JP2003165185A - Anti-staining waterproof sheet excellent in thermal fusing properties - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-staining waterproof sheet susceptible to thermal fusing sewing and excellent in rain streak stain preventing properties and thermal fusing properties. <P>SOLUTION: The anti-staining waterproof sheet excellent in thermal fusing properties has a waterproof resin intermediate layer formed on a fiber cloth substrate material, and an outermost layer formed on the intermediate layer and comprising a anti-staining fusible resin containing a copolymer. At least, one of a homopolymer and a copolymer containing at least one kind of a polymerization unit selected from a hydroxylalkyl (meth)acrylate and N-methylol (meth)acrylamide is grafted to a main chain polymer segment comprising an acrylic polymer as a graft polymer segment, as a main component and, if necessary, has a back outermost layer containing a thermoplastic resin such as an acrylic resin or the like. <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 excellent heat-sealing property. More specifically, the present invention is a truck hood, tent, eaves tent,
The present invention relates to an antifouling waterproof sheet having excellent heat-sealing property, which is used for the purpose of forming a waterproof space using a membrane material such as a tent warehouse, an event tent, and a permanent membrane structure building. More specifically, the present invention relates to a waterproof sheet having good heat-sealing property, excellent antifouling property, and particularly improved prevention of adhesion of dirt due to rain streaks.

[0002]

2. Description of the Related Art Recently, a waterproof sheet used for applications where heat-sealing property and high waterproof property are required comprises a base cloth and a vinyl chloride resin layer covering one side or both sides thereof. It has been used a lot. Such a conventional waterproof sheet, a liquid additive such as a plasticizer contained in a vinyl chloride resin migrates to the surface of the waterproof sheet, so that dirt substances in the air or rain are easily adsorbed on the surface of the waterproof sheet, The once adsorbed dirt substance could not be removed by a washing treatment such as washing with water. In order to solve this problem, a vinyl chloride resin-coated waterproof sheet whose surface is further coated with acrylic resin has appeared. However, even with this, there is a problem that the stain adhesion preventing property is not sufficient and the stain is relatively early. The stain resistance is required to have a higher level, and a vinyl chloride resin-coated waterproof sheet having a surface coated with a fluorine-containing resin or a film laminate has been developed.
These waterproof sheets have antifouling properties such as little adhesion of dirt and removal of dirt by simple washing. However, even with this tarpaulin,
It is not possible to sufficiently prevent dirt from rain streaks on vertical surfaces in buildings such as tents, or there is a small amount of dirt on the roof, and there is a problem that dirt on the vertical surfaces stands out. Further, the durability of the heat-sealed portion may be insufficient in some cases, and the use of the large-scale membrane structure may be limited.

Further, recently, a photocatalytic titanium oxide coating which exerts a self-cleaning action on the coated surface has been put into practical use. The waterproof sheet coated with photocatalytic titanium oxide does not have the heat-sealing property between the waterproof sheets, and when the waterproof sheets are joined by the heat-sealing method, the photocatalytic titanium oxide coating layer coated on that part is used. It is not practical because it requires removal operations such as scraping.
Furthermore, a waterproof sheet with a waterproof layer made of a general-purpose vinyl chloride resin coated with a photocatalytic titanium oxide is relatively early because the photocatalytic titanium oxide decomposes the plasticizer that elutes. In some cases, the waterproof resin layer is hardened, the texture becomes hard, and the waterproof resin layer is likely to be cracked when subjected to a deforming action such as bending.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to enhance the versatility of a waterproof sheet, and has a high heat fusion property, a high level of antifouling property, and a rain streak antifouling property. The present invention is intended to provide an antifouling waterproof sheet. More specifically, the present invention has the same heat fusion property as the good heat fusion property of the waterproof sheet having a vinyl chloride resin or the like which has been widely used conventionally as a waterproof resin layer, It is an object of the present invention to provide an antifouling waterproof sheet which has a small amount of attachment and fixation of a dirt substance, and in particular, an extremely small amount of adhesion and fixation of a stain due to a rain line on a vertical surface of a sheet structure or the like.

[0005]

The antifouling waterproof sheet having excellent heat-sealing property according to the present invention comprises a base cloth made of fiber cloth and a waterproof intermediate layer formed on at least one surface of the base cloth. When,
For the outermost layer of the antifouling fusible resin, the outermost layer of the antifouling fusible resin is formed on the waterproof intermediate layer and has the antifouling fusible resin as a main component. The resin has a main chain polymer segment made of an acrylic polymer, hydroxyalkyl (meth) acrylate and N-methylol (meth)
At least one kind of homopolymers and copolymers containing at least one kind of polymerized units selected from acrylamide is used as a graft polymer segment, and one or more kinds of graft-copolymerized copolymers are used as main component resins. It is characterized by including. In the antifouling waterproof sheet having excellent heat-sealing property of the present invention, the hydroxyalkyl (meth)
It is preferred that the hydroxyalkyl groups in the acrylate polymerized units contain from 2 to 8 carbon atoms. In the antifouling waterproof sheet having excellent heat fusible properties of the present invention, it is preferable that the outermost layer of the antifouling fusible resin further contains colloidal silica. In the antifouling waterproof sheet of the present invention, which has excellent heat fusion properties, it is preferable that the outermost layer of the antifouling fusible resin further contains a blocked isocyanate. In the antifouling waterproof sheet having excellent heat fusible properties of the present invention, the outermost layer of the antifouling fusible resin is the main component resin and an additional component resin composed of at least one thermoplastic resin different from the main component resin. It is preferable to include and. In the antifouling waterproof sheet having excellent heat-sealing property of the present invention, it is preferable that the waterproof intermediate layer contains at least one selected from natural rubber, synthetic rubber or synthetic resin. In the antifouling waterproof sheet having excellent heat-sealing property of the present invention, the waterproof intermediate layer synthetic resin is at least selected from a vinyl chloride resin, a thermoplastic urethane resin, and a fluoroolefin resin. It is preferable to include one kind. In the antifouling waterproof sheet excellent in heat fusion property of the present invention, the waterproof intermediate layer and the antifouling fusible resin outermost layer are formed on the surface of the base fabric, and a block is formed on the back surface thereof. The outermost layer of the back surface of the thermoplastic resin containing isocyanate may be further formed. In the antifouling waterproof sheet having excellent heat fusible properties of the present invention, it is preferable that the outermost layer of the antifouling fusible resin is formed by a coating method. In the antifouling waterproof sheet having excellent heat-sealing property of the present invention, it is preferable that the outermost layer of the back surface of the thermoplastic resin containing the blocked isocyanate is formed by a coating method. The heat-sealable sewn product of the antifouling waterproof sheet of the present invention is at least a part of the outermost layer of the antifouling fusible resin of the antifouling waterproof sheet excellent in the heat fusible property of the present invention. Alternatively, it is characterized in that it is superposed on a part of a sheet of a different type and subjected to heat fusion treatment. In the heat fusion sewing method of the antifouling waterproof sheet having excellent heat fusion property of the present invention, it is preferable that the heat fusion treatment is performed at a temperature of 150 to 650 ° C.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the antifouling waterproof sheet of the present invention, the fiber cloth forming the base cloth includes natural fibers (eg cotton, hemp etc.), synthetic fibers (eg polyester, polyamide, polyvinyl alcohol, Aromatic polyamide,
A spun yarn, a monofilament yarn, or a multi-filament containing one kind or two or more kinds of an acrylic polymer, an olefin polymer, or a vinyl chloride polymer) and an inorganic fiber (for example, a fiber made of glass or carbon) Plain weave, twill weave formed from filament yarn or tape yarn of synthetic resin used for the synthetic fiber,
It is preferable to use a woven fabric such as a ridge weave, a satin weave, an Oxford weave, and a entangled weave. When the antifouling waterproof sheet having excellent heat-sealing property of the present invention is used for an event tent, a permanent membrane structure building, etc., its base cloth is made of polyester, polyamide, aromatic polyamide, or polyvinyl alcohol. Synthetic fibers, such as
Alternatively, it is preferable to use a woven cloth made of an inorganic fiber such as glass or carbon fiber. The basis weight of the fiber cloth for base cloth is preferably in the range of 80 to 550 g / m ² . When the antifouling waterproof sheet having excellent heat-sealing property of the present invention is used for a structure such as a truck hood, a tent, an eaves tent, a tent warehouse, an event tent, and a permanent membrane structure building, its required strength, etc. From the above, the basis weight of the base cloth and the structure may be appropriately set. The fiber cloth for the base cloth may be subjected to a water repellent treatment or an adhesive treatment, if necessary.

In the antifouling waterproof sheet having excellent heat-sealing property of the present invention, the waterproof intermediate layer may contain at least one selected from natural rubber, synthetic rubber, and synthetic resin. As the synthetic rubber, neoprene rubber, chloroprene rubber, silicone rubber, chlorosulfonated polyethylene and the like can be used. As the synthetic resin, vinyl chloride resin, ethylene vinyl acetate copolymer resin, acrylic resin, silicone resin, urethane resin, polyethylene resin, polypropylene resin, polyester resin, fluororesin or the like can be used.

In the antifouling waterproof sheet having excellent heat-sealing property of the present invention, the synthetic resin used for the waterproof intermediate layer preferably contains a thermoplastic resin as a main component, more preferably a vinyl chloride resin. , A thermoplastic urethane resin, or a fluoroolefin resin is used as the main component of the waterproof intermediate layer. The vinyl chloride resin used in the waterproof intermediate layer of the present invention means a vinyl chloride polymer, and a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-acrylic acid ester copolymer, and a vinyl chloride-vinylidene chloride copolymer. A plasticizer or a polymer having a plasticizing action, and a stabilizer, an ultraviolet absorber, a mildew-proofing agent, a flame retardant, a filler, and the like are blended into the combination or the like, or a mixture of two or more thereof. It is a thing.

The phthalate ester plasticizer used as the plasticizer for the vinyl chloride resin is dibutyl phthalate, diethyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, dinonyl phthalate, di-n-decyl. It includes phthalate, diisodecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate and the like. As the polyester plasticizer, adipic acid and glycols such as 2-methyl-1,8-octanediol, 1,2-propanediol, 1,3-butanediol, 2-ethylhexanol, and n-octanol are used. It is possible to use those obtained by esterifying the above. Furthermore, as the trimellitic acid-based plasticizer, tri-2-ethylhexyl trimellilate, triisodecyl trimellilate, or the like can be used. As other plasticizers, pyromellitic acid-based plasticizers such as 2-ethylhexylpyromellilate and biphenyltetracarboxylic acid ester-based plasticizers can be used.

Examples of the polymer having a plasticizing action for vinyl chloride resin include ethylene-vinyl acetate polymer and ethylene-
A polymer prepared by introducing carbon monoxide into an acrylate polymer can be used. These plasticizers and polymers having a plasticizing action can be used alone or in admixture of two or more.
The addition amount of the plasticizer and the polymer having a plasticizing action is from 40 parts by mass to 120 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
It is preferably part by mass.

As the vinyl chloride-based resin stabilizer, calcium / zinc based, barium / zinc based, cadmium / barium based, lead based, organotin laurate based, organotin mercaptite based, epoxy based and the like can be used. The amount of the stabilizer added is 0.5 to 1 with respect to 100 parts by mass of the vinyl chloride resin.
It is preferably 0 part by mass. As the ultraviolet absorber for the vinyl chloride resin, a triazole-based, benzophenone-based, cyanoacrylate-based, salicylic acid-based, hydroquinone-based ultraviolet absorber or the like can be used. Among these, 2- (5-methyl-2-hydroxylphenyl) benzotriazole, 2- (3,5-di-t-butyl-2)
-Hydroxyphenyl) benzotriazole and 2-ethylhexyl-2-cyano3,3-diphenylacrylate are particularly preferably used alone or as a mixture of two or more thereof. For example, 2- (5-methyl-
2-hydroxyphenyl) benzotriazole and 2
-Ethylhexyl-2-cyano 3,3-diphenyl acrylate is effective for preventing the deterioration and coloration of the vinyl chloride resin when used in an amount of 0.5 to 1.0 part by weight per 100 parts by weight of the vinyl chloride resin. is there. As the filler for the vinyl chloride resin, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, magnesium hydroxide or the like can be used. The addition amount of the filler is preferably up to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

As flame retardants for vinyl chloride resins, antimony compounds such as antimony trioxide and antimony pentoxide, calcium zinc molybdate, potassium molybdate,
Molybdenum compounds such as sodium molybdate, calcium molybdate carbonate, and ammonium molybdate can be used. In addition, bromine-based flame retardants such as decabromodiphenyl ether, pentabromomethylbenzene, hexabromobenzene, phosphates such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and chlorinated paraffin are used as flame retardants. it can.

The thermoplastic urethane resin which can be used in the waterproof intermediate layer of the present invention has at least one selected from a diisocyanate compound and a compound containing two or more hydroxyl groups and a functional group capable of reacting with the isocyanate group. It can be selected from those obtained by reacting with a compound. Aromatic, aliphatic, and alicyclic diisocyanate compounds are used as the diisocyanate compound for the thermoplastic urethane-based resin for the waterproof intermediate layer. For example, 2,4-
Tolylene diisocyanate, 2,6-4-tolylene diisocyanate, phenylene diisocyanate, 4,4 '
-Diphenylmethane diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-
Diisocyanates such as diisocyanate, o-, m- or p-xylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane diisocyanate and dicyclohexylmethane diisocyanate are used.

The compound containing two or more hydroxyl groups for the thermoplastic urethane resin has a molecular weight of 300.
1 to 10,000, preferably 500 to 5000, containing a group reactive with diisocyanate,
It can be selected from glycols having 2 to 8 carbon atoms. For example, ethylene, trimethylene, tetramethylene, hexene, propylene glycol, etc., with 4 to 1 carbon atoms
0 saturated aliphatic dicarboxylic acids such as adipic acid, succinic acid, glutaric acid, speric acid and sebacic acid, or aromatic dicarboxylic acids such as phthalic acid and isophthalic acid,
Condensates obtained from terephthalic acid and the like, polyester glycols obtained by copolymerizing alkylene glycol and lactone group, such as polylactone diol, polycaprolactone diol, polyenant lactone diol, etc., and alkylene oxides having 2 to 4 carbon atoms. A condensate, a condensate of an alkylene oxide having 2 to 4 carbon atoms and an alkylene glycol, a polyalkylene glycol having 2 to 4 carbon atoms, a polyalkylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran, and the like are used. Similarly, dihydroxypolyesteramides, dihydroxypolyacetals, dihydroxypolyalkylenes, dihydroxypolycarbonates and the like can be used. In addition to the diol compound, a compound having a functional group capable of reacting with an isocyanate group may be co-condensed as a molecular chain extender. Examples of the molecular chain extender include saturated fatty acids having 2 to 6 carbon atoms. Group glycols, specifically ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, butane 1,2-diol, butane 1,3-diol, butane 1,4-diol, butane 2,3-diol, butane 2,4-diol, hexanediol, etc., or, for example, Aromatic glycols, specifically, 1,4-xylene glycol, phenylene bis-β-hydroxyethyl ether and the like are used. In addition, for example, a small amount of trifunctional or higher functional alcohols, trimethylolpropane, glycerin, hexanetriol and the like may be simultaneously used as a cocondensation component. In the present invention, the thermoplastic urethane-based resin may be one produced by a known method using the above compound.

These thermoplastic urethane-based resins may be used as a mixture of two or more kinds. Above all, it is preferable to use a polycarbonate urethane resin in order to improve weather resistance, hydrolysis resistance and the like. However, the polycarbonate-based urethane resin has a low heat-welding property by a high-frequency welder or the like as compared with other thermoplastic urethane-based resins, and therefore, in order to impart a stable heat-fusing property,
For the back surface where the weather resistance of the waterproof sheet is not considered important, it is preferable to use a polyester-based or polyether-based thermoplastic urethane resin having excellent heat fusion properties such as a high-frequency welder. Stabilizers, ultraviolet absorbers, flame retardants, colorants and the like can be added to these thermoplastic urethane-based resins as appropriate. To form a waterproof intermediate layer with a thermoplastic urethane resin, extruding and thermocompression-bonding the thermoplastic urethane resin filmed by a calender, etc. to the base cloth, or dissolving the thermoplastic urethane resin in a solvent and applying it to the base cloth. And the like can be used.

The fluoroolefin resin used for the waterproof intermediate layer of the antifouling waterproof sheet having excellent heat-sealing property of the present invention is a vinylidene fluoride polymer, a vinylidene fluoride / tetrafluoroethylene copolymer, A vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer can be used. Further, in the present invention, the waterproof intermediate layer may be formed by using two or more kinds of vinyl chloride resin, thermoplastic urethane resin, and fluoroolefin resin.

The outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties of the present invention contains, as a main component,
At least one of a homopolymer and a copolymer containing at least one polymerized unit selected from hydroxyalkyl (meth) acrylate and N-methylol (meth) acrylamide in the main chain polymer segment composed of an acrylic polymer It contains, as a main component resin, one or more kinds of copolymers graft-polymerized as a graft polymer segment. The graft ratio at this time, that is, the molecular weight ratio of the graft polymer segment and the main chain polymer segment,
It is preferably 3: 1 to 2: 3. When the graft ratio is small, the hydrophilicity of the outermost layer of the antifouling fusible resin to be obtained becomes insufficient, and the rain line stain prevention property may not be sufficiently imparted. Further, if the graft ratio is large, the heat-sealing sewability of the antifouling waterproof sheet having excellent heat-sealing property may be deteriorated. The number of carbon atoms of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate polymer unit is preferably 2-8. When it exceeds 8, the hydrophilicity of the outermost layer of the antifouling fusible resin obtained is insufficient, the antifouling property becomes insufficient, and rain streak stains are likely to occur. The molecular weight of the hydroxyalkyl (meth) acrylate polymer and the N-methylol (meth) acrylamide polymer unit is preferably 500 to 50,000. When it is less than 500, the resin strength of the outermost layer of the antifouling fusible resin to be obtained may be insufficient, and the strength of the heat-sealing portion may be insufficient. Also, when it exceeds 50,000, the heat-sealing property of the outermost layer of the antifouling fusible resin to be obtained decreases, and it becomes difficult to heat-bond the antifouling waterproof sheets having excellent heat fusible property. May be.

In the present invention, the resin for the outermost layer of the antifouling fusible resin is, in addition to the main component resin, an additional component resin composed of a different thermoplastic resin, for example, an acrylic resin different from the main component resin, One or more kinds selected from urethane resin and vinylidene fluoride resin may be mixed,
At this time, the addition amount of the additional component resin composed of the different thermoplastic resin of the main component resin is preferably 100 parts by mass or less with respect to 100 parts by mass of the main component resin. If the addition amount exceeds 100 parts by mass, the hydrophilicity of the outermost layer of the antifouling fusible resin obtained is insufficient, and the rain line stain prevention property may not be sufficiently imparted.

In the outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusion property of the present invention, the different acrylic resin which can be mixed with the main resin is acrylic acid or methacrylic acid. It is preferable to select from a polymer having an ester of an acid C1 to C4 alcohol as a main constituent monomer or an acrylic resin containing a copolymer as a main component. The main constituent monomer of such an acrylic ester-based resin is specifically preferably selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate, particularly methyl. Preference is given to using acrylates and methyl methacrylate. As the comonomer of the acrylic resin to be copolymerized with the main constituent monomer, acrylic acid or methacrylic acid C1 is used.
Monomers such as ester of C4 alcohol, vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, and butadiene can be used.

In the outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties of the present invention, the urethane resin mixed with the main component resin is a polymer polyol or polyisocyanate. , And, if necessary, a resin obtained by reacting a chain extender 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,
Aromatic polyisocyanates such as hydrogenated xylylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate, and aliphatic polyisocyanates,
Alicyclic polyisocyanates can be used. 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.

In the outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties of the present invention, the vinylidene fluoride resin mixed with the main component resin is polyvinylidene fluoride alone. Besides one polymer, a polymer containing vinylidene fluoride, for example, a monomer copolymerizable with vinylidene fluoride, for example, one or more kinds of monomers selected from tetrafluoroethylene, trifluoroethylene, fluoroethylene, etc. A copolymer obtained by copolymerizing is used. These copolymers are not limited to random copolymers, and may be graft copolymers. It is also possible to use a mixture containing another resin having good compatibility with these monomers or copolymers. Examples of the resin having good compatibility with such vinylidene fluoride resin include, for example, an acrylic polymer or copolymer mainly composed of methyl methacrylate or methyl acrylate, or a cyanoethylated ethylene-vinyl alcohol copolymer. is there.

In the antifouling waterproof sheet according to the present invention having an excellent heat-fusible property, the outermost layer of the antifouling fusible resin has a thickness of 0.2.
It is preferably from 10 to 10 μm, more preferably from 0.
It is 5 to 5 μm. If this thickness is less than 0.2 μm, the outermost layer of the antifouling fusible resin obtained may not have sufficient hydrophilicity, and the antifouling property may be deteriorated and rain streak stains may easily occur. . When the thickness exceeds 10 μm, cracks are likely to occur in the outermost layer of the antifouling fusible resin when the resulting antifouling waterproof sheet having excellent heat fusible properties is folded,
Or, the appearance and aesthetics of the antifouling waterproof sheet which is excellent in heat-sealing property may be impaired due to the remaining traces of bending.

In the antifouling waterproof sheet having excellent heat-sealing property of the present invention, colloidal silica is contained in the outermost layer of the antifouling fusible resin to form the outermost layer of the antifouling fusible resin. It is possible to further improve the hydrophilicity and thereby further improve the rain line stain prevention property. Colloidal silica is fine particles of silicon dioxide (SiO ₂ ) or a dispersion thereof, and specifically, TT600 of Nippon Aerosil, Snowtex 30 of Nissan Chemical Co., Ltd., Cataloid 20HL of Japan Catalyst, SI-.
30 and the like. The amount of colloidal silica added is 30 with respect to 100 parts by mass of the outermost layer of the antifouling fusible resin.
It is preferable that the content is not more than mass parts. If the addition amount exceeds 30 parts by mass, the heat-sealing property of the obtained antifouling waterproof sheet having excellent heat-sealing property may be insufficient.

In the antifouling waterproof sheet having excellent heat fusible properties of the present invention, when a block isocyanate is contained in the outermost layer of the antifouling fusible resin, when the heat fusible treatment is applied. The durability of the heat-sealed portion can be remarkably improved. The outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties of the present invention is, for example, a vinyl chloride resin used as a waterproofing-imparting intermediate resin layer and having excellent antifusing property. In the dirty waterproof sheet, the outermost layer of the antifouling fusible resin initially has sufficient heat fusibility with the soft vinyl chloride resin intermediate layer forming the lower layer, If exposed to wind, rain, heat, ultraviolet rays, etc. outdoors for a certain period,
The strength of the heat-sealed portion may decrease. On the other hand, if a block isocyanate is contained in the outermost layer of the antifouling fusible resin, when the antifouling waterproof sheet having excellent thermal adhesiveness is heated during thermal fusion, the heat blocks the blocked isocyanate. The agent is dissociated, and the resulting isocyanate is used to cure and crosslink the heat-sealed portion, whereby the durability of the heat-sealed portion can be remarkably enhanced.

In the antifouling waterproof sheet of the present invention having excellent heat-sealing property, a blocked isocyanate is added to the surface opposite to the outermost layer of the antifouling fusible resin, that is, the outermost layer of the back surface. At least one kind of the thermoplastic resin layer is disposed, and the blocking agent is dissociated from the blocked isocyanate by the heat applied to the antifouling waterproof sheet having excellent heat fusion property at the time of heat fusion. It is also possible to cure and crosslink the heat-sealed portion with the isocyanate to remarkably enhance the durability of the heat-sealed portion. An acrylic resin, a urethane resin, and a cyanoethylated ethylene-vinyl alcohol copolymer resin can be used as the thermoplastic resin for the outermost layer on the back surface. The blocked isocyanate used in the present invention, trimethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, or a dimer of tolylene diisocyanate, trimer, etc., methyl alcohol, ethyl alcohol, diethanolamine, caprolactam,
Those blocked with a blocking agent such as methylethylketoxime can be used. The addition amount of such blocked isocyanate is 15% to 150% with respect to the equivalent amount of the isocyanate group and the OH group contained in the outermost layer of the antifouling fusible resin or the thermoplastic resin back surface. preferable. When it is less than 15%, the effect of improving the strength of the heat-sealed portion is insufficient, and when it exceeds 150%, the strength improving effect obtained is saturated. As a method of forming the outermost layer of the antifouling fusible resin containing block isocyanate or the outermost layer of the back surface of the thermoplastic resin containing block isocyanate, a method of applying a solvent solution of a resin may be used. Further, when the solvent is dried after applying the solvent solution of the resin, it is preferable that the temperature is not higher than the dissociation temperature of the blocking agent for the blocked isocyanate. This drying temperature is generally 120 ° C or lower, and more preferably 80 ° C to 110 ° C.

Normally, a truck hood, a tent, an eaves tent,
For heat fusion stitching of antifouling waterproof sheet excellent in heat fusion performed to form a waterproof space using a membrane material for permanent membrane structure such as tent warehouse and event tent,
A hot air heating fusion method, a high frequency internal heat fusion method, a hot iron heat fusion method, an ultrasonic fusion method, a hot plate heating press fusion method, or the like is used. When performing this heat fusion, the antifouling waterproof sheet having excellent heat fusion property is preferably heated to a temperature of 150 ° C or higher, more preferably 150 to 650 ° C, and 150 to 600 ° C. It is even more preferable to heat to. When fusion is performed at a temperature of less than 150 ° C., the dissociation of the blocking agent of the blocked isocyanate added to the outermost layer of the antifouling fusion-bondable resin and the outermost layer of the back surface of the thermoplastic resin and the active hydrogen contained in the resin Occurrence of the reaction of the isocyanate group may be insufficient and the durability of the heat-sealed portion may not be improved.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Description of Test Methods The tests used in the examples and comparative examples of the present invention are as follows. 1. Heat-fusion test (1) Peel strength test for heat-sealed part From the antifouling waterproof sheet excellent in heat-sealing property, vertical 40 cm,
Two 5 cm-wide sample pieces were prepared, superposed so that the front and back sides were aligned, and fused by a high-frequency welder to prepare a heat-welded portion having a vertical length of 30 cm and a width of 4 cm. High frequency welder: YF-700 manufactured by Yamamoto Vinita Co., Ltd.
Type 0, weld bar 4 cm x 30 cm Weld condition: Anode current value of 1.25 A, energizing time of 5 seconds, cooling time of 3 seconds From this heat-sealed portion, a 20 cm long and 3 cm wide peel strength measurement sample was taken. The initial peel strength in the vertical direction and the sunshine weather meter acceleration test (JIS A 141
5-1997 WS type) 1,000 hours later, JIS
It was measured according to the peel test of K 63285.3, and evaluated as follows. Peel strength = 3.0 kgf / 3 cm or more: ○ Less than 3.0 kgf / 3 cm: × (2) Heat-sealing creep resistance heat-resistant creep test From an antifouling waterproof sheet with excellent heat-sealing property, a vertical length of 65 cm,
Two 20 cm wide sample pieces were prepared, and 2.5 cm widths were overlapped from the ends in the horizontal direction so that the front and back sides were aligned, and fusion was performed using a high-frequency welder, and a heat fusion portion was provided at the center in the horizontal direction. A sheet-like sample having a size of 65 cm and a width of 37.5 cm was prepared. High frequency welder: YF-700 manufactured by Yamamoto Vinita Co., Ltd.
Type 0, weld bar 2.5 cm × 65 cm Weld condition: Anode current value of 1.25 A, energizing time of 5 seconds, cooling time of 3 seconds Cut from this sheet-shaped sample in a width direction of 3 cm,
A heat-resistant creep test sample having a width of 3 cm and a length of 37.5 cm having a heat-sealed portion in the center was prepared and subjected to initial and sunshine weather meter acceleration tests (JIS A 1415-19).
97 WS type) 1,000 hours later, JIS K 68
According to 59-1974, 1/10 at an ambient temperature of 60 ° C
Load (15kgf / 3cm) and 1/2 load (75kgf / 3)
cm) and the state of the heat-sealed portion after 6 hours was observed and evaluated as follows. No abnormality in the heat-sealed part under 1/2 load: ◎ No abnormality in the heat-sealed part under 1/10 load: ○ ((Company) Membrane Material Performance Evaluation Criteria of Japan Membrane Structure Association) : × 2. The antifouling test sample was installed facing south, with an inclination angle of 30 degrees, and vertically.
The sample was subjected to a continuous outdoor exposure test for one year, and the stain resistance of the sample and the generation state of rain streaks were visually observed and the color difference ΔE on the sample surface was measured, and evaluated in four levels as follows.

(Example 1) Two 20-count polyester spun yarns were twisted, and this yarn was woven at a density of 50 vertical / inch and 48 horizontal / inch, and the basis weight was 250 g / m.
² base fabrics were obtained. Both sides of the base cloth are coated with 170 g / m ^{2 of} vinyl chloride paste sol having the composition shown below at a rate of 170 g / m ² per side, and heat-treated at 180 ° C. for 2 minutes,
Both sides were pressed with a mirror surface roll, cast on a mirror surface, and cooled to prepare a waterproof sheet. Vinyl paste sol composition Ingredient parts by paste polyvinyl chloride resin chloride (Geon 121) 100 plasticizer (DOP) 70 liquid stabilizer (Ba-St based) 3 UV absorber 1 filler (calcium carbonate) 20 flame retardant ( Antimony trioxide) 20 Colorant (pigment, titanium oxide) 10 Furthermore, a solution-type coating solution having the following composition as the outermost layer of the antifouling fusible resin is applied to the mirror-cast and cooled surface of this waterproof sheet as a gravure coater. Coated with 1
The outermost layer of the antifouling fusible resin was formed by drying with hot air at 10 ° C for 1 minute to obtain an antifouling waterproof sheet having excellent thermal fusibility. The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 1. Bokitanasei fusible resin top composition Ingredient weight of the outer layer coating liquid portion hydroxyethyl methacrylate polymer grafted methacrylate resin 10 methylcellosolve 50 MEK 85 IPA 35

(Example 2) In the same manner as in Example 1, an antifouling waterproof sheet having excellent heat-sealing property was produced. However, the composition of the coating liquid for the outermost layer of the antifouling fusible resin was changed as follows. The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 1. Composition formed of Bokitanasei fusible resin outermost layer coating liquid content mass parts N- methylolacrylamide polymer grafted methacrylate resin 10 methylcellosolve 50 MEK 85 IPA 35

(Example 3) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat fusion property was produced. However, the composition of the coating liquid for the outermost layer of the antifouling fusible resin was changed as follows. The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 1. Bokitanasei fusible resin outermost layer coating liquid composition Ingredient parts by hydroxymethyl methacrylate N- methylol acryl amide copolymer grafted methacrylate resin 10 methylcellosolve 50 MEK 85 IPA 35

(Example 4) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat fusion property was produced. However, the composition of the coating liquid for the outermost layer of the antifouling fusible resin was changed as follows. The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 1. Bokitanasei fusible resin top composition Ingredient weight of the outer layer coating liquid portion hydroxyethyl methacrylate polymer grafted methacrylate resin 10 Methyl methacrylate resin 5 Methyl cellosolve 50 MEK 85 IPA 35

(Example 5) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat fusion property was produced. However, the composition of the coating liquid for the outermost layer of the antifouling fusible resin was changed as follows. The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 1. Heat obtained in Bokitanasei fusible resin composition Ingredient parts by weight of the outermost layer coating solution for N- methylolacrylamide polymer grafted methacrylate resin 10 Methyl methacrylate resin 5 Methyl cellosolve 50 MEK 85 IPA 35 Examples 1-5 As shown in Table 1, the antifouling antifouling waterproof sheet exhibiting excellent fusing property exhibits excellent heat fusing property and excellent antifouling property in outdoor exposure, and has a particularly small amount of fouling in the vertical portion, It was a useful antifouling waterproof sheet having excellent heat-sealing property.

(Example 6) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat fusion property was produced. However, colloidal silica was added to the outermost layer of the antifouling fusible resin, and the composition of the coating liquid for the outermost layer of the antifouling fusible resin was changed as follows. The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 1. Bokitanasei fusible resin outermost layer coating liquid composition Ingredient mass parts hydroxyethyl methacrylate polymer grafted methacrylate resin 10 methylcellosolve 50 Snowtex MEK-ST (colloidal silica 30% MEK dispersion) 10 MEK 85 IPA 35 As shown in Table 1, the antifouling waterproof sheet excellent in heat fusion property obtained in Example 6 was further improved in antifouling property as compared with Example 1 (ΔE = 2 or less), and is extremely It was a stain-proofing waterproof sheet having excellent heat-sealing property and excellent anti-staining property.

(Example 7) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat fusion property was produced. However, adding block isocyanate to the outermost layer of the antifouling fusible resin,
The composition of the coating solution for the outermost layer of the antifouling fusible resin was changed as follows. The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 1. Bokitanasei fusible composition Ingredient resin outermost layer coating liquid mass parts hydroxyethyl methacrylate polymer grafted methacrylate resin 10 methylcellosolve 50 oxime blocked (hexamethylene diisocyanate) isocyanurate 3 MEK 85 IPA 35

(Example 8) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat fusion property was produced. However, as the outermost layer of the thermoplastic resin containing the block sisocyanate on the outermost layer on the back side, a solvent diluent of the resin composition having the following composition is applied using a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form. did. Thermoplastic resin backside top composition Ingredients for the outer layer coating liquid parts by mass of methyl methacrylate resin 10 oxime blocked (hexamethylene diisocyanate) isocyanurate 3 toluene 30 MEK 70

(Example 9) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat-sealing property was produced. However, a layer containing a block dissocyanate is formed in the outermost layer of the antifouling fusible resin by the following coating solution composition for the outermost layer of the antifouling fusible resin, and the back surface of the thermoplastic resin contains the block isocyanate. The outermost layer was formed by the following coating composition for the outermost layer of the thermoplastic resin. Bokitanasei fusible composition Ingredient resin outermost layer coating liquid mass parts hydroxyethyl methacrylate polymer grafted methacrylate resin 10 methylcellosolve 50 oxime blocked (hexamethylene diisocyanate) isocyanurate 3 MEK 85 IPA 35 thermoplastic resin backside Composition of the coating liquid for the outermost layer Composition parts by mass Methyl methacrylate resin 10 Oxime blocked (hexamethylene isocyanate) Isocyanurate 3 Toluene 30 MEK 70 Antifouling and waterproof having excellent heat-sealing properties obtained in Examples 7 to 9 As shown in Table 1, the sheet has further improved peel strength at the heat-sealed portion as compared with Example 1 (4.0 kgf / 3 cm or more after 1000 hours of accelerated weathering resistance), and the durability of the heat-sealed portion is improved. Remarkably excellent (heat-resistant creep, 60 ° C, 1/2 load, 6
It was an antifouling waterproof sheet which was excellent in antifouling property and was very useful in heat fusion.

Comparative Example 1 A waterproof sheet was prepared in the same manner as in Example 1. However, the outermost layer of the antifouling fusible resin was not formed. This waterproof sheet was subjected to the above test. The results are shown in Table 2. The tarpaulin obtained in Comparative Example 1 is significantly inferior in antifouling property to the antifouling waterproof sheet excellent in heat fusion property obtained in Example 1, and is practically used as an antifouling waterproof sheet. It was not suitable.

(Comparative Example 2) In the same manner as in Example 1, an antifouling waterproof sheet excellent in heat fusion property was produced. However, the composition of the coating liquid for the outermost layer of the antifouling fusible resin was as follows.
The antifouling waterproof sheet having excellent heat-sealing property was subjected to the above test. The results are shown in Table 2. Bokitanasei fusible resin antifouling waterproof sheet excellent in thermal adhesiveness obtained in most compositions Ingredient weight of the outer layer coating liquid of methyl methacrylate resin 12 Toluene 35 MEK 65 Comparative Example 2 Example 1 Compared with the antifouling waterproof sheet with excellent heat-sealing property obtained in step 1, the antifouling property is inferior, especially the rain streaks on the vertical part are noticeable, and the antifouling waterproof sheet with excellent heat-sealing property It was not suitable for practical use.

Comparative Example 3 A waterproof sheet was prepared in the same manner as in Example 1. However, after forming adhesive layers on both front and back surfaces of the waterproof sheet, a vinylidene fluoride resin layer was formed on the outermost layers on the front and back surfaces. This antifouling waterproof sheet was subjected to the above test.
The results are shown in Table 2. <Composition A> adhesive composition formed of the treatment liquid content mass of methyl methacrylate resin 12 Toluene 35 MEK 65 <Composition B> top- antifouling fusible resin outermost layer coating solution composition Ingredient mass parts of polyvinylidene fluoride 12 toluene 35 MEK 55 DMF 10 The antifouling waterproof sheet obtained in Comparative Example 3 has an antifouling property on a 30 ° inclined surface as compared with the antifouling waterproof sheet excellent in heat fusion property obtained in Example 1. Although it was almost at the same level, the dirt on the vertical streak was easily noticeable, and the durability of the heat-sealed part was inferior, which is an insufficient level as an antifouling waterproof sheet with excellent heat-sealed property. It was

Comparative Example 4 An antifouling waterproof sheet was prepared in the same manner as in Example 1. However, the following photocatalytic titanium oxide coating layer was formed in place of the outermost layer of the antifouling fusible resin. This antifouling waterproof sheet was subjected to the above test. The results are shown in Table 2. Formation of Photocatalytic Titanium Oxide Coating Layer An adhesive / protective layer treatment liquid having the following composition A was applied on the surface of the waterproof sheet with a gravure coater at an application amount of 15 g / m ² , dried and cooled at 100 ° C. for 1 minute. , 1.5 g /
An adhesion / protection layer of m ² was formed. A coating solution for forming a photocatalyst antifouling layer having the following composition B was further applied thereon with a coating amount of 15 g / m ² with a gravure coater, dried at 100 ° C. for 1 minute and then cooled to 1.5 g / m ² The photocatalyst antifouling layer was formed to produce an antifouling waterproof sheet. <Composition A> Adhesive / protective layer treatment liquid composition : parts by mass Silicon content Ethanol-ethyl acetate (50/50 mass ratio) solution containing 8 mass% (solid content) of 3 mol% acrylic silicon resin 100 Methyl as polysiloxane 20% ethanol solution of silicate MS51 (Colcoat Co., Ltd.) 8 γ-glycidoxypropyl trimethoxysilane as a silane coupling agent 1 <Composition B> Photocatalyst treatment liquid composition : mass part Titanium oxide content corresponds to 10 mass% Water-ethanol (50/50 mass ratio) dispersion in which nitric acid acidic titanium oxide sol is dispersed 50 Water-ethanol (50/50 mass ratio) dispersion in which nitric acid acidic silica sol corresponding to silicon oxide content of 10 mass% is dispersed Liquid 50 The antifouling waterproof sheet obtained in Comparative Example 4 was obtained in Example 1 and has an excellent antifouling property against heat fusion. Compared with the waterproof sheet, it shows more excellent antifouling property (ΔE = 2 or less), but it is not suitable for practical use because it is not fused by the conventional heat fusion method.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

EFFECTS OF THE INVENTION The antifouling waterproof sheet having excellent heat-sealing property of the present invention can be easily heat-sealed by using the conventional heat-sealing method, and the durability of the heat-sealing portion can be improved. It also has excellent antifouling properties, and is extremely effective for preventing rain streaks on vertical surfaces in particular, and is used in a wide range of applications such as membrane structure buildings, eaves tents, and truck hoods.

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[Procedure amendment]

[Submission date] December 19, 2001 (2001.12.
19)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

The phthalate ester plasticizer used as the plasticizer for the vinyl chloride resin is dibutyl phthalate, diethyl phthalate, diheptyl phthalate, di-
2-ethylhexyl phthalate, dinonyl phthalate,
Di-n-decyl phthalate, diisodecyl phthalate,
It includes ditridecyl phthalate, butylbenzyl phthalate and the like. As the polyester plasticizer, adipic acid and glycols such as 2-methyl-1,8-octanediol, 1,2-propanediol, 1,3-butanediol, 2-ethylhexanol, and n-octanol are used. It is possible to use those obtained by esterifying the above. Furthermore, as the trimellitic acid-based plasticizer, tri-2-ethylhexyl trimellilate, triisodecyl trimellilate, or the like can be used. As other plasticizers, pyromellitic acid-based plasticizers such as 2-ethylhexylpyromellilate and biphenyltetracarboxylic acid ester-based plasticizers can be used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

The compound containing two or more hydroxyl groups for the thermoplastic urethane resin has a molecular weight of 300.
1 to 10,000, preferably 500 to 5000, containing a group reactive with diisocyanate,
It can be selected from glycols having 2 to 8 carbon atoms. For example, ethylene, trimethylene, tetramethylene, hexene, propylene glycol, etc., with 4 to 1 carbon atoms
0 saturated aliphatic dicarboxylic acids such as adipic acid, succinic acid, glutaric acid, speric acid and sebacic acid, or aromatic dicarboxylic acids such as phthalic acid and isophthalic acid,
Condensates obtained from terephthalic acid and the like, polyester glycols obtained by copolymerizing alkylene glycol and lactone group, such as polylactone diol, polycaprolactone diol, polyenant lactone diol, etc., and alkylene oxides having 2 to 4 carbon atoms. A condensate, a condensate of an alkylene oxide having 2 to 4 carbon atoms and an alkylene glycol, a polyalkylene glycol having 2 to 4 carbon atoms, a polyalkylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran, and the like are used. Similarly, dihydroxypolyesteramides, dihydroxypolyacetals, dihydroxypolyalkylenes, dihydroxypolycarbonates and the like can be used. In addition to the diol compound, a compound having a functional group capable of reacting with an isocyanate group may be co-condensed as a molecular chain extender. Examples of the molecular chain extender include saturated fatty acids having 2 to 6 carbon atoms. Group glycols, specifically ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, butane 1,2-diol, butane 1,3-diol, butane 1,4-diol, butane 2,3-diol, butane 2,4-diol, hexanediol, etc., or, for example, Aromatic glycols, specifically, 1,4-xylene glycol, phenylene bis-β-hydroxyethyl ether and the like are used. In addition, for example, a small amount of trifunctional or higher functional alcohols, trimethylolpropane, glycerin, hexanetriol and the like may be simultaneously used as a cocondensation component. In the present invention, the thermoplastic urethane-based resin may be one produced by a known method using the above compound.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

The outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties of the present invention contains, as a main component,
At least one of a homopolymer and a copolymer containing at least one polymerized unit selected from hydroxyalkyl (meth) acrylate and N-methylol (meth) acrylamide in the main chain polymer segment composed of an acrylic polymer It contains, as a main component resin, one or more kinds of copolymers graft-polymerized as a graft polymer segment. The graft ratio at this time, that is, the molecular weight ratio of the graft polymer segment and the main chain polymer segment,
It is preferably 3: 1 to 2: 3. When the graft ratio is small, the hydrophilicity of the outermost layer of the antifouling fusible resin to be obtained becomes insufficient, and the rain line stain prevention property may not be sufficiently imparted. Further, if the graft ratio is large, the heat-sealing sewability of the antifouling waterproof sheet having excellent heat-sealing property may be deteriorated. The number of carbon atoms of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate polymer unit is preferably 2-8. When it exceeds 8, the hydrophilicity of the outermost layer of the antifouling fusible resin obtained is insufficient, the antifouling property becomes insufficient, and rain streak stains are likely to occur. The molecular weight of the graft polymer segment is 500 to 50.
It is preferably 000. When it is less than 500, the resin strength of the outermost layer of the antifouling fusible resin to be obtained may be insufficient, and the strength of the heat-sealing portion may be insufficient. Also, when it exceeds 50,000, the heat-sealing property of the outermost layer of the antifouling fusible resin to be obtained decreases, and it becomes difficult to heat-bond the antifouling waterproof sheets having excellent heat fusible property. May be.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

In the outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties of the present invention, the urethane resin mixed with the main component resin is a polymer polyol or polyisocyanate. , And, if necessary, a resin obtained by reacting a molecular chain extender can be used. As the polymer polyol used for such urethane-based resin, polyester-based polyol having hydroxyl groups at both ends of the molecular chain, polyether-based polyol, polycarbonate-based polyol, polyester amide polyol,
Alternatively, an acrylate-based polyol or the like can be used. As the polyisocyanate, aromatic polyisocyanates such as 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate, and aliphatic polyisocyanates, Alicyclic polyisocyanates can be used.
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.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

In the outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties of the present invention, the vinylidene fluoride resin mixed with the main component resin is polyvinylidene fluoride alone. Besides one polymer, a polymer containing vinylidene fluoride, for example, a monomer copolymerizable with vinylidene fluoride, for example, one or more kinds of monomers selected from tetrafluoroethylene, trifluoroethylene, fluoroethylene, etc. A copolymer obtained by copolymerizing is used. These copolymers are not limited to random copolymers, and may be graft copolymers. It is also possible to use a mixture in which another resin having good compatibility with these homopolymers or copolymers is added. Examples of the resin having good compatibility with such vinylidene fluoride resin include, for example, an acrylic polymer or copolymer mainly composed of methyl methacrylate or methyl acrylate, or a cyanoethylated ethylene-vinyl alcohol copolymer. is there.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

In the antifouling waterproof sheet according to the present invention having an excellent heat-fusible property, the outermost layer of the antifouling fusible resin has a thickness of 0.2.
It is preferably from 10 to 10 μm, more preferably from 0.
It is 5 to 5 μm. If this thickness is less than 0.2 μm, the outermost layer of the antifouling fusible resin obtained may not have sufficient hydrophilicity, and the antifouling property may be deteriorated and rain streak stains may easily occur. . When the thickness exceeds 10 μm, cracks are likely to occur in the outermost layer of the antifouling fusible resin when the resulting antifouling waterproof sheet having excellent heat fusible properties is folded,
Otherwise, the appearance and aesthetics of the antifouling waterproof sheet having excellent heat-sealing property may be impaired due to the remaining traces of bending.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

(Example 1) 20th polyester spinning
Twist two threads, and use 50 threads / inch for this thread
Woven with a density of 48 strands / inch and a basis weight of 250 g / m
² I got the base cloth. The composition shown below on both sides of this base cloth
170g / m per side of vinyl chloride paste sol² Without
Coating and heat treating it at 180 ℃ for 2 minutes,
Both sides are pressed with a mirror roll to cast a mirror surface and then cooled.
To produce a waterproof sheet.   Vinyl chloride paste sol composition             Component                                            Mass part   Polyvinyl chloride resin for paste (Zeon 121) 100   Plasticizer (DOP) 70   Liquid stabilizer (Ba-St type) 3   UV absorber 1   Filler (calcium carbonate) 20   Flame retardant (antimony trioxide) 20   Colorants (pigments, titanium oxide) 10 Furthermore, the mirror-cast and cooled surface of this tarpaulin
In addition, as the outermost layer of the antifouling fusible resin,
Apply the liquid coating solution with a gravure coater and
Dry for 1 minute with hot air at 10 ° C
Form a layer to obtain an antifouling waterproof sheet with excellent heat fusion properties
It was This antifouling waterproof sheet with excellent heat fusion property was tested
I went to The results are shown in Table 1.   Composition of coating liquid for outermost layer of antifouling fusible resin             Component                                            Mass part   Hydroxyethyl methacrylate polymer graft   Methyl methacrylate resin 10   Methyl cellosolve 50   MEK 85   IPA 35

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

Comparative Example 3 A waterproof sheet was prepared in the same manner as in Example 1. However, after forming adhesive layers on both front and back surfaces of the waterproof sheet, a vinylidene fluoride resin layer was formed on the outermost layers on the front and back surfaces. This antifouling waterproof sheet was subjected to the above test.
The results are shown in Table 2. <Composition A> adhesive composition formed of the treatment liquid content mass of methyl methacrylate resin 12 Toluene 35 MEK 65 <Composition B> top- antifouling fusible resin outermost layer coating solution composition Ingredient mass parts of polyvinylidene fluoride 12 toluene 35 MEK 55 DMF 10 The antifouling waterproof sheet obtained in Comparative Example 3 has an antifouling property on a 30 ° inclined surface as compared with the antifouling waterproof sheet excellent in heat fusion property obtained in Example 1. Although it was almost at the same level, the dirt on the vertical streak was easily noticeable, and the durability of the heat-sealed part was inferior, which is an insufficient level as an antifouling waterproof sheet with excellent heat-sealed property. It was

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Comparative Example 4 An antifouling waterproof sheet was prepared in the same manner as in Example 1. However, the following photocatalytic titanium oxide coating layer was formed in place of the outermost layer of the antifouling fusible resin. This antifouling waterproof sheet was subjected to the above test. The results are shown in Table 2. Formation of Photocatalytic Titanium Oxide Coating Layer An adhesive / protective layer treatment liquid having the following composition A was applied on the surface of the waterproof sheet with a gravure coater at an application amount of 15 g / m ² , dried and cooled at 100 ° C. for 1 minute. , 1.5 g /
An adhesion / protection layer of m ² was formed. A coating solution for forming a photocatalyst antifouling layer having the following composition B was further applied thereon with a coating amount of 15 g / m ² with a gravure coater, dried at 100 ° C. for 1 minute and then cooled to 1.5 g / m ² The photocatalyst antifouling layer was formed to produce an antifouling waterproof sheet. <Composition A> Adhesive / protective layer treatment liquid composition : parts by mass Silicon content Ethanol-ethyl acetate (50/50 mass ratio) solution containing 8 mass% (solid content) of 3 mol% acrylic silicon resin 100 Methyl as polysiloxane 20% ethanol solution of silicate MS51 (Colcoat Co., Ltd.) 8 γ-glycidoxypropyl trimethoxysilane as a silane coupling agent 1 <Composition B> Photocatalyst treatment liquid composition : mass part Titanium oxide content corresponds to 10 mass% Water-ethanol (50/50 mass ratio) dispersion in which nitric acid acidic titanium oxide sol is dispersed 50 Water-ethanol (50/50 mass ratio) dispersion in which nitric acid acidic silica sol corresponding to silicon oxide content of 10 mass% is dispersed Liquid 50 The antifouling waterproof sheet obtained in Comparative Example 4 has the antifouling property excellent in heat fusion property obtained in Example 1. Compared with the waterproof sheet, it shows more excellent antifouling property (ΔE = 2 or less), but it is not suitable for practical use because it is not fused by the conventional heat fusion method.

Continued front page    F-term (reference) 4F100 AA08 AA20C AA21 AA29                       AH05B AK01B AK01D AK15B                       AK25C AK26C AK41 AK51B                       AK51D AL04C AL05C AL06B                       AN01B AN02B BA03 BA04                       BA10C BA10D CA04 CA05                       CA08 CA13 CA23 CB01C                       CB01D DG11A EC03 EH46                       GB07 GB31 GB90 JB16C                       JB16D JD05B JL06C JL12C

Claims (12)

[Claims] 1. A base cloth made of a fiber cloth, a waterproof intermediate layer formed on at least one surface of the base cloth, and an antifouling heat-sealing property formed on the waterproof intermediate layer. It has an antifouling fusible resin outermost layer containing a resin as a main component, and the resin for the antifouling fusible resin outermost layer is a main chain polymer segment made of an acrylic polymer, and a hydroxyalkyl (meth ) A copolymer in which at least one of a homopolymer and a copolymer containing at least one polymerized unit selected from acrylate and N-methylol (meth) acrylamide is graft-copolymerized as a graft polymer segment. An antifouling waterproof sheet having excellent heat-sealing properties, which comprises at least one resin as a main component resin. 2. The antifouling waterproof sheet according to claim 1, wherein the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate polymerized unit contains 2 to 8 carbon atoms. 3. The antifouling waterproof sheet according to claim 1 or 2, wherein the outermost layer of the antifouling fusible resin further contains colloidal silica. 4. The antifouling waterproof sheet according to claim 1, wherein the outermost layer of the antifouling fusible resin further contains a blocked isocyanate. 5. The antifouling fusible resin outermost layer contains the main component resin and an additional component resin which is different from the main component resin and is made of at least one thermoplastic resin. An antifouling waterproof sheet having excellent heat-sealing property according to item 1. 6. The protective layer having excellent heat-sealing property according to claim 1, wherein the waterproof intermediate layer contains at least one selected from natural rubber, synthetic rubber and synthetic resin. Dirty tarpaulin. 7. The heat according to claim 6, wherein the waterproof intermediate layer synthetic resin contains at least one selected from a vinyl chloride resin, a thermoplastic urethane resin, and a fluoroolefin resin. Antifouling waterproof sheet with excellent fusion properties. 8. The waterproof intermediate layer and the antifouling fusible resin outermost layer are formed on the surface of the base fabric, and a thermoplastic resin back outermost layer containing a blocked isocyanate is further formed on the back surface thereof. The antifouling waterproof sheet according to any one of claims 1 to 7, which is excellent in heat fusion property. 9. The antifouling waterproof sheet according to claim 1, wherein the outermost layer of the antifouling fusible resin is formed by a coating method. . 10. The antifouling waterproof sheet according to claim 8 or 9, wherein the outermost layer of the back surface of the thermoplastic resin containing the blocked isocyanate is formed by a coating method. 11. At least a part of the outermost layer of the antifouling fusible resin of the antifouling waterproof sheet having excellent heat fusible properties according to any one of claims 1 to 8, A heat-sealed sewn product of an antifouling waterproof sheet, which is obtained by stacking a part of different kinds of sheets on each other and subjecting the sheets to heat-sealing. 12. The method for sewing heat-sealing antifouling waterproof sheet according to claim 11, wherein the heat-sealing treatment is performed at a temperature of 150 to 650 ° C.