JP2017122051A - Film material for tent structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film material for a tent structure which can suppress occurrence of mold or algae for a long period of time to the minimum so as to prevent appearance contamination of the tent structure caused by occurrence of the mold or the algae.SOLUTION: In a flexible sheet having a soft vinyl chloride resin coating layer on at least one surface while using a fiber fabric as a base material, the soft vinyl chloride resin coating layer contains one or more chelate complexes selected from a silver ligand, a copper ligand, a zinc ligand and a nickel ligand, and an antibacterial organic compound and stabilizes an antibacterial effect, and the chelate complex and/or the antibacterial organic compound are used which are carried on inorganic porous particles, as needed, and thereby the antibacterial effect is stabilized and kept for a long period of time.SELECTED DRAWING: None

Description

  The present invention relates to a technique for maintaining the beauty of a tent structure. Specifically, the present invention relates to a medium to large tent structure (stadium roof, dome stadium, openable roof dome, pavilion, etc.), awning tent structure (public Tent structures such as facility monuments, station building roofs, connecting aisle roofs, arcade roofs, for shops, and residences), internally-lit tent structures (such as electric signs, video projection domes, art moldings, etc.) Excellent waterproofing and algae-proof properties suitable for tent structures that can prevent long-term contamination of the tent structure due to the generation of soot and algae. It relates to the film material.

  General-purpose sheet material used for tent structures is a composite sheet material obtained by coating fiber woven fabric with a soft compounded vinyl chloride resin composition on the surface. These are tent structures. And has a durability of 10 to 20 years. However, since the vinyl chloride resin of soft blending contains a large amount of plasticizer in the blending, the plasticizer bleeds on the surface of the sheet-like film material as time passes, and dust gradually accumulates on the bleed plasticizer, There is a problem that the sheet-like film material is soiled. For this reason, the surface of the soft film-form vinyl chloride resin sheet film material is provided with a coating of acrylic resin, urethane resin, fluorine resin, etc. to control the bleed of the plasticizer and ensure the antifouling effect. The means to do is common.

  Since these tent structures are designed in various design forms depending on applications and scales, the tent structures are three-dimensional structures that include various horizontal portions, vertical portions, arch portions, and the like made of sheet-like film materials and have various useful lives. In these tent structures, dust dirt accumulates over the surface of the sheet-like film material depending on the shape, but the larger and more complex the tent structure, the greater the cleaning that the person climbs, The actual situation is that the cleaning timing is after the dirt starts to become noticeable. By the way, every time the summer when the temperature of the sheet-like film material constituting the tent structure is 50 ° C. or more and the softening of the soft vinyl chloride resin is maximized, dust deposits adhere to the surface of the sheet-like film material. Therefore, it becomes sediment dirt that does not easily flow down in the case of rainfall. This accumulated dirt becomes a fungal bed of spore and algae spores and causes generation of cocoons and algae in the tent structure. By leaving the cocoons and algae, the mycelium erodes (secrets) on the surface of the sheet-like membrane material. Even if the tent structure is later cleaned by erosion by an enzyme, it becomes a trace of deterioration, which is a cause of deterioration of the appearance of the tent structure.

  For countermeasures against wrinkles and algae in these tent structures, it is effective to add an organic antifungal agent to the sheet film material, and the organic antifungal agent sequentially bleeds on the sheet surface together with the plasticizer, Efficiently exhibits anti-fungus and anti-algae effects, but it deteriorates with UV rays, elutes in the rain, and the organic anti-fungal agent escapes from the sheet-like membrane material over a long period of use, thus preventing anti-fungus and anti-algae Have the problem of gradually losing the effect. On the other hand, in a kneaded blended system of inorganic antifungal agents in which a metal element such as silver is supported on the surface of porous ceramic particles such as zeolite and hydroxyapatite, the porous ceramic particles themselves become a non-bleeding filler. The successive filling of the metal element to the sheet surface becomes inefficient, and there is a tendency that the fungicidal and algal resistant properties are gradually lowered. Therefore, an antibacterial effect using a metal element such as silver and a phenolic compound as an antibacterial composition having a long-term stable antibacterial effect due to a metal element such as silver and preventing discoloration (Patent Document 1), silver An organic antibacterial agent composed of a colloidal solution of metal oxide and ethylenediaminetetraacetic acid (Patent Document 2), silver oxide and phytic acid dissolved in an aqueous solvent, and a chelating agent such as ethylenediaminetetraacetic acid Complexes such as aqueous complex solutions (Patent Document 3) have been proposed to ensure long-term stability and durability, but liquid complexes are poorly compatible with soft compounded vinyl chloride resins containing plasticizers, resulting in poor mixing. It is practically difficult to use. Therefore, as a film material made of a vinyl chloride resin by soft blending for producing a film material for a tent structure, there has been a demand for a film material particularly capable of long-term and stable antifungal / algae-proof effects.

JP-A-6-227924 JP 2008-94738 A JP 2010-202611 A

  The present invention provides a membrane material for a tent structure capable of minimizing the generation of wrinkles and algae so that the tent structure does not cause appearance contamination due to the generation of wrinkles and algae. It is something to try.

  As a result of repeated research and examination in view of the above-mentioned present situation, the present invention provides a flexible sheet having a soft vinyl chloride resin coating layer on at least one surface of a textile fabric as a base material. Including at least one chelate complex selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand, and an antifungal organic compound. As a membrane material for a tent structure, the present invention has been completed by finding that the problem of improving the sustainability of the antifungal effect of suppressing drought and algae to a minimum for a long time can be solved.

  That is, the membrane material for a tent structure of the present invention is a flexible sheet having a textile fabric as a base material and having a soft vinyl chloride resin coating layer on at least one surface thereof, and the soft vinyl chloride resin coating layer has a silver coating. It is preferable to include at least one chelate complex selected from a ligand, a copper ligand, a zinc ligand, and a nickel ligand, and an antifungal organic compound. This stabilizes metals and metal ions such as silver, copper, zinc, and nickel, making it difficult for them to be discharged out of the system. A suitable film material can be obtained.

  In the membrane material for a tent structure of the present invention, the ligand of the chelate complex is one or more selected from amino acids, ethylenediamine, triethylenetetramine, piperidine, ethyleneamineacetic acid, pyrithione, phenanthroline, porphyrin, and crown ether. It is preferable that This stabilizes metals and metal ions such as silver, copper, zinc, and nickel, making it difficult for them to be discharged out of the system. A suitable film material can be obtained.

  In the membrane material for a tent structure of the present invention, the chelate complex includes mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, silicic acid. It is preferably supported on one or more inorganic porous particles selected from calcium, magnesium aluminate silicate, diatomaceous earth, and these silane coupling agent-treated products. This makes it difficult for the chelate complex to be discharged out of the system, and by exhibiting sustained release, it is possible to obtain a membrane material suitable for a tent structure capable of effectively suppressing the generation of soot and algae for a long period of time. it can.

  In the film material for a tent structure of the present invention, the antifungal organic compound is an imidazole compound, a thiazole compound, an isothiazoline compound, a pyridine compound, a triazine compound, a triazole compound, an N-haloalkylthio compound, It is preferably at least one selected from quaternary ammonium salt compounds and organometallic compounds. As a result, it is possible to obtain a membrane material suitable for a tent structure that can effectively suppress generation of cocoons and algae for a long period of time.

  In the membrane material for a tent structure of the present invention, the antifungal organic compound is mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina It is preferably supported on one or more inorganic porous particles selected from calcium silicate, magnesium aluminate silicate, diatomaceous earth, and treated products of these silane coupling agents. As a result, it becomes difficult for the antifungal organic compound to be discharged out of the system, and by developing sustained release, a membrane material suitable for a tent structure capable of effectively suppressing the generation of soot and algae for a long period of time. Can be obtained.

  In the tent structure film material of the present invention, a photocatalyst substance-containing antifouling layer is formed on at least one surface of the soft vinyl chloride resin coating layer, and the photocatalyst substance contained in the photocatalyst substance-containing antifouling layer contains titanium oxide, It is preferably at least one selected from titanium peroxide (peroxotitanic acid), zinc oxide, tin oxide, strontium titanate, tungsten oxide, and bismuth oxide. Effectively self-cleaning dust dirt by oxidation / reduction action of photocatalyst substance (by washing by rain due to hydrophilicity of antifouling layer by photocatalyst and decomposition action of soot and algae by photocatalyst) It is possible to obtain a membrane material for a tent structure that is effective and can be suppressed for a long period of time.

  The film material for a tent structure of the present invention is one or more chelate complexes in which the photocatalytic substance-containing antifouling layer is selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand It is preferable to contain. Effectively self-cleaning dust dirt by oxidation / reduction action of photocatalyst substance (by washing by rain due to hydrophilicity of antifouling layer by photocatalyst and decomposition action of soot and algae by photocatalyst) to reduce generation of soot and algae It is possible to obtain a membrane material for a tent structure that is effective and can be suppressed for a longer period of time.

  In the film material for tent structure of the present invention, the chelate complex contained in the photocatalyst substance-containing antifouling layer contains mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotal Supported on one or more inorganic porous particles selected from sites, hydroxyapatite, silica alumina, calcium silicate, magnesium aluminate silicate, diatomaceous earth, and these silane coupling agent treated products preferable. This effectively cleans up the dust dirt (by washing with rain due to the hydrophilicity of the antifouling layer by the photocatalyst and the decomposition action of soot and algae by the photocatalyst), and at the same time, the chelate complex becomes difficult to be discharged out of the system. Moreover, by exhibiting sustained release properties, it is possible to obtain a membrane material suitable for a tent structure that can effectively suppress generation of cocoons and algae for a long period of time.

  According to the present invention, since a membrane material for a tent structure that suppresses generation of moths and algae to a minimum for a long period of time can be obtained, the membrane material of the present invention can be used for medium to large tent structures (stadium roofs, dome stadiums). , Openable roof dome, pavilion, etc.), awning tent structure (public facilities monument, station building roof, access passage roof, arcade roof, for shops, residences, etc.), internally illuminated tent structure (lighted signboard, video) It can be widely used for tent structures (projection dome, art molding, etc.) and the like (a structure in which a waterproof fiber composite sheet is attached to a metal frame).

  The membrane material for a tent structure according to the present invention is a flexible sheet having a soft vinyl chloride resin coating layer on at least one surface of a fiber fabric as a base material, the soft vinyl chloride resin coating layer being a silver ligand. , A copper ligand, a zinc ligand, and one or more chelate complexes selected from nickel ligands and an antifungal organic compound. If necessary, use a material in which a chelate complex is supported on a porous particle, and if necessary, use a material in which an inorganic porous particle is supported on an antifungal organic compound, and soften it if necessary. A photocatalytic substance-containing antifouling layer containing a chelate complex is formed on the vinyl chloride resin coating layer, and if necessary, the chelate complex having inorganic porous particles supported on the chelate complex may be used. it can.

  The fiber woven fabric as the base material used in the present invention can be used in any form such as woven fabric, knitted fabric, and non-woven fabric. As the woven fabric, a plain woven fabric (minimum structural unit using at least two warps and wefts). ), Basket fabric (eg, regular basket weaves such as 2 × 2, 3 × 3, 4 × 4, 3 × 2, 4 × 2, 4 × 3, 5 × 3, 2 × 3, 2 × 4, 3 × 4, 3 × 5 irregular basket weave), twill fabric (with minimum 3 units of warp and weft): 3 slant, 4 slant, 5 slant, 6 (Slashes, 8-slashes, etc.), satin fabric (having a minimum unit of 5 warps and wefts: 2 regular jumps, 3 jumps, 4 jumps, 5 regular jumps), and change plain fabrics , Change twill fabric, change satin fabric, honeycomb fabric, pear fabric, broken oblique fabric, day / night satin fabric, moji fabric Woven fabrics, sewn fabrics, double fabrics, etc., but plain fabrics and 2 × 2 basket fabrics are particularly preferred because of excellent balance of physical properties. The above woven fabric is subjected to one or more known fiber treatments such as scouring, bleaching, dyeing, softening, water repellency, waterproofing, flameproofing, hair burning, calendering, binder fixing, adhesive coating, etc. It can also be used.

  The yarn constituting the fiber fabric can be any of synthetic fiber, natural fiber, semi-synthetic fiber, inorganic fiber or a mixed fiber composed of two or more of these, but polypropylene fiber, polyethylene fiber, polyvinyl alcohol fiber, polyester Synthetic fibers such as (PET, PBT, PNT) fibers, nylon fibers, wholly aromatic polyamide fibers, aromatic heterocyclic polymer (PBI, PBO, PBT) fibers, acrylic fibers, polyurethane fibers, or mixed fibers thereof are used. In particular, polyester (PET: polyethylene terephthalate) fibers are preferable. These yarns are monofilament, multifilament, short fiber spinning (span), split, tape, etc., but in order to ensure the flexibility and tear strength of the membrane material, multifilament or short fiber spinning. (Span) is preferred. Multifilament yarns such as glass fiber, silica fiber, alumina fiber, silica alumina fiber, and carbon fiber can also be used. These inorganic fibers are especially non-combustible materials approved by the Minister of Land, Infrastructure, Transport and Tourism (incombustible film materials for tent structures). Glass fiber multifilament yarns are particularly preferred.

The fiber fabric used in the present invention is preferably a fabric made of multifilament yarn or a short fiber spun fabric (span), and the multifilament yarn is in the range of 250 to 3000 denier (277 to 3333 dtex), particularly 500 to 2000 denier (555 to 2222 dtex) is preferable, and a non-twisted yarn (the cross section is elliptical or flat) or a twisted yarn can be used as necessary. Short fiber spun yarn ranges from 10th (591 dtex) to 60th (97 dtex), especially 10th (591 dtex), 14th (422 dtex), 16th (370 dtex), 20th (295 dtex), 24th ( 246 dtex), 30th count (197 dtex), etc. These single yarns, or double yarns (single twisted yarns), double twisted yarns (twisted yarns) of two or more single yarns, etc. are preferred. There are no restrictions on the density of the warp and weft threads of the fabric, and any design is possible depending on the thickness of the yarn used (denier, count), but the fabric porosity (missing) is 0-30%. A woven fabric having a weight per unit area of 100 to 500 g / m ² is suitable as a base material for a membrane material for a tent structure. The porosity can be obtained as a value obtained by subtracting 100 from the area of the yarn occupying in the unit area of the fiber fabric as a percentage. Suitable for manufacturing a soft vinyl chloride resin coating layer by heat laminating a soft vinyl chloride resin film on both sides of a woven fabric (porosity 7.5 to 30%) woven with multifilament yarns. In the case of a fiber spun fabric (spun), a short fiber spun fabric (span) having a porosity of 0 to 5% is preferably coated on both sides with a soft vinyl chloride resin paste sol, gelled heat treatment, or depping-gelled. Suitable for forming soft vinyl chloride resin coating layer by heat treatment.

The soft vinyl chloride resin coating layer is formed from a soft vinyl chloride resin composition containing a chelate complex and an antifungal organic compound as essential components in a soft vinyl chloride resin comprising at least a vinyl chloride resin and a plasticizer. In a paste vinyl chloride resin (emulsion polymerization type) using a vinyl chloride resin paste sol to gelation heat treatment, or using a straight vinyl chloride resin (suspension polymerization type), calender rolling or T-die extrusion molding Formation with a vinyl chloride resin film (sheet) is possible. In the present invention, about 25% by mass of vinyl chloride copolymer resin may be mixed in the soft vinyl chloride resin coating layer, and further urethane elastomer, acrylic copolymer rubber, chlorinated polyethylene, chlorosulfonated About 25% by mass of rubber components such as polyethylene, chloroprene and EPDM can be mixed. The plasticizer is a phthalate ester plasticizer having an average molecular weight of 380 to 560, an isophthalate ester plasticizer, a terephthalate ester plasticizer, a cyclohexanedicarboxylic ester plasticizer, a chlorinated paraffin plasticizer, and an average molecular weight of 1000 to 1000. 3200 polyester plasticizer, ethylene-vinyl acetate-carbon monoxide terpolymer resin, ethylene- (meth) acrylate-carbon monoxide terpolymer resin, etc. can be used. It is preferable from the viewpoint of the dispersibility of the chelate complex to use a mixture of the chelate complex in advance. Soft vinyl chloride resin coating layer, a value obtained by subtracting the weight of the textile fabric from tent structure membrane material of the present invention, 200 to 2000 g / ^{m 2,} in particular 300~1000g / ^{m 2} is preferred.

  The chelate complex included in the soft vinyl chloride resin coating layer is at least one selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand, and these chelate complexes (metal ions) are An effect that inhibits enzymes and proteins necessary for life activity by reacting with SH groups of proteins involved in cell permeability on the surface layer of Aspergillus or metal ions that have entered the cell crosslink double-stranded DNA of Aspergillus oryzae. Inhibits replication and inhibits the growth of moths and algae. Silver ions are supplied from silver salts such as silver bromide, silver chloride, silver citrate, silver iodide, silver lactate, silver nitrate, silver oxide and silver picrate, and copper is disodium copper citrate and triethanolamine copper. Copper salts such as copper carbonate, cuprous ammonium carbonate, cupric hydroxide, copper chloride, cupric chloride, ethylenediamine copper complex, copper oxychloride, copper sulfate oxychloride, cuprous oxide, copper thiocyanate Zinc is zinc acetate, zinc oxide, zinc carbonate, zinc chloride, zinc sulfate, zinc hydroxide, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, zinc phosphate, Sources of zinc salts such as zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerate, zinc gluconate, zinc undecylate , Nickel and sources of nickel chloride, nickel hydroxide, nickel sulfate, nickel oxide, nickel salts such as nickel sulfamate. The chelate complex is obtained by ion-bonding the metal salt of the ion source and the ligand through an appropriate solvent, and a product obtained by drying and isolating it is used in the present invention.

  The ligand is at least one amino acid selected from glycine, histidine, and methionine, ethylenediamine, triethylenetetramine, piperidine, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, 1,3-propanediamine. One or more ethyleneamine acetic acid selected from tetraacetic acid, diethyltriaminepentaacetic acid, triethylenetetraminehexaacetic acid, pyrithione, phenanthroline, porphyrin, and 9-crown-3, 12-crown-4,15-crown-5 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, 30-crown-10, 33-crown-11, 36-crown-12, dibenzo12-crown-4, dibenzo 18-Crown- , Tribenzo 18-crown-6, dibenzo 24-crown-8, tribenzo 27-crown-9, dibenzo 30-crown-10, dibenzo 36-crown-12, tribenzo 36-crown-12, tetrabenzo 36-crown-12 ( These are simplified representations of the ether ring of a crown ether, with the initial number representing the total number of atoms and the last number representing the number of oxygen atoms), cryptands [2.2], cryptands that are three-dimensional structures of crown ethers. [2.2.2], and aza crown ethers in which some or all of the oxygen atoms of these crown ethers are substituted with nitrogen atoms (NH), and one or more crown ethers selected from these derivatives 1 or more types selected, and a plurality of ligands coordinated to one metal atom, Including those sandwiched by a plurality of crown ether respect genus atoms. Specific examples include histidine silver, glycine copper, pyrithione zinc, pyrithione copper, triethylenetetramine copper, dibenzo24-crown-8 copper, dibenzo24-crown-8 zinc, dibenzo24-crown-8 nickel and the like.

  Moreover, chelate complexes, such as a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand, are 0.05-5 mass% with respect to a soft vinyl chloride resin coating layer, Especially 0.1. It is preferably present at ˜2% by mass, and the chelate complex is previously mixed in a plasticizer to form a soft vinyl chloride resin coating layer, thereby improving the dispersibility of the chelate complex. On the other hand, the chelate complex is present in a state of being supported on the inorganic porous particles, so that the chelate complex can be improved to a stable sustained release property, thereby stably maintaining a long-term antifungal and algal control effect. . Specific examples of inorganic porous particles include mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, calcium calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium aluminate silicate. And diatomaceous earth, and these silane coupling agent treated products. Preferable ligands supported on the inorganic porous particles are amino acids, ethylenediamine, triethylenetetramine, piperidine, ethyleneamineacetic acid, pyrithione and the like. The method of supporting the chelate complex on the inorganic porous particles is a method in which the inorganic porous particles are mixed and stirred in the solvent at the time of production of the chelate complex, and the chelate complex is adsorbed and supported on the inorganic porous particles, and then dried and isolated. Are used in the present invention. The chelate complex supported by this method is either a two-stage process in which the chelate complex is formed and adsorbed and supported on the inorganic porous particles, or a one-stage process in which the chelate complex is formed and adsorbed and supported in the inorganic porous particles. May be. Although the support rate of the chelate complex with respect to the inorganic porous particles is not particularly limited, it is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. In this case, the inorganic porous particles can be simultaneously adsorbed and supported by the antifungal organic compound and the chelate complex, thereby making it possible to aggregate the blending amount of the inorganic porous particles. The particle diameter of the inorganic porous particles is not particularly limited, but is preferably 0.1 to 5 μm, particularly preferably 0.3 to 2 μm. Moreover, the content rate of these inorganic porous particles contained in a soft vinyl chloride resin coating layer is 0.5-50 mass% with respect to a soft vinyl chloride resin coating layer, Preferably it is 1-20 mass%.

On the other hand, as an antifungal organic compound contained in the soft vinyl chloride resin coating layer, it inhibits oxidative phosphorylation against cell walls, cell membranes, cytoplasm, and cell nuclei such as sputum, bacteria (gram positive, gram negative), fungi, etc. It is an organic compound that exerts actions such as electron transport system inhibition, -SH group inhibition, DNA synthesis inhibition, cell epidermal function inhibition, lipid metabolism inhibition, chelate formation and the like. These are specifically A). Imidazole compounds such as 2- (4-thiazolyl) -benzimidazole (abbreviation TBZ), 2- (carbomethoxyamino) benzimidazole (abbreviation BCM), methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate, B ). Thiazole compounds such as 2-n-octyl-4-isothiazolin-3-one, 2-mercaptobenzothiazole, 2- (4-thiocyanomethylthio) benzothiazole, 2- (thiocyanomethylsulfonyl) benzothiazole, C) . 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n- Octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2- Methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, Nn-butyl-1,2-benzisothiazolin-3-one, 2-methylthio-4- isothiazoline-based compounds such as t-butylamino-6-cyclopropylamino-S-thiazine, D). Bis (pyridin-2-thiol-1-oxide) zinc salt (abbreviation ZPT), (2-pyridine-1-oxide) sodium salt, 2,2 ^'- dithio - bispyridine-1-oxide, 2-pyridylthio -1 -Oxide copper salts, pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, E). Hexahydro-N, N ', N "-tris (2-hydroxyethyl) -S-triazine, hexahydro-N, N', N" -triethyl-S-triazine, 2-methylthio-4-t-butylamino-6 -Cyclopropylamino-S-triazine, 2-chloro-4,6-diethylamino-S-triazine, 2-chloro-4-ethylamino-6-isopropylamino-S-triazine, 2-methylthio-4-ethylamino- Triazine compounds such as 6- (1,2-dimethylpropylamino) -S-triazine, F). α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1-[[2- (2,4-dichlorophenyl ) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole, 1-[[2- (2,4-dichlorophenyl) -1,3-dioxolane -2-yl] methyl] -1H-1,2,4-triazole, α- (4-chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol, etc. G). N- (fluorodichloromethylthio) phthalimide, N-trichloromethylthiotetrahydrophthalimide, N- (trichloromethylthio) -4-cyclohexane 1,2-dicarboximide, N, N-dimethyl-N ^′ -(fluorodimethylthio) -N ^'- phenyl sulfamide, N- dichlorofluoromethylthio -N', N'-dimethyl -N-p-tolyl-sulfamide such as N- haloalkylthio compounds, H). Quaternary ammonium salt compounds such as benzaconium chloride, benzethonium chloride, N-decyl-N-isononyl-N, N-dimethylammonium chloride, I). 10, 10 ^'- oxy bisphenoxy sialic Shin (abbreviation OBPA), 8- oxyquinoline copper, 2 although nickel ethylhexanoate, and others, is not limited to, other aldehydes, phenols, Piguanaido In combination with nitrile, nitrile, organic iodine, anilide, disulfide, thiocarbamate, haloallylsulfone, organotin, thiadiazine, and natural product extract components (hinokitiol, tea catechin, chitosan, etc.) You can also. The content of these antifungal organic compounds contained in the soft vinyl chloride resin coating layer is 0.05 to 5% by mass, preferably 0.1 to 2% by mass with respect to the soft vinyl chloride resin coating layer.

  Further, the above-mentioned antifungal organic compound is preferably present at 0.05 to 5% by mass, particularly 0.1 to 2% by mass with respect to the soft vinyl chloride resin coating layer. The dispersibility of the antifungal organic compound is improved by forming a soft vinyl chloride resin coating layer using a material previously mixed in a plasticizer. On the other hand, the controlled release property of the antifungal organic compound is stably controlled in the system in which the antifungal organic compound is supported on the inorganic porous particles, thereby stably maintaining the long-term antifungal and algal control effects. It is possible to make it. Specific examples of inorganic porous particles include mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, calcium calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium aluminate silicate. And diatomaceous earth, and these silane coupling agent treated products. The method for supporting an antifungal organic compound on the inorganic porous particles is to mix and stir the inorganic porous particles in a solvent containing the antifungal organic compound dissolved therein or in a solvent containing the antifungal organic compound dispersed. This is a product obtained by adsorbing and supporting an antifungal organic compound on inorganic porous particles and drying and isolating it, or obtained by adsorbing and supporting an antifungal organic compound by sublimation or heat melting. Used in the invention. In this case, the inorganic porous particles can be simultaneously adsorbed and supported by the antifungal organic compound and the chelate complex, thereby making it possible to aggregate the blending amount of the inorganic porous particles. Although the carrying | support rate of the antifungal organic compound with respect to an inorganic porous particle does not have limitation in particular, 0.1-10 mass%, Especially 1-5 mass% is preferable. The particle diameter of the inorganic porous particles is not particularly limited, but is preferably 0.1 to 5 μm, particularly preferably 0.3 to 2 μm. Moreover, the content rate of these inorganic porous particles contained in a soft vinyl chloride resin coating layer is 0.5-50 mass% with respect to a soft vinyl chloride resin coating layer, Preferably it is 1-20 mass%.

  In addition, a flameproofing agent should be added to the soft vinyl chloride resin coating layer to ensure flameproofness that complies with the Fire Service Act, and to be a noncombustible material (noncombustible film material for tent structures) approved by the Minister of Land, Infrastructure, Transport and Tourism. Is preferred. What is necessary is just to mix | blend 10-100 mass parts flame retardants, such as a phosphorus containing compound, a nitrogen containing compound, an inorganic compound, with respect to 100 mass parts of vinyl chloride resin (a plasticizer is not included). , Red phosphorus, (metal) phosphate, (metal) organic phosphate, ammonium polyphosphate, etc., and nitrogen-containing compounds include (iso) cyanurate compounds, (iso) cyanuric acid compounds, Guanidine compounds, urea compounds and their derivative compounds, inorganic compounds include metal oxides (antimony trioxide, antimony pentoxide, etc.), metal hydroxides (such as aluminum hydroxide, magnesium hydroxide), Metal composite oxide (zirconium-antimony composite oxide), metal composite hydroxide (zinc hydroxystannate, hydrotalcite, etc. ), And the like. These flame retardants can improve a flame retardance by using 2 or more types together.

  In addition, the soft vinyl chloride resin coating layer may contain one or more stabilizers such as calcium zinc composite, barium zinc composite, organic tin laurate, organic tin mercaptite, and epoxy as stabilizers for soft vinyl chloride resin. Is used to suppress thermal deterioration and discoloration during the production of the film material for a tent structure of the present invention, and further improve the weather resistance. The film material for a tent structure according to the present invention can be freely pigmented. In particular, coloring such as white and pastel colors makes the contrast of ink jet printing and marking film lettering clear. In addition, the soft vinyl chloride resin coating layer can contain various arbitrary amounts of known additives for vinyl chloride resin. If necessary, a light-resistant stabilizer (HALS), an ultraviolet absorber (benzotriazole-based, Benzophenone, etc.), antioxidant (phenol), fluorescent brightener, antistatic agent, curing agent (isocyanate, etc.), insect repellent (pyrethroid, etc.), deodorant (silicon oxide / metal oxide composite) Etc.), thermal barrier fillers (hollow particles, coarse titanium oxide, etc.), fragrances, phosphorescent pigments (strontium aluminate, etc.), aluminum flake pigments, pearl pigments, inorganic fillers (calcium carbonate, barium sulfate, etc.) Can be included.

  As one aspect of the membrane material for a tent structure of the present invention, a photocatalytic substance-containing antifouling layer is preferably formed on at least one surface of the soft vinyl chloride resin coating layer. Effectively self-cleans dust dirt (by washing by rain due to hydrophilicity of the antifouling layer by photocatalyst and decomposition action of soot and algae by photocatalyst), effectively generating soot and algae for a long time It is possible to stably maintain the appearance of the tent structure by deterring over the range. In the photocatalyst-containing antifouling layer, one or more particles selected from titanium oxide, titanium peroxide (peroxotitanic acid), zinc oxide, tin oxide, strontium titanate, tungsten oxide, and bismuth oxide are used as the photocatalytic substance. As a chelate complex effective for antifungal and anti-algae, one or more chelate complexes selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand (paragraph [0020] And the same as those described in [0021]. The photocatalytic substance-containing antifouling layer is composed of 10 to 70% by mass of a photocatalytic substance, 25 to 90% by mass of a metal oxide gel and / or metal hydroxide gel (silica sol, alumina sol, zirconia sol, niobium oxide sol, etc.), a silicon compound (poly A chelgel complex-containing sol-gel thin film mainly composed of an inorganic substance having a thickness of 0.1 to 15 μm is preferred, with a composition of 1 to 20% by mass and chelate complex of 1 to 10% by mass (siloxane, colloidal silica, silica, etc.). In this case, an intermediate protective layer for protecting the soft vinyl chloride resin coating layer from the redox action of the photocatalytic material is provided between the photocatalyst material-containing antifouling layer and the soft vinyl chloride resin coating layer. From the viewpoint of improving durability, the intermediate protective layer is preferably a sol-gel thin film mainly composed of an inorganic substance having a thickness of 0.1 to 15 μm by a composition obtained by omitting the photocatalytic substance from the composition of the antifouling layer containing the photocatalytic substance. The other photocatalytic substance-containing antifouling layer is applied to a fluorine-containing copolymer resin (polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, etc.). The surface of the photocatalytic material particles (preferably titanium oxide) is partially coated with an inorganic compound such as silica, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydroxyapatite, silica alumina, calcium silicate, magnesium aluminate silicate, etc. A chelate complex-containing coating having a thickness in the range of 5 to 50 μm containing the photocatalytic activity control type photocatalytic substance composite particles can be used.

  The chelate complex contained in the photocatalytic substance-containing antifouling layer is mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, silica It is supported on one or more inorganic porous particles selected from magnesium aluminate, diatomaceous earth, and treated products of these silane coupling agents, and the controlled release of the chelate complex is controlled for a long time. It is possible to stably maintain the antifungal / algae-proof effect. The inorganic porous particles described in paragraph [0022] can be used in the same manner. Although the support rate of the chelate complex with respect to the inorganic porous particles is not particularly limited, it is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. The inorganic porous particles can simultaneously adsorb and carry the antifungal organic compound and the chelate complex.

  In order to construct a tent structure, the membrane material for the tent structure of the present invention can be joined by high frequency vibration using a high frequency welder machine. A membrane material is placed between two electrodes (one electrode is a weld bar), and the resin layer of the membrane material is heated by molecular frictional heat by applying a potential difference that oscillates at a high frequency (1 to 200 MHz) while being pressed by the weld bar. It fuse | melts by setting it as a melt-softening state, and it solidifies by cooling in that state, and obtains a joined body. In addition, an ultrasonic fusion method that amplifies the amplitude of ultrasonic energy (16 to 30 KHz) generated from the ultrasonic vibrator and performs fusion using frictional heat generated on the boundary surface of the film material, or heater electric A hot air fusion method in which hot air set in a stepless manner at 100 to 700 ° C. is blown between the membrane materials through the control, the surface of the membrane material is melted and softened, and the membrane material is pressed and fused immediately after passing through the nozzle, It can be joined by a hot plate fusion method in which adherends are pressure-bonded and fused using a metal mold (trowel) heated in the heater at a temperature higher than the melting temperature of the soft vinyl chloride resin coating layer.

Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the range of these examples. In the following examples and comparative examples, the criteria used for evaluating the performance of the film material for a tent structure, such as anti-mold properties, are based on the following test methods.
(I) Evaluation of antifungal / algae resistance by outdoor spreading exposure Inclination of an exposure table (base is made of mossy concrete) with a membrane material for a tent structure measuring 20 cm wide x 2 m long 30 The exposure was carried out for 18 months by continuously spreading 1 m each in the ° direction and in the vertical direction, and outdoors. By observing the entire membrane material for tent structures after 12 months, 24 months, and 36 months after expansion, the presence or absence of wrinkles and algae, and their growth status are ranked, and the fungicidal properties (or antialgal properties) ) Was evaluated.
* Outdoor exhibition started in April in Soka City, Saitama Prefecture.
1: No generation of traces (algae) is observed (mainly maintained)
2: Slight generation (traces) of cocoons (algae) is observed 3: Partial generation (areas within 9% of the test specimen) shows pods (algae) generation (traces) 4: Partial (10% of the test specimens) (II) Evaluation of antifungal properties (JIS Z2911 culture test)
A membrane material for a tent structure having a width of 3 cm and a length of 3 cm is inoculated with spores of the following test sputum, placed on a potato-dextrose agar medium, and sprinkles are generated in a petri dish at 28 ° C. for 7 days and 14 days. The situation was observed and evaluated according to the following criteria.
1: No hyphal growth is observed in the inoculated part of the test piece 2: The area of the hyphal growing part observed in the inoculated part of the test piece is
It does not exceed 1/3 of the total area. 3: The area of the mycelial growth part observed in the inoculated part of the test piece is
Over 1/3 of the total area <Test cage> a + b + c mixed cage a: Aspergillus niger NBRC 105649 (black panther)
b: Penicillium citrinum NBRC 6352 (blue cocoon)
c: Cladosporium cladosporioides NBRC 6348
(III) Sustainability evaluation of antifungal properties (culture test based on JIS Z2911)
A test piece was prepared by immersing a membrane material for a tent structure having a width of 3 cm and a length of 3 cm in 200 cc of water (ethanol 35% concentration) and leaving it to stand at 30 ° C. for 1 week. (II) The test was conducted.
1: No hyphal growth is observed in the inoculated part of the test piece. 2: The area of the hyphal growing part observed in the inoculated part of the test piece is
It does not exceed 1/3 of the total area. 3: The area of the mycelial growth part found in the inoculated part of the test piece is
More than 1/3 of the total area

[Example 1]
Polyester fiber plain weave base fabric (warp 1111 dtex multifilament yarn: 19 yarn density / 2.54 cm x weft 1111 dtex multifilament yarn: yarn density 21 yarns / 2.54 cm: porosity 12%: mass 180 g / m ² ) As a substrate, a film (soft vinyl chloride resin coating layer) having a thickness of 0.2 mm obtained by calender molding under the conditions of 180 to 190 ° C. using the following soft vinyl chloride resin composition (1) on both sides, 180 A film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained by hot pressing with a laminator under a condition of ˜190 ° C.
<Soft vinyl chloride resin composition (1)>
Vinyl chloride resin (degree of polymerization 1050) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl (plasticizer) 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Glycine copper (chelate complex) 0.5 part by mass Histidine silver (chelate complex) 0.5 part by mass * Chelate complex or its carrier used in advance mixed in plasticizer 10,10'-oxybisphenoxy Arsine (antifungal organic compound) 0.15 parts by mass 2- (4-thiazolyl) -benzimidazole (antifungal organic compound) 0.15 parts by mass * An antifungal organic compound or a carrier thereof is previously a plasticizer. Chlorinated n-paraffin (flameproof plasticizer) 10 parts by mass epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimony trioxide (difficult Flame retardant) 10 parts by mass Rutile-type titanium oxide (white pigment) 5 parts by mass Benzotriazole (ultraviolet absorber) 0.3 parts by mass

[Example 2]
In the soft vinyl chloride resin composition (1) of Example 1, the same procedure as in Example 1 was performed except that 0.5 part by mass of glycine copper (chelate complex) was replaced with 0.5 part by mass of pyrithione zinc (chelate complex). A film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained.

[Example 3]
Example 1 except that 0.5 parts by mass of glycine copper (chelate complex) was replaced with 0.5 parts by mass of 24-crown-8 copper (chelate complex) in the soft vinyl chloride resin composition (1) of Example 1. In the same manner as above, a film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained.

[Example 4]
In Example 1, 0.5 part by mass of glycine copper (chelate complex) and 0.5 part by mass of histidine silver (chelate complex) were previously added to 0.5 parts by mass of glycine copper (chelate complex) and histidine silver ( Chelate complex) 0.55 parts by weight, glycine copper (chelate complex) / histidine silver (chelate complex) -supported mesoporous silica A film material having a mass of 698 g / m ² was obtained.
* Preparation of glycine copper (chelate complex) and histidine silver (chelate complex) -supported mesoporous silica In 200 ml of a water-ethanol solution containing 0.5 g of glycine copper (chelate complex) and 0.5 g of histidine silver (chelate complex), mesoporous Add 30 g of silica (average particle size 2.5 μm), stir with 1 g of silane coupling agent (γ-glycidoxypropyltrimethoxysilane) for 1 hour at room temperature, remove water-ethanol solvent under reduced pressure, and dry at 100 ° C. As a result, about 31 g of powder was obtained. The amount of glycine copper (chelate complex) carried by 31 g of this powder and the amount of silver histidine (chelate complex) are each 0.5 g.

[Example 5]
Except for replacing 11 parts by mass of glycine copper (chelate complex) / histidine silver (chelate complex) -supported mesoporous silica of Example 4 with 31 parts by mass of glycine copper (chelate complex) / histidine silver (chelate complex) -supported zirconium phosphate. In the same manner as in Example 4, a film material having a thickness of 0.65 mm and a mass of 698 g / m ² was obtained.
* Preparation of zirconium phosphate supporting glycine copper (chelate complex) / silver histidine (chelate complex) In 200 ml of water-ethanol solution containing 0.5 g of glycine copper (chelate complex) and 0.5 g of histidine silver (chelate complex), Add 30 g of zirconium phosphate (average particle size 3 μm), stir with 1 g of silane coupling agent (γ-glycidoxypropyltrimethoxysilane) for 1 hour at room temperature, remove water-ethanol solvent under reduced pressure, and dry at 100 ° C. As a result, about 31 g of powder was obtained. The amount of glycine copper (chelate complex) carried by 31 g of this powder and the amount of silver histidine (chelate complex) are each 0.5 g.

[Example 6]
0.5 parts by mass of silver histidine (chelate complex) of Example 2 and 0.5 parts by mass of zinc pyrithione (chelate complex) were added to 31 parts by mass of synthetic zeolite carrying histidine silver (chelate complex) and pyrithione zinc (chelate complex). A membrane material having a thickness of 0.65 mm and a mass of 698 g / m ² was obtained in the same manner as in Example 2 except that the substitution was performed.
* Preparation of synthetic zeolite carrying histidine silver (chelate complex) and zinc pyrithione (chelate complex) In 200 ml of a water-ethanol solution containing 0.5 g of histidine silver (chelate complex) and 0.5 g of pyrithione zinc, synthetic zeolite (average particle size) (2 μm in diameter) 30 g was added, and 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane) was stirred at room temperature for 1 hour, and the water-ethanol solvent was removed under reduced pressure, followed by drying at 100 ° C. to obtain about 31 g of powder. Obtained. The amount of histidine silver (chelate complex) carried by 31 g of this powder and the amount of pyrithione zinc are 0.5 g each.

[Example 7]
0.5 parts by mass of histidine silver (chelate complex) of Example 3 and 0.5 parts by mass of 24-crown-8 copper (chelate complex) were mixed with histidine silver (chelate complex) / 24-crown-8 copper (chelate complex). ) A membrane material having a thickness of 0.65 mm and a mass of 698 g / m ² was obtained in the same manner as in Example 3 except that 31 parts by mass of the supported diatomaceous earth was substituted.
* Preparation of diatomaceous earth carrying histidine silver (chelate complex) and 24-crown-8 copper (chelate complex) Water-ethanol solution containing 0.5 g of histidine silver (chelate complex) and 0.5 g of 24-crown-8 copper Add 200 g of diatomaceous earth (average particle size 2 μm) to 200 ml, stir with 1 g of silane coupling agent (γ-glycidoxypropyltrimethoxysilane) for 1 hour at room temperature, remove water-ethanol solvent under reduced pressure, and then 100 ° C. To obtain about 31 g of powder. The amount of histidine silver (chelate complex) carried by 31 g of this powder and the amount of 24-crown-8 copper are each 0.5 g.

[Example 8]
In Example 4, 10, 10 ^'- oxy bisphenoxy sialic Shin (antifungal organic compound: Abbreviation OBPA) 0.15 parts by weight, and 2- (4-thiazolyl) - benzimidazole (antifungal organic compound: Abbreviation TBZ Example 4) except that 0.15 parts by mass was replaced with 10.5 parts by mass of an antifungal organic compound-supported mesoporous silica in which 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were previously supported on mesoporous silica. In the same manner as above, a film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained.
* Preparation of OBPA / TBZ-supported mesoporous silica To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of mesoporous silica (average particle size 2.5 μm) was added, and a silane coupling agent (γ- 1 g of glycidoxypropyltrimethoxysilane) was stirred at room temperature for 1 hour, and the water-ethanol solvent was removed under reduced pressure, followed by drying at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA supported by 10.5 g of this powder and the amount of TBZ are each 0.15 g.

[Example 9]
In Example 5, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ, zirconium phosphate carrying an antifungal organic compound in which 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were previously supported on zirconium phosphate A film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained in the same manner as in Example 5 except that 10.5 parts by mass was replaced.
* Preparation of OBPA / TBZ-supported zirconium phosphate To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of zirconium phosphate (average particle size 3 μm) was added, and a silane coupling agent (γ- 1 g of glycidoxypropyltrimethoxysilane) was stirred at room temperature for 1 hour, and the water-ethanol solvent was removed under reduced pressure, followed by drying at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA supported by 10.5 g of this powder and the amount of TBZ are each 0.15 g.

[Example 10]
In Example 6, an antibacterial organic compound-supported synthetic zeolite in which 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were previously supported on a synthetic zeolite by 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ. A film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained in the same manner as in Example 6 except that the content was replaced with 5 parts by mass.
* Preparation of OBPA / TBZ-supported synthetic zeolite To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of synthetic zeolite (average particle size 2 μm) is added, and a silane coupling agent (γ-glycid 1 g of xylpropyltrimethoxysilane) was stirred at room temperature for 1 hour, and the water-ethanol solvent was removed under reduced pressure, followed by drying at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA supported by 10.5 g of this powder and the amount of TBZ are each 0.15 g.

[Example 11]
In Example 7, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were previously supported on diatomaceous earth, and 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ. A membrane material having a thickness of 0.65 mm and a mass of 695 g / m ² was obtained in the same manner as in Example 7 except that the content was replaced with 5 parts by mass.
* Preparation of diatomaceous earth supporting OBPA / TBZ To 100 ml of water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of diatomaceous earth (average particle size 2 μm) is added, and a silane coupling agent (γ-glycid 1 g of xylpropyltrimethoxysilane) was stirred at room temperature for 1 hour, and the water-ethanol solvent was removed under reduced pressure, followed by drying at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA supported by 10.5 g of this powder and the amount of TBZ are each 0.15 g.

[Example 12]
In Example 8, 10.5 parts by mass of glycine copper (chelate complex) / histidine silver (chelate complex) -supported mesoporous silica and 10.5 parts by mass of OBPA / TBZ-supported mesoporous silica were added to mesoporous silica in advance. ) 0.5 parts by mass and 0.5 parts by mass of histidine silver (chelate complex), and 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ, 41 parts by mass of mesoporous silica supporting chelate complex and antifungal organic compound A film material having a thickness of 0.65 mm and a mass of 690 g / m ² was obtained in the same manner as in Example 8 except that
* Preparation of chelate complex and antifungal organic compound-supported mesoporous silica 100 ml of water-ethanol solution containing 0.5 g of glycine copper (chelate complex), 0.5 g of histidine silver (chelate complex), 0.15 g of OBPA and 0.15 g of TBZ 40 g of mesoporous silica (average particle size 2.5 μm) was added, and the mixture was stirred with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane) at room temperature for 1 hour, and the water-ethanol solvent was removed under reduced pressure, then 100 The powder was dried at 0 ° C. to obtain about 41 g of powder. The amount of glycine copper (chelate complex) and the amount of histidine silver (chelate complex) carried by 41 g of the powder is 0.15 g, the amount of OBPA and the amount of TBZ are 0.15 g each.

[Examples 13 to 15]
What formed the photocatalyst substance containing antifouling layer in the film material of Examples 1-3 was made into Examples 13-15.
* Formation of intermediate protective layer Apply the coating solution of the following silicon compound-containing resin with a coater with 80 mesh gravure roll (wet) 15g / m ^{2 and} dry it in a 100 ° C hot air oven for 1 minute to form an intermediate protective layer. Formed. (Solid content 3 g / m ² )
<Silicon compound-containing resin layer coating solution>
Acrylic-silicone copolymer resin solution (solid content 8% by mass) 100 parts by mass Methyl silicate solution (solid content 20% by mass) 8 parts by mass γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by mass Glycine Copper (chelate complex) 0.5 part by mass Histidine silver (chelate complex) 0.5 part by mass

* Formation of photocatalytic substance-containing antifouling layer The coating liquid for forming the photocatalyst substance-containing antifouling layer was applied at 15 g / m ² with a coater having an 80-mesh gravure roll (1) in a 100 ° C hot air oven. After drying for a minute, the photocatalytic substance-containing antifouling layer was sol-gel formed (solid content 2 g / m ² ) to obtain film materials of Examples 13 to 15 having a thickness of 0.65 mm and a mass of 705 g / m ² .
<Coating liquid for forming antifouling layer containing photocatalyst substance>
Nitric acid acidic titanium oxide sol (equivalent to 10% by mass of titanium oxide) 100 parts by mass Nitric acid acidic silica sol (equivalent to 10% by mass of silicon oxide) 100 parts by mass Glycine copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by weight

[Examples 16 to 24]
What formed the photocatalyst substance containing antifouling layer in the film material of Examples 4-12 was set as Examples 16-24.
* Formation of intermediate protective layer According to the same composition and formation method as in Examples 13-15.
* Formation of photocatalytic substance-containing antifouling layer The coating liquid for forming the photocatalytic substance-containing antifouling layer was applied with a coater having an 80-mesh gravure roll (25 g / m ² ) and heated in a 100 ° C hot air oven. The film was dried for 5 minutes to form a photocatalyst substance-containing antifouling layer (solid content 7 g / m ² ), and the film materials of Examples 16 to 24 having a thickness of 0.65 mm and a mass of 707 g / m ² were obtained.
<Coating liquid for forming antifouling layer containing photocatalyst substance>
Vinylidene fluoride resin solution (solid content 15% by mass) 100 parts by mass photocatalytic titanium oxide (average particle size 1 μm) 8 parts by mass * Partial coating with surface coverage of 4 to 10% by hydroxyapatite)
Glycine copper (chelate complex) / histidine silver (chelate complex) supported mesoporous silica
10 parts by mass
* Preparation of glycine copper (chelate complex) and histidine silver (chelate complex) -supported mesoporous silica In 200 ml of a water-ethanol solution containing 0.5 g of glycine copper (chelate complex) and 0.5 g of histidine silver (chelate complex), mesoporous Add 30 g of silica (average particle size 2.5 μm), stir with 1 g of silane coupling agent (γ-glycidoxypropyltrimethoxysilane) for 1 hour at room temperature, remove water-ethanol solvent under reduced pressure, and dry at 100 ° C. As a result, about 31 g of powder was obtained. The amount of glycine copper (chelate complex) carried by 31 g of this powder and the amount of silver histidine (chelate complex) are each 0.5 g.

[Anti-mold effect of Examples 1-12]
All the film materials for tent structures of Examples 1 to 12 containing a chelate complex and an antifungal organic compound in the soft vinyl chloride resin coating layer are all subjected to an antifungal test (I): outdoor expansion exposure. After 36 months, no sputum or algae were observed (no traces), and the initial state was maintained. Antifungal test (II): Mycelial growth was not observed in the JIS Z2911 culture test. From these results, it was revealed that a sufficient antifungal effect can be expected as a film material for a tent structure. Further, the superiority or inferiority in the antifungal test (III) assuming long-term use is most prevented by the membrane materials of Examples 8 to 12 in which a chelate complex and an antifungal organic compound are supported on inorganic porous particles. The film material of Examples 4-7, which has a long-term durability of inertia and is then used by supporting the chelate complex on inorganic porous particles, has high antifouling durability, and the film materials of Examples 1-3 are implemented. Although it is somewhat inferior in long-term sustainability in the examples, it is clear that it is superior to conventional membrane materials. In addition, the film materials for tent structures of Examples 13 to 24 in which the photocatalyst substance-containing antifouling layer was formed on the film materials for tent structures of Examples 1 to 12 were prominent such as accumulation of dust dirt and rain line dirt. Occurrence is not observed for a long time, and the initial appearance is further improved than the film material for tent structures of Examples 1 to 12 due to the antifouling effect by the rain self-cleaning by the antifouling layer containing the photocatalyst substance and the organic matter decomposing effect such as bacilli. In particular, the membrane materials for tent structures of Examples 16 to 24 were superior in duration to the membrane materials for tent structures of Examples 13 to 15.

[Comparative Example 1]
As in Example 1, except that 0.5 part by mass of glycine copper (chelate complex) and 0.5 part by mass of histidine silver (chelate complex) were omitted from the soft vinyl chloride resin composition (1) of Example 1. A film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained. Although the film material of Comparative Example 1 has only the antifungal effect due to the antifungal organic compound by omitting the chelate complex, the initial antifungal effect appears well, but after 36 months of the antifungal test (I) Occurrence of wrinkles was partially observed (area of about 6% of the specimen) due to factors such as bleed of organic compounds, wash-out due to rain, and deterioration. As a result of the extraction of the compound, the area of the mycelial growth part observed in the inoculated part of the test piece exceeds 1/3 of the total area, and the long-term stable durability of the antifungal property compared with the membrane material of Example 1 It was a big loss.

[Comparative Example 2]
From the soft vinyl chloride resin composition (1) of Example 1, 0.5 parts by mass of glycine copper (chelate complex) and 0.5 parts by mass of histidine silver (chelate complex) were omitted, and instead a silver ion-supported zeolite 1 A film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained in the same manner as in Example 1 except that the mass part was changed. Although the film material of Comparative Example 2 had a silver ion-carrying zeolite and an antifungal organic compound, it could exhibit an antifungal property for a relatively long period of time. Occurrence of soot was observed due to factors such as bleed of organic compounds, wash-out due to rainfall, and deterioration. In anti-wetting test (III), it was detected in the inoculated part of the test piece by extraction of anti-organic compounds. Although the area of the growth part of the mycelium to be obtained does not exceed 1/3 of the total area, it is better than Comparative Example 1, but the long-term stable durability of the antifungal property is inferior to the film material of Example 1 Met.

[Comparative Example 3]
A soft vinyl chloride resin composition of Example 1 (1), 10, 10 ^'- 0.15 part by weight oxy bisphenoxy sialic Shin (antifungal organic compound), and 2- (4-thiazolyl) - benzimidazole (proof Membrane material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained in the same manner as in Example 1 except that 0.15 parts by mass of the organic compound) was omitted. In the film material of Comparative Example 3, the antifungal organic compound was omitted, so that only the antifungal effect by the chelate complex was obtained and the initial antifungal effect was well expressed, but after 36 months of the antifungal test (I) Is partially observed (an area of about 6% of the specimen), and in the antifungal test (III), the area of the mycelial growth observed in the inoculated part of the test piece is 1 / of the total area. Compared to the film material of Example 1, such as exceeding 3, the long-term stability and sustainability of the fender is greatly impaired.

[Comparative Example 4]
When the soft vinyl chloride resin composition (1) of Example 1 was changed to a calendar molding type polyurethane resin composition (1) and subjected to 180 ° C. calendar molding, glycine copper (chelate complex) and histidine silver ( The chelate complex) was seized onto a calendered hot roll, making film processing impossible, and a film material could not be obtained.
<Polyurethane resin composition (1)>
Polyurethane resin (ether type) 100 parts by mass Glycine copper (chelate complex) 0.5 part by mass Histidine silver (chelate complex) 0.5 part by mass 10,10′-oxybisphenoxyarsine (antifungal organic compound) 0.15 Parts by mass 2- (4-thiazolyl) -benzimidazole (antifungal organic compound) 0.15 parts by mass ammonium polyphosphate (flame retardant) 10 parts by weight melamine cyanurate (flame retardant) 10 parts by weight rutile titanium oxide (white) Pigment) 5 parts by mass Benzotriazole (ultraviolet absorber) 0.3 part by mass Montanic acid wax (lubricant) 0.5 part by mass

[Comparative Example 5]
When the soft vinyl chloride resin composition (1) of Example 1 was changed to a calendar molding type polyethylene resin composition (1) and subjected to 150 ° C. calendar molding, glycine copper (chelate complex) and histidine silver ( The chelate complex) was seized onto a calendered hot roll, making film processing impossible, and a film material could not be obtained.
<Polyethylene resin composition (1)>
Polyurethane resin (ether type) 100 parts by mass Glycine copper (chelate complex) 0.5 part by mass Histidine silver (chelate complex) 0.5 part by mass 10,10′-oxybisphenoxyarsine (antifungal organic compound) 0.15 Parts by mass 2- (4-thiazolyl) -benzimidazole (antifungal organic compound) 0.15 parts by mass ammonium polyphosphate (flame retardant) 10 parts by weight melamine cyanurate (flame retardant) 10 parts by weight rutile titanium oxide (white) Pigment) 5 parts by mass Benzotriazole (ultraviolet absorber) 0.3 part by mass Montanic acid wax (lubricant) 0.5 part by mass

  As is clear from the above Examples and Comparative Examples, according to the present invention, since a film material capable of suppressing the generation of cocoons and algae can be obtained to the minimum, the film material of the present invention is medium to Large tent structures (stadium roofs, dome stadiums, openable roof domes, pavilions, etc.), awning tent structures (public facility monuments, station building roofs, connecting passage roofs, arcade roofs, shops, residences, etc.), interior lighting It can be widely used for tent structures (structures in which a waterproof fiber composite sheet is attached to a metal frame) such as a type tent structure (electric decoration signboard, video projection dome, art molding, etc.).

Claims (8)

  A flexible sheet comprising a textile fabric as a base and a soft vinyl chloride resin coating layer on at least one surface thereof, wherein the soft vinyl chloride resin coating layer comprises a silver ligand, a copper ligand, and a zinc ligand. And a film material for a tent structure, comprising one or more chelate complexes selected from nickel ligands and an antifungal organic compound.   The tent structure according to claim 1, wherein a ligand of the chelate complex is at least one selected from amino acids, ethylenediamine, triethylenetetramine, piperidine, ethyleneamineacetic acid, pyrithione, phenanthroline, porphyrin, and crown ether. Film material.   The chelate complex is mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium silicate aluminate, diatomaceous earth, The membrane material for a tent structure according to claim 1 or 2, wherein the membrane material is supported on one or more kinds of inorganic porous particles selected from those treated with silane coupling agents.   The antifungal organic compound includes an imidazole compound, a thiazole compound, an isothiazoline compound, a pyridine compound, a triazine compound, a triazole compound, an N-haloalkylthio compound, a quaternary ammonium salt compound, and an organometallic compound. The film material for a tent structure according to any one of claims 1 to 3, wherein the film material is one or more selected from compounds.   The antifungal organic compound is mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium aluminate silicate, The membrane material for a tent structure according to claim 4, wherein the membrane material is supported on one or more kinds of inorganic porous particles selected from diatomaceous earth and treated products of these silane coupling agents.   A photocatalytic substance-containing antifouling layer is formed on at least one surface of the soft vinyl chloride resin coating layer, and the photocatalytic substance contained in the photocatalytic substance-containing antifouling layer comprises titanium oxide, titanium peroxide (peroxotitanic acid), or zinc oxide. The film material for a tent structure according to any one of claims 1 to 5, wherein the film material is one or more selected from the group consisting of tin oxide, strontium titanate, tungsten oxide, and bismuth oxide.   The tent structure according to claim 6, wherein the photocatalytic substance-containing antifouling layer contains one or more chelate complexes selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand. Film material.   The chelate complex contained in the photocatalytic substance-containing antifouling layer is mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate The membrane material for a tent structure according to claim 7, wherein the membrane material is supported on one or more inorganic porous particles selected from the group consisting of magnesium aluminate silicate, diatomaceous earth, and these silane coupling agent-treated products.