silica fine particles is further formed on at least one layer of the waterproof resin layer. It is a feature. In the antifouling waterproof sheet of the present invention which is excellent in the rain line stain prevention effect, it is preferable that the resin component in the antifouling layer further contains at least one acrylic resin together with the fluorine-containing resin. In the antifouling waterproof sheet having excellent rain line stain prevention effect of the present invention, the content of the fluorine-containing resin in the resin component of the antifouling layer is 30% by mass or more based on the total mass of the resin components. It is preferable. In the antifouling waterproof sheet excellent in the rain streak antifouling effect of the present invention, further comprising an adhesive layer and / or an additive migration preventing layer formed between the waterproof resin layer and the antifouling layer. preferable. In the antifouling waterproof sheet having an excellent effect of preventing rain stains of the present invention, the adhesive layer is an acrylic resin,
At least 1 selected from polyurethane resin and cyanoethylated ethylene-vinyl alcohol copolymer resin
It is preferable to include a seed. In the antifouling waterproof sheet of the present invention which is excellent in the effect of preventing rain streaks, it is preferable that an additive migration preventing layer is formed on the outermost back surface of the antifouling waterproof sheet. In the antifouling waterproof sheet having excellent rain line stain prevention effect of the present invention, the additive migration prevention layer comprises a fluorine-containing resin, an acrylic resin, a polyurethane resin, and a cyanoethylated ethylene-vinyl alcohol copolymer resin. It is preferable to contain at least one selected. The antifouling waterproof sheet of the present invention, which has an excellent effect of preventing rain streak stains, may be a roll-up body.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

The fibers forming the fiber cloth in the base cloth may be any shape such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn and the like. The structure of the fiber cloth for the base cloth may be a woven fabric, a knitted fabric, a non-woven fabric, or a composite thereof. There is no particular limitation on the knitting or weaving structure of the fiber cloth for the base cloth, for example, at least a coarse knitted woven fabric composed of yarns including warps and wefts arranged in parallel with a gap between the yarns, and Non-coarse knitted fabrics (knitted fabrics having substantially no gaps formed between yarns) are included. The coarse fabric preferably has a basis weight of 30 to 700 g / m ² , and the through area ratio of the coarse knit fabric is preferably about 10 to 95% with respect to the total surface area of the coarse knit fabric. When the fibrous base fabric is a non-coarse knitted fabric, there are no restrictions on its structure, basis weight, thickness, etc., but knitted fabrics such as plain weave, twill weave, circular knit, weft knit, and warp knit according to the purpose of use. Can be selected, and the basis weight is 50-100
It is preferably about 0 g / m ² . There is no particular limitation on the strength of the base cloth, but for use as a stretchable membrane material that is fixed under tension, 392 N /
It is preferable to have a tensile strength of 3 cm (40 kgf / 3 cm) or more. Fiber for base cloth The base cloth may be previously subjected to water repellent treatment with a water repellent such as a fluorine compound or a silicone compound, or may be softened with a softening agent such as an amino-modified silicone compound. .

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

In the antifouling waterproof sheet of the present invention, the fluorine-containing resin used in the antifouling layer formed on the waterproof resin layer is, for example, a tetrafluoroethylene polymer or a tetrafluoroethylene-perfluoroolefin copolymer. (For example, tetrafluoroethylene-hexafluoropropylene copolymer), tetrafluoroethylene-perfluoroalkylvinylether copolymer, tetrafluoroethylene-perfluoroalkylvinylethylene copolymer, chlorotrifluoroethylene polymer, vinylidene fluoride copolymer At least one selected from coalesce, chlorotrifluoroethylene-ethylene copolymer and the like can be used. Particularly, as vinylidene fluoride-based polymer, a monomer copolymerizable with vinylidene fluoride, for example, tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, fluoroethylene, and (meth) acrylic acid ester 1 selected from compounds, vinyl ethers, vinyl esters, etc.
A copolymer obtained by copolymerizing one or more kinds of monomers is preferably used. These copolymers are not limited to random copolymers, and may be graft copolymers. The fluorine-containing resin used in the antifouling layer of the antifouling waterproof sheet of the present invention is preferably contained in an amount of 30% by mass or more based on the total mass of the resin components in the antifouling layer.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

The fine silica particles used in the antifouling layer of the antifouling waterproof sheet of the present invention are selected from crystalline silica (natural silica), fused silica (amorphous silica) and synthetic silica (synthetic amorphous silica). One or more types of fine particles of silica can be used. As a synthetic silica, a dry method,
It may be obtained by either a wet method or an airgel method. By adding silica fine particles to the antifouling layer, the surface of the silica fine particles is exposed on the surface of the antifouling layer, which imparts hydrophilicity to the antifouling layer and improves the antifouling properties of the sheet and the rain line antifouling effect. . In the antifouling waterproof sheet of the present invention, the silica fine particles preferably have an average particle diameter of 30 μm or less as a powder. When the average particle diameter of the silica fine particles exceeds 30 μm, the coating strength of the antifouling layer is lowered, or when the antifouling layer is formed using a solution, the silica fine particles are likely to settle. In the antifouling waterproof sheet of the present invention, the silica fine particles are B
Preferably ET specific surface area of 40~500m ² / g, and more preferably 40 to 400 ² / g. Particularly, it is preferable to use silica fine particles having the BET specific surface area range and manufactured by a dry method or a wet method. The silica fine particles having a BET specific surface area of less than 40 m ² / g or the silica fine particles of more than 500 m ² / g have a low effect of imparting hydrophilicity to the antifouling layer. The addition amount of the silica fine particles used in the antifouling layer is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass based on the total mass of the antifouling layer. If it is less than 5% by mass, sufficient antifouling property cannot be obtained, and if it exceeds 70% by mass, the film strength of the antifouling layer is remarkably reduced and the antifouling layer may be easily damaged.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

If desired, the antifouling layer may contain additives such as an ultraviolet absorber, a light stabilizer, a mildew proofing agent, a coloring agent and a filler, and an epoxy type curing agent. Various curing agents such as an isocyanate curing agent, a silane coupling agent, an oxazoline crosslinking agent, and an aziridine crosslinking agent may be added. In particular, when an ultraviolet absorber is added, it is preferable to use at least one selected from copolymers containing ultraviolet absorbing monomers such as benzotriazole compounds and benzophenone compounds. As the filler, either an inorganic filler or an organic filler may be used, and as the inorganic filler, for example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, Titanium oxide, zinc oxide, zinc sulfate, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, silica, alumina, magnesium oxide, magnesium hydroxide, etc. can be used. Organic filler For example, porous resin fine particles such as styrene beads, acrylic beads, chitosan beads, cellulose beads, nylon beads, and urea resin beads can be used. You may use these fillers individually or in mixture. As the colorant, either an organic colorant or an inorganic colorant may be used.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

In the antifouling waterproof sheet of the present invention, as a method for forming an adhesive layer, a film, a solution, an emulsion or the like containing the above-mentioned adhesive layer polymer is used, and a known method such as topping or laminating is used. It can be formed on the sheet by a method such as coating, or the like. The thickness of the adhesive layer is not particularly limited, for example,
It is preferably 0.3 to 200 μm. If the thickness of the adhesive layer is less than 0.3 μm, a special processing machine is required, which may cause manufacturing difficulties. On the other hand, if the thickness exceeds 200 μm, the resulting antifouling sheet may have a bad texture and may cause adverse effects.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[Evaluation Method] The performance of the antifouling waterproof sheet of the present invention was measured and evaluated by the following test method. 1. Evaluation of Contamination Property The test sheet was installed facing the south with a tilt angle of 30 degrees and vertically, and an outdoor exposure test was performed to evaluate the antifouling property of the test sheet and the generation state of rain streaks. (B) About the sheet installed at the antifouling inclination angle of 30 degrees, the difference in lightness (Δ of the surface of the sample for one year after the exposure, based on the sample before the exposure)
L) was measured. A color reader CR-10 (measurement diameter: 8 mm) manufactured by Minolta Co., Ltd. was used for measuring the difference in lightness, and the measurement was performed on the day following the day when there was rainfall at the sampling time. The evaluation was performed based on the following criteria. ◯: ΔL = −5 or more (slightly dirty) Δ: ΔL = −10 or more and less than −5 (dirty) ×: ΔL = −10 or less (significantly dirty) (b) Rain streak stain prevention effect vertical With respect to the sheet installed in the above, the state of occurrence of rain streak stains was visually observed and evaluated based on the following criteria. ◯: Almost no stain on the rain streak is observed. Δ: Light rain streaks are observed. X: Heavy rain stains are observed.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043]

[Table 1]

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

[0044]

[Table 2]

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

The antifouling waterproof sheets obtained in Examples 14 to 19 below were subjected to the following tests. 3. Antifouling property of roll-up rolls after production and accelerated test
Evaluation The test sheet was wound around a paper tube having a diameter of 5.08 cm with the antifouling layer inside (sheet length: 40 cm) to prepare a roll-shaped roll of the antifouling waterproof sheet. This roll-shaped roll was left in an oven set at 50 ° C.-90% relative humidity for 3 days or 2 weeks to carry out an accelerated test. Table 3 shows the evaluation results of the antifouling property of the sheet after the acceleration test.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[Example 18] An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, an additive migration preventing layer coating solution having the following composition 16 is coated on the polyvinyl chloride resin layer (1) on the side opposite to the antifouling layer forming surface with a gravure coater and dried at 100 ° C. for 2 minutes. Thus, an additive migration preventing layer having a thickness of 4 μm was formed. Table 3 shows the evaluation results of the roll-shaped roll of the obtained antifouling waterproof sheet. <Composition 16> Methyl methacrylate polymer resin 90 parts by mass Silica fine particles (average particle size: 5 μm) 10 parts by mass Methyl ethyl ketone 400 parts by mass

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

[0051]

[Table 3]

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

The antifouling waterproof sheet roll-shaped roll of Example 14 exhibited good antifouling properties when the acceleration time was short, but exhibited antifouling properties and rain line stain prevention effects when the acceleration time was long. A decrease was observed. In each of the antifouling waterproof sheet roll-shaped rolls of Examples 15 to 17, the antifouling layer was formed on both surfaces, and therefore the antifouling property and the rain streak antifouling effect were hardly reduced. In the antifouling waterproof sheet roll-shaped rolls of Examples 18 and 19, the antifouling layer was formed on only one surface as in Example 14, but the additive migration preventing layer was formed. Antifouling property even when the promotion time is long,
There was almost no decrease in the rain line stain prevention effect. The roll-shaped rolls of the antifouling waterproof sheet of Examples 14 and 18 and 19 were wound up with the antifouling layer formed on one surface of the sheet-like substrate inside, so that the antifouling layer was formed during handling. No dirt was attached or scratched.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

The antifouling waterproof sheet of the present invention has an excellent antifouling property by forming an antifouling layer containing a fluorine-containing resin and silica fine particles, and particularly has a good effect of preventing rain streak stains. Is. INDUSTRIAL APPLICABILITY The antifouling tarpaulin of the present invention can be used for industrial materials such as medium and large tents, tent warehouses, eaves tents, truck hoods and backlits for signboards to protect the rain line from stains over a long period of time. It is extremely useful in practice because it can maintain its beautiful appearance.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2E141 AA00 AA02 EE03 EE04 EE05                 4F100 AA20C AK15B AK17C AK17D                       AK25C AK25D AK25G AK41                       AK51G AK68D AK68G AR00C                       AS00D BA03 BA04 BA07                       BA10A BA10C CB00 DE01E                       DG04 DG07 DG11A DG12                       GB07 GB90 JD05B JL06C

Claims (8)

[Claims] 1. A base fabric containing at least one layer of fiber cloth, and a waterproof resin layer formed on at least one surface of the base fabric and containing a polyvinyl chloride resin. At least one of the waterproof resin layers. An antifouling waterproof sheet having an excellent effect of preventing rain streaks, characterized in that an antifouling layer containing a resin component containing a fluorine-containing resin and a dispersed particle component containing silica fine particles is further formed on the layer. . 2. The antifouling waterproof having an excellent rain line stain prevention effect according to claim 1, wherein the resin component in the antifouling layer further contains at least one acrylic resin together with the fluorine-containing resin. Sheet. 3. The rain streak stain prevention according to claim 1 or 2, wherein the content of the fluorine-containing resin in the resin component of the antifouling layer is 30% by mass or more based on the total mass of the resin components. Antifouling waterproof sheet with excellent effect. 4. The rain according to claim 1, further comprising an adhesive layer and / or an additive migration prevention layer formed between the waterproof resin layer and the antifouling layer. An antifouling waterproof sheet with excellent streak prevention effect. 5. The rain streak preventing effect according to claim 4, wherein the adhesive layer contains at least one selected from acrylic resins, polyurethane resins, and cyanoethylated ethylene-vinyl alcohol copolymer resins. Excellent antifouling waterproof sheet. 6. An antifouling material having an excellent effect of preventing rain stains according to claim 1, wherein an additive migration prevention layer is formed on the outermost back surface of the antifouling waterproof sheet. Waterproof tarpaulin. 7. The additive migration prevention layer contains at least one selected from a fluorine-containing resin, an acrylic resin, a polyurethane resin, and a cyanoethylated ethylene-vinyl alcohol copolymer resin. An antifouling waterproof sheet having an excellent effect of preventing rain streak contamination according to item 6. 8. A roll-shaped wound body of the antifouling waterproof sheet having an excellent effect of preventing rain streak contamination according to any one of claims 1 to 7.