JP6678032B2 - Membrane materials for tent structures - Google Patents

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 (a stadium roof, a dome stadium, a retractable roof dome, a pavilion, etc.), a sunshade tent structure (public). Tent structures (metal frames, etc.) such as facility monuments, station building platform roofs, access passage roofs, arcade roofs, stores, residences, etc., and internally illuminated tent structures (electrical signs, video projection dome, art molding, etc.) (Waterproof fiber composite sheet attached structure) with excellent antifungal and antialgal properties suitable for tent structures that can prevent appearance contamination due to mold and algae generation on tent structures for a long time It relates to a film material.

  The general-purpose sheet-like membrane material used for the tent structure is a composite sheet material obtained by coating the surface of a fiber woven fabric with a soft-blended vinyl chloride resin composition on a surface of the tent structure. Has a durability of 10 to 20 years. However, since the vinyl chloride resin of the soft blend contains a large amount of plasticizer in the blend, the plasticizer bleeds over the surface of the sheet-like film material over time, and dust gradually accumulates in the bleed plasticizer. There is a problem that the sheet-like film material becomes dirty. For this reason, the bleeding of the plasticizer is controlled by providing a coating film of acrylic resin, urethane resin, fluorine-based resin, etc. on the surface of the sheet-like film material made of soft blended vinyl chloride resin, and the antifouling effect is secured. The means to do it is common.

  Since these tent structures are designed in various design forms depending on the use and scale, they are three-dimensional structures including various portions such as a horizontal portion, a vertical portion, and an arch portion made of a sheet-like film material, and have various service lives. In these tent structures, dust and dirt accumulates on the surface of the sheet-like film material over time, depending on the shape, but the larger and more complex the tent structure, the more extensive cleaning by people climbs. The actual situation is that the cleaning is started after the dirt is extremely noticeable. By the way, each time the temperature of the sheet-like film material constituting the tent structure becomes 50 ° C. or more and the summer when the softening of the soft blended vinyl chloride resin is maximized, the dust accumulation adheres to the surface of the sheet-like film material. As a result, sediment that does not easily flow down when rainfall occurs is generated. The accumulated dirt becomes a bed of mold and algae spores, and causes mold and algae to be generated in the tent structure. When the mold and algae are left, the hyphae erode (secretion) the sheet-like membrane material surface. Even if the tent structure was cleaned later due to enzymatic erosion), the tent structure could become a sign of deterioration even if the tent structure was cleaned.

  In order to prevent mold and algae in these tent structures, it is effective to add an organic fungicide to the sheet-like film material, and the organic fungicide bleeds sequentially with the plasticizer on the sheet surface. Effectively exerts the fungicidal and anti-algae effects, but deteriorates with ultraviolet rays, elutes with rain, and the organic anti-fungal agent comes out of the sheet-like membrane material during long-term use to prevent fungicide and alga. Has a problem that the effect of the above is gradually lost. On the other hand, in a kneading compound system of an inorganic fungicide 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. In addition, the sequential replenishment of the sheet surface with the metal element becomes inefficient, and the fungicidal and algal resistance tend to gradually decrease. Therefore, as an antibacterial composition in which the antibacterial effect of a metal element such as silver is stably maintained for a long period of time, and a discoloration prevention antibacterial composition using a complex of a metal such as silver and a phenolic compound (Patent Document 1), silver Antibacterial agent consisting of a colloidal solution of an inorganic oxide formed into a complex with a metal such as ethylenediaminetetraacetic acid (Patent Document 2), an organic solvent in which silver oxide and phytic acid are dissolved in an aqueous solvent and a chelating agent such as ethylenediaminetetraacetic acid is contained. Complexes such as aqueous complex solutions (Patent Document 3) have been proposed, and their long-term stability is ensured. However, liquid complexes have poor compatibility with a soft-blended vinyl chloride resin containing a plasticizer, and poor mixing may occur. It is practically difficult to use. Therefore, as a film material made of a soft-blended vinyl chloride resin for producing a film material for a tent structure, a film material having a long-term stable and stable mold- and alga-proof effect has been required.

JP-A-6-227924 JP 2008-94738 A JP 2010-202561 A

  The present invention provides a membrane material for a tent structure capable of minimizing the generation of mold and algae so that the tent structure does not cause appearance contamination due to the generation of mold and algae. What you want to do.

  The present invention has been studied and studied in view of the above-mentioned situation, and as a result of repeating the studies, a flexible sheet having a soft vinyl chloride resin coating layer on at least one surface of a fiber woven fabric as a base material has a soft vinyl chloride resin coating layer. By containing at least one chelate complex selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand, and a fungicidal organic compound, As a film material for a tent structure, the present inventors have found that it is possible to solve the problem of improving the antifungal effect of suppressing mold and algae to a minimum for a long period of time, thereby completing the present invention.

That is, the film material for a tent structure of the present invention is a flexible sheet having a fiber woven fabric as a base material and having a soft vinyl chloride resin coating layer on at least one surface thereof, wherein the soft vinyl chloride resin coating layer has a silver distribution. ligand, Dohaiiko, zinc ligands, and with one or more chelate complex selected from nickel ligands, see contains an antifungal organic compounds, ligands of the chelate complex is at least crown Preferably, the chelate complex is an ether and an amino acid, and the chelate complex is a combination of a crown ether complex and an amino acid complex, and the amino acid is at least one selected from glycine, histidine, and methionine . This stabilizes metals such as silver, copper, zinc, and nickel, and metal ions, and makes it difficult for them to be discharged out of the system. A suitable film material can be obtained.

Tent structures for film material of the present invention, the ligand of the chelate complex, ethylenediamine, triethylenetetramine, Pipirijin, ethyleneamine acetate, pyrithione, further phenanthroline, porphyrin, and one or more species selected from crown ethers It is preferred to include . This stabilizes metals such as silver, copper, zinc, and nickel, and metal ions, and makes it difficult for them to be discharged out of the system. A suitable film material can be obtained.

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

  In the film material for a tent structure of the present invention, the antifungal 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. This makes it possible to obtain a film material suitable for a tent structure capable of effectively suppressing the generation of mold and algae for a long period of time.

  In the film material for a tent structure of the present invention, the antifungal organic compound is preferably mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina It is preferably carried on one or more inorganic porous particles selected from calcium silicate, magnesium silicate aluminate, diatomaceous earth, and a silane coupling agent-treated product thereof. This makes it difficult for the fungicidal organic compound to be discharged out of the system, and by exhibiting a sustained release property, a film material suitable for a tent structure capable of effectively suppressing the generation of mold and algae for a long period of time. Obtainable.

  In the film material for a tent structure of the present invention, 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 is 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-cleans dust and dirt by the redox effect of the photocatalytic substance (washing by rainfall by making the antifouling layer hydrophilic by the photocatalyst, and by decomposition of mold and algae by the photocatalyst), and reduces the generation of mold and algae A film material for a tent structure that is effective and can be suppressed for a long period of time can be obtained.

  In the film material for a tent structure of the present invention, the photocatalytic substance-containing antifouling layer is preferably one or more chelate complexes selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand. It is preferable to include Effectively self-cleans dust and dirt by the redox effect of the photocatalytic substance (washing by rainfall by making the antifouling layer hydrophilic by the photocatalyst, and by decomposition of mold and algae by the photocatalyst), and reduces the generation of mold and algae It is possible to obtain a film material for a tent structure that is effective and can be suppressed for a long period of time.

  In the membrane material for a tent structure of the present invention, the chelate complex contained in the photocatalytic substance-containing antifouling layer is a mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotal Site, hydroxyapatite, silica alumina, calcium silicate, magnesium silicate aluminate, diatomaceous earth, and a silane coupling agent-treated product thereof, and may be supported on one or more inorganic porous particles. preferable. As a result, dust and dirt are effectively self-cleaned (washing by rainfall due to hydrophilicity of the antifouling layer with the photocatalyst, and decomposition of mold and algae by the photocatalyst), and at the same time, the chelate complex is hardly discharged out of the system. By exhibiting a sustained release property, it is possible to obtain a film material suitable for a tent structure capable of effectively suppressing the generation of mold and algae for a long period of time.

  According to the present invention, it is possible to obtain a membrane material for a tent structure that suppresses the generation of mold and algae to a minimum for a long period of time. Therefore, the membrane material of the present invention can be used for a medium to large tent structure (stadium roof, dome ballpark). , Openable dome, pavilion, etc.), awning tent structure (public facility monument, station building home roof, access passage roof, arcade roof, store, residence, etc.), internally illuminated tent structure (illuminated signboard, video 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 projection dome and art molding.

  The membrane material for a tent structure of the present invention is a flexible sheet having a fiber woven fabric as a base material and having a soft vinyl chloride resin coating layer on at least one surface thereof, wherein the soft vinyl chloride resin coating layer has a silver ligand. And one or more chelate complexes selected from copper, zinc, and nickel ligands, and a fungicidal organic compound. If necessary, the chelate complex may contain an inorganic porous material. Use a material in which a chelate complex is supported on porous particles, and if necessary, use a material in which an inorganic porous particle supports a fungicide organic compound, and if necessary, use a soft 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 may be one in which inorganic porous particles carry the chelate complex. it can.

  The fiber woven fabric as the base material used in the present invention can be used in any form such as a woven fabric, a knitted fabric, and a nonwoven fabric. As the woven fabric, a plain woven fabric (the minimum structural unit using a minimum of two warp yarns and two weft yarns) is used. ), Basket fabrics (eg, regular basket weaves such as 2 × 2, 3 × 3, 4 × 4, etc., 3 × 2, 4 × 2, 4 × 3, 5 × 3, 2 × 3, 2 × 4, 3) × 4, 3 × 5, etc., irregular basket weave), twill fabric (warp and weft have the minimum constitutional unit using at least 3 pieces: 3 pieces, 4 pieces, 5 pieces, 5 pieces, 6 pieces) Oblique, 8 oblique, etc.), satin fabric (having the minimum structural unit using a minimum of 5 each for both warp and weft: regular satin such as 2 jumps, 3 jumps, 4 jumps, 5 jumps), and changing plain fabrics , Change twill fabric, change satin fabric, etc., beehive fabric, rishiji fabric, torn oblique fabric, day and night satin fabric, woven fabric , Woven fabrics), sewing fabrics, double woven fabrics, etc., but plain woven fabrics and 2 × 2 basket woven fabrics are particularly preferred because of their excellent balance of properties. The above-mentioned woven fabric has been subjected to single or multiple known fiber treatment processes such as scouring, bleaching, dyeing, softening, water repellency, waterproofing, flameproofing, scalding, calendering, binder fixing, and adhesive application. Can also be used.

  As the yarn constituting the fiber woven fabric, any of synthetic fiber, natural fiber, semi-synthetic fiber, inorganic fiber or a mixed fiber of two or more of these can be used, 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. The form of these yarns is monofilament, multifilament, short fiber spinning (spun), split, tape, etc. In order to secure the flexibility and tear strength of the membrane material, multifilament or short fiber spinning is used. (Span) is preferred. In addition, multifilament yarns such as glass fiber, silica fiber, alumina fiber, silica-alumina fiber, and carbon fiber can also be used. These inorganic fibers are particularly non-combustible materials approved by the Minister of Land, Infrastructure, Transport and Tourism (non-combustible film materials for tent structures). In particular, glass fiber multifilament yarn is preferable.

The fiber woven fabric used in the present invention is preferably a woven fabric composed of multifilament yarns or a staple fiber spun cloth (spun), 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 (elliptical or flat in cross section) or a twisted yarn can be used as necessary. The short fiber spun yarn ranges from 10th (591 dtex) to 60th (97 dtex), particularly 10th (591 dtex), 14th (422 dtex), 16th (370 dtex), 20th (295 dtex), and 24th ( Preferred are such single yarns, such as 246 dtex and 30 count (197 dtex), or twin yarns (single twisted yarns), ply twisted yarns (twisted yarns) of two or more single yarns, and the like. There is no limitation on the driving density of the warp and the weft of the woven fabric, and any design is possible according to the thickness (denier, count) of the yarn to be used. However, the porosity (opening) of the woven fabric is 0 to 30%. A woven fabric having a basis weight of 100 to 500 g / m ² at a driving density in the range of 1 to ² is suitable as a base material of a membrane material for a tent structure. The porosity can be obtained as a value obtained by calculating the area of the yarn occupying in a unit area of the fiber woven fabric as a percentage and subtracting it from 100. Suitable for the production of 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%), preferably with a multifilament yarn. In the case of a fiber spun cloth (span), preferably, a short fiber spun cloth (span) having a porosity of 0 to 5% is coated on a both surfaces with a soft vinyl chloride resin paste sol to perform gelation heat treatment or depping to gelation. Suitable for forming a soft vinyl chloride resin coating layer by heat treatment.

The soft vinyl chloride resin coating layer is formed of a soft vinyl chloride resin composition containing a chelate complex as an essential component and a fungicidal organic compound in a soft vinyl chloride resin comprising at least a vinyl chloride resin and a plasticizer. Then, a vinyl chloride resin paste sol using paste vinyl chloride resin (emulsion polymerization type) was formed by gelation heat treatment, or calender roll molding or T-die extrusion molding was performed using straight vinyl chloride resin (suspension polymerization type). It can be formed from a vinyl chloride resin film (sheet). In the present invention, about 25% by mass of a 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 A rubber component such as polyethylene, chloroprene, and EPDM can be mixed at about 25% by mass. The plasticizer is a phthalate plasticizer having an average molecular weight of 380 to 560, an isophthalate ester plasticizer, a terephthalate ester plasticizer, a cyclohexanedicarboxylate ester plasticizer, a chlorinated paraffin plasticizer, and an average molecular weight of 1,000 to 5,000. 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 that a chelate complex is mixed 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 contained 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 used. The effect of inhibiting the enzymes and proteins necessary for life activity by reacting with the SH group of the protein involved in the cell permeability of the mold fungal surface, or the metal ions entering the cells crosslink the double-stranded DNA of the mold, Inhibiting replication prevents the growth of molds and algae. Silver ion is supplied from silver salts such as silver bromide, silver chloride, silver citrate, silver iodide, silver lactate, silver nitrate, silver oxide, silver picrate, and copper is disodium copper citrate, copper triethanolamine. 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 As a source, 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 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, etc. , 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 via a suitable solvent, and the dried and isolated product is used in the present invention.

  The ligand is one or more amino acids selected from glycine, histidine, and methionine, ethylenediamine, triethylenetetramine, piperidine, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, and 1,3-propanediamine. One or more ethyleneamine acetic acids selected from tetraacetic acid, diethyltriaminepentaacetic acid, and 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- , Tribenzo18-crown-6, dibenzo24-crown-8, tribenzo27-crown-9, dibenzo30-crown-10, dibenzo36-crown-12, tribenzo36-crown-12, tetrabenzo36-crown-12 ( These are simplified representations of the ether rings of crown ethers. The numbers at the top indicate the total number of atoms, and the numbers at the end indicate the number of oxygen atoms.) Cryptands [2.2], which are three-dimensional structures of crown ethers, [2.2.2] and aza crown ethers obtained by substituting a part or all of the oxygen atoms of these crown ethers with nitrogen atoms (NH), and one or more crown ethers selected from derivatives thereof. One or more selected ones, one in which multiple ligands coordinate to one metal atom, one Including those sandwiched by a plurality of crown ether respect genus atoms. Specific examples include silver histidine, glycine copper, zinc pyrithione, copper pyrithione, copper triethylenetetramine, copper dibenzo24-crown-8, zinc zinc dibenzo24-crown-8, nickel nickel dibenzo24-crown-8, and the like.

  The chelate complex such as a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand is used in an amount of 0.05 to 5% by mass, especially 0.1% by mass, based on the soft vinyl chloride resin coating layer. Preferably, it is present in an amount of about 2% by mass, and the dispersibility of the chelate complex is improved by forming a soft vinyl chloride resin coating layer using a premixed chelate complex in a plasticizer. On the other hand, the chelate complex is present in a state of being supported on the inorganic porous particles, thereby improving the chelate complex to a stable sustained-release property, thereby stably maintaining a long-term antifungal / algae effect. . Specific examples of the inorganic porous particles include mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, and magnesium aluminate silicate. , Diatomaceous earth, and a treated product of these silane coupling agents. Preferred ligands to be supported on the inorganic porous particles are amino acids, ethylenediamine, triethylenetetramine, pyridine, ethyleneamineacetic acid, and pyrithione. 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 a solvent during the production of the chelate complex, and the chelate complex is adsorbed and supported on the inorganic porous particles, and then dried and isolated. Is used in the present invention. The support of the chelate complex by this method is either a two-step process in which the chelate complex is adsorbed and supported on the inorganic porous particles, or a one-step process in which the chelate complex formation and the adsorption and support are performed in the inorganic porous particles. You may. The loading ratio of the chelate complex to the inorganic porous particles is not particularly limited, but is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. At this time, the inorganic porous particles can simultaneously adsorb and support the fungicidal organic compound and the chelate complex, thereby making it possible to consolidate the compounding 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. The content of the inorganic porous particles contained in the soft vinyl chloride resin coating layer is 0.5 to 50% by mass, and preferably 1 to 20% by mass, based on the soft vinyl chloride resin coating layer.

On the other hand, as a fungicidal organic compound contained in the soft vinyl chloride resin coating layer, it inhibits oxidative phosphorylation of molds, bacteria (gram-positive, gram-negative), cell walls of fungi, etc. It is an organic compound that exerts effects such as electron transfer system inhibition, -SH group inhibition, DNA synthesis inhibition, cell epidermal function inhibition, lipid metabolism inhibition, and chelate formation. These are specifically described in A). Imidazole compounds such as 2- (4-thiazolyl) -benzimidazole (abbreviation: TBZ), 2- (carbomethoxyamino) benzimidazole (abbreviation: BCM), methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate, B ). Thiazole compounds such as 2-n-octyl-4-isothiazolin-3-one, 2-mercaptobenzothiazole, 2- (4-thiocyanomethylthio) benzothiazole and 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 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 Pyridine compounds such as -oxide copper salts and 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-based 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 and the like G). N- (fluorodichloromethylthio) phthalimide, N-trichloromethylthiotetrahydrophthalimide, N- (trichloromethylthio) -4-cyclohexane1,2-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 benzalkonium 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 System, nitrile system, organic iodine system, anilide system, disulfide system, thiocarbamate system, haloallyl sulfone system, organic tin system, thiadiazine system, and natural product extraction components (hinokitiol, tea catechin, chitosan, etc.) Can also. The content of these fungicidal 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, based on the soft vinyl chloride resin coating layer.

  The above-mentioned fungicidal organic compound is preferably present at 0.05 to 5% by mass, particularly 0.1 to 2% by mass, based on the soft vinyl chloride resin coating layer. The dispersibility of the fungicidal 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, in the use system in which the fungicidal organic compound is supported on the inorganic porous particles, the sustained release of the fungicidal organic compound is stably controlled, thereby stably maintaining the long-term fungicidal and anti-algal effects. It is possible to make. Specific examples of the inorganic porous particles include mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, and magnesium aluminate silicate. , Diatomaceous earth, and a treated product of these silane coupling agents. The method of supporting the fungicidal organic compound on the inorganic porous particles is carried out by mixing and stirring the inorganic porous particles in a solvent containing the fungicidal organic compound dissolved therein or a solvent containing the fungicidal organic compound dispersed therein. The inorganic porous particles are made to adsorb and carry the antifungal organic compound on the inorganic porous particles, and are dried and isolated, and those obtained by adsorption and carrying of the antifungal organic compound by sublimation or heat melting are used in this study. Used in the invention. At this time, the inorganic porous particles can simultaneously adsorb and support the fungicidal organic compound and the chelate complex, thereby making it possible to consolidate the compounding amount of the inorganic porous particles. The loading ratio of the fungicidal organic compound to the inorganic porous particles is not particularly limited, but is preferably 0.1 to 10% by mass, and particularly preferably 1 to 5% by mass. 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. The content of the inorganic porous particles contained in the soft vinyl chloride resin coating layer is 0.5 to 50% by mass, and preferably 1 to 20% by mass, based on the soft vinyl chloride resin coating layer.

  In addition, the flame retardant that complies with the Fire Service Act shall be secured by blending a flame retardant into the soft vinyl chloride resin coating layer, and it shall be a nonflammable material (nonflammable film material for tent structures) certified by the Minister of Land, Infrastructure, Transport and Tourism. Is preferred. A flame retardant such as a phosphorus-containing compound, a nitrogen-containing compound, or an inorganic compound may be blended in an amount of 10 to 100 parts by mass with respect to 100 parts by mass of a vinyl chloride resin (not including a plasticizer). , Red phosphorus, (metal) phosphate, (metal) organic phosphate, ammonium polyphosphate, and the like. Examples of the nitrogen-containing compound include (iso) cyanurate compounds, (iso) cyanuric acid compounds, Guanidine-based compounds, urea-based compounds and derivatives thereof, and inorganic compounds include metal oxides (such as antimony trioxide and antimony pentoxide), metal hydroxides (such as aluminum hydroxide and magnesium hydroxide), Metal composite oxide (zirconium-antimony composite oxide), metal composite hydroxide (zinc hydroxystannate, hydrotalcite, etc.) ), And the like. The flame retardancy can be improved by using two or more of these flame retardants.

  In addition, the soft vinyl chloride resin coating layer may be used alone or in combination with a plurality of stabilizers such as a calcium zinc composite, a barium zinc composite, an organic tin laurate, an organic tin mercaptite, and an epoxy as a stabilizer for the soft vinyl chloride resin. When used, the thermal deterioration and discoloration during production of the film material for a tent structure of the present invention are suppressed, and the weather resistance is further improved. The film material for a tent structure of the present invention can be freely colored with a pigment. In particular, coloring such as white or pastel color makes the contrast of ink jet printing or marking film characters clear. In addition, in the soft vinyl chloride resin coating layer, various known additives for the vinyl chloride resin can be blended in various optional amounts. If necessary, a light stabilizer (HALS), an ultraviolet absorber (benzotriazole, Benzophenone type), antioxidant (phenol type), optical brightener, antistatic agent, curing agent (isocyanate type), insect repellent (pyrethroid type), deodorant (silicon oxide / metal oxide composite type) ), Thermal barrier fillers (hollow particles, coarse-grained titanium oxide, etc.), fragrances, luminous pigments (strontium aluminate, etc.), aluminum flake pigments, pearl pigments, inorganic fillers (calcium carbonate, barium sulfate, etc.) Can be included.

  As one aspect of the film 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, and the photocatalytic substance has a redox effect. Effective self-cleaning of dust and dirt (washing by rainfall by making the antifouling layer hydrophilic with a photocatalyst, and decomposition of molds and algae by the photocatalyst), and effective and long-term generation of molds and algae This makes it possible to stably maintain the appearance of the tent structure. The photocatalytic substance-containing antifouling layer includes, as the photocatalytic substance, at least one particle selected from titanium oxide, titanium peroxide (peroxotitanic acid), zinc oxide, tin oxide, strontium titanate, tungsten oxide, and bismuth oxide. And at least one chelate complex selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand (see paragraph [0020] ] And [0021]). The photocatalyst substance-containing antifouling layer comprises 10 to 70% by mass of a photocatalyst material, 25 to 90% by mass of a metal oxide gel and / or a metal hydroxide gel (silica sol, alumina sol, zirconia sol, niobium oxide sol, etc.), a silicon compound (poly) A sol-gel thin film containing an inorganic substance and having a thickness of 0.1 to 15 μm and having a composition of 1 to 20% by mass (siloxane, colloidal silica, silica, etc.) and 1 to 10% by mass of a chelate complex is preferable. In this case, an intermediate protective layer may be provided between the photocatalytic substance-containing antifouling layer and the soft vinyl chloride resin coating layer to protect the soft vinyl chloride resin coating layer from the redox action of the photocatalytic substance. It is preferable from the viewpoint of improving durability, and 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, which is a composition obtained by omitting the photocatalytic substance from the composition of the photocatalytic substance-containing antifouling layer. The other antifouling layer containing a photocatalytic substance is coated on a fluorine-containing copolymer resin (polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, etc.). The surface of photocatalytic substance 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 silicate aluminate, etc. A chelate complex-containing coating film having a thickness of 5 to 50 μm containing the photocatalytic substance composite particles of the photocatalytic activity control type can be used.

  The chelate complex contained in the photocatalytic substance-containing antifouling layer includes mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, silica Magnesium aluminate, diatomaceous earth, and those treated with a silane coupling agent, are supported on one or more inorganic porous particles, and the controlled release of the chelate complex is controlled for a long time. Can stably maintain the fungicidal and anti-algae effects of. The inorganic porous particles described in paragraph [0022] can be used in the same manner. The loading ratio of the chelate complex to the inorganic porous particles is not particularly limited, but is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. A fungicidal organic compound and a chelate complex can be simultaneously adsorbed and carried on the inorganic porous particles.

  In order to construct a tent structure, the bonding of the membrane material for a tent structure of the present invention (end overlapping bonding) can be performed by high-frequency vibration using a high-frequency welding machine. A resin material is placed between two electrodes (one electrode is a weld bar), and the resin layer of the film material is heated by molecular friction heat by applying a potential difference oscillating at a high frequency (1 to 200 MHz) while applying pressure with the weld bar. By being in a melt-softened state, they are fused and then cooled and solidified in that state to obtain a joined body. Also, an ultrasonic fusion method of amplifying the amplitude of ultrasonic energy (16 to 30 KHz) generated from the ultrasonic vibrator and performing fusion using frictional heat generated at a boundary surface of the film material, or an electric heater. A hot air fusion method in which hot air set in a stepless manner at 100 to 700 ° C. is blown between the film materials through a nozzle by control to melt and soften the surface of the film material, and to press and fuse the film material immediately after passing through the nozzle, It can be joined by a hot plate fusion method in which the adherend is pressed and fused using a mold (trowel) with a heater built in above the melting temperature of the soft vinyl chloride resin coating layer or higher.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples. In the following Examples and Comparative Examples, the criteria used for evaluating the performance such as the antifungal property of the membrane material for tent structures are based on the following test methods.
(I) Evaluation of fungicidal and anti-algal properties by outdoor extension exposure The slope of an exposure table (base is made of moss-grown concrete) on a tent structure membrane with a width of 20 cm and a length of 2 m facing north. The film was continuously stretched 1 m each in the ° direction and the vertical direction, and exposed outdoors for 18 months. After 12 months, 24 months, and 36 months after the expansion, the entire membrane material for tent structures was observed, and the presence or absence of mold and algae, and the state of their growth were classified into ranks, whereby fungicidal (or algal) resistance was evaluated. ) Was evaluated.
* The outdoor exhibition started in April in Soka City, Saitama Prefecture.
1: No occurrence (trace) of mold (algae) is observed (maintain initial state)
2: Slight mold (algae) generation (trace) is observed. 3: Partial (area within 9% of test sample) mold (algae) generation (trace) is recognized. 4: Partial (10% of test sample). Mold (algae) generation (trace) in the above areas) (II) Evaluation of fungicide resistance (JIS Z2911 culture test)
The following test mold spores were inoculated into a membrane material for a tent structure having a width of 3 cm and a length of 3 cm, placed on a potato dextrose agar medium, and generated at 28 ° C. for 7 days and 14 days in a petri dish. The situation was observed and evaluated according to the following criteria.
1: No hyphal growth was observed in the inoculated portion of the test piece. 2: The area of the hyphal growth portion observed in the inoculated portion of the test piece was:
Not more than 1/3 of the total area 3: The area of the hyphal growth area observed in the inoculated part of the test piece is
<Test mold> More than 1/3 of the total area <Mold for test> a + b + c mixed mold a: Aspergillus niger NBRC 105649 (black mold)
b: Penicillium citrinum NBRC 6352 (blue mold)
c: Cladosporium cladosporioides NBRC 6348 (Kurokawa mold)
(III) Persistence evaluation of antifungal property (culture test according to JIS Z2911)
A test piece was prepared by immersing a membrane material for a tent structure having a width of 3 cm × a length of 3 cm in 200 cc of water (ethanol 35% concentration) and allowing it to stand at 30 ° C. for 1 week as a test piece (II). Was tested.
1: No hyphal growth was observed in the inoculated portion of the test piece. 2: The area of the hyphal growth in the inoculated portion of the test piece was:
Not more than 1/3 of the total area 3: The area of mycelial growth observed in the inoculated part of the test piece was
Over 1/3 of total area

[ Reference Example 1]
Polyester fiber plain woven base cloth (warp 1111 dtex multifilament yarn: yarn density 19 / 2.54 cm × weft 1111 dtex multifilament yarn: yarn density 21 / 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 surfaces thereof was 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 laminating machine at a temperature of 190 ° C.
<Soft vinyl chloride resin composition (1)>
Vinyl chloride resin (degree of polymerization 1050) 100 parts by mass Diisononyl 1,2-cyclohexanedicarboxylate (plasticizer) 50 parts by mass * Trade name: Hexamol DINCH (manufactured by BASF)
Glycine copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by mass * A chelate complex or a carrier thereof was used by previously mixing in a plasticizer. 10,10'-oxybisphenoxy 0.15 parts by mass of arsine (antifungal organic compound) 0.15 parts by mass of 2- (4-thiazolyl) -benzimidazole (antifungal organic compound) * The antifungal organic compound or its carrier is a plasticizer in advance. 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 Combustion agent) 10 parts by mass Rutile type titanium oxide (white pigment) 5 parts by mass Benzotriazole (ultraviolet absorber) 0.3 parts by mass

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

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

[ Reference Example 4]
In Reference Example 1, 0.5 parts by mass of glycine copper (chelate complex) and 0.5 parts by mass of histidine silver (chelate complex) were previously added to mesoporous silica by 0.5 parts by mass of glycine copper (chelate complex) and histidine silver ( (Chelate complex) A thickness of 0.65 mm was obtained in the same manner as in Reference Example 1 except that the glycine copper (chelate complex) / histidine silver (chelate complex) -supported mesoporous silica, which supported 0.5 part by mass, was replaced by 31 parts by mass. A film material having a mass of 698 g / m ² was obtained.
* Preparation of mesoporous silica supporting glycine copper (chelate complex) / histidine silver (chelate complex) Mesoporous 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). 30 g of silica (average particle diameter 2.5 μm) was added, and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). The water-ethanol solvent was removed under reduced pressure, and then dried at 100 ° C. As a result, about 31 g of a powder was obtained. The amount of copper glycine (chelate complex) and the amount of silver histidine (chelate complex) supported by 31 g of this powder are each 0.5 g.

[ Reference Example 5]
Except that 11 parts by mass of mesoporous silica carrying glycine copper (chelate complex) / histidine silver (chelate complex) of Reference Example 4 was replaced by 31 parts by mass of zirconium phosphate carrying glycine copper (chelate complex) / histidine silver (chelate complex). In the same manner as in Reference 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) and histidine silver (chelate complex) In a 200 ml water-ethanol solution containing 0.5 g of glycine copper (chelate complex) and 0.5 g of histidine silver (chelate complex), 30 g of zirconium phosphate (average particle size: 3 μm) was added, and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). The water-ethanol solvent was removed under reduced pressure, followed by drying at 100 ° C. As a result, about 31 g of a powder was obtained. The amount of copper glycine (chelate complex) and the amount of silver histidine (chelate complex) supported by 31 g of this powder are each 0.5 g.

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

[Example 7]
0.5 parts by mass of silver histidine (chelate complex) and 0.5 parts by mass of 24-crown-8 copper (chelate complex) of Example 3 were combined with silver histidine (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 the diatomaceous earth was replaced with 31 parts by mass of diatomaceous earth.
* Preparation of diatomaceous earth supporting histidine silver (chelate complex) / 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 To 200 ml, 30 g of diatomaceous earth (average particle size: 2 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 about 31 g of a powder was obtained. The amount of silver histidine (chelate complex) supported by 31 g of this powder and the amount of 24-crown-8 copper are each 0.5 g.

[ Reference Example 8]
Reference 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 Reference Example 4) except that 0.15 parts by mass was replaced with 10.5 parts by mass of a fungicidal 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 in the 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 diameter 2.5 μm) was added, and a silane coupling agent (γ- The mixture was stirred at room temperature for 1 hour together with 1 g of (glycidoxypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.

[ Reference Example 9]
In Reference Example 5, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were added to 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ in advance on zirconium phosphate. A film material having a thickness of 0.65 mm and a weight of 700 g / m ² was obtained in the same manner as in Reference Example 5 except that the replacement was carried out with 10.5 parts by mass.
* 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, add 10 g of zirconium phosphate (average particle diameter: 3 μm), and add a silane coupling agent (γ- The mixture was stirred at room temperature for 1 hour together with 1 g of (glycidoxypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.

[ Reference Example 10]
9. In Reference Example 6, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were added to 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ in advance on a synthetic zeolite. 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 Reference Example 6, except that the amount was changed to 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 diameter 2 μm) was added, and a silane coupling agent (γ-glycidide) was added. The mixture was stirred at room temperature for 1 hour together with 1 g of (xypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.

[Example 11]
9. In Example 7, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were added to diatomaceous earth in advance to carry 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 weight of 695 g / m ² was obtained in the same manner as in Example 7 except that the amount was changed to 5 parts by mass.
* Preparation of diatomaceous earth carrying OBPA / TBZ To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of diatomaceous earth (average particle diameter 2 μm) was added, and a silane coupling agent (γ-glycidide) was added. The mixture was stirred at room temperature for 1 hour together with 1 g of (xypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.

[ Reference Example 12]
In Reference Example 8, 10.5 parts by mass of mesoporous silica supporting glycine copper (chelate complex) / histidine silver (chelate complex) and 10.5 parts by mass of mesoporous silica supporting OBPA / TBZ were previously added to mesoporous silica to form glycine copper (chelate complex). ) 41 parts by mass of mesoporous silica carrying a chelate complex and a fungicidal organic compound carrying 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 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 Reference Example 8 except that the film material was replaced.
* Preparation of mesoporous silica supporting chelate complex and antifungal organic compound 100 ml of a water-ethanol solution containing 0.5 g of glycine copper (chelate complex), 0.5 g of histidine silver (chelate complex), and 0.15 g of OBPA and 0.15 g of TBZ Was added with 40 g of mesoporous silica (average particle size 2.5 μm), and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). It dried at ℃ and obtained about 41g of powder. The amount of glycine copper (chelate complex) and the amount of silver histidine (chelate complex) supported by 41 g of this powder are 0.15 g, and the amounts of OBPA and TBZ are each 0.15 g.

[ Reference Examples 13 , 14 and Example 15]
The film materials of Reference Examples 1 and 2 and Example 3 with a photocatalytic substance-containing antifouling layer formed thereon were referred to as Reference Examples 13 and 14 and Example 15.
* Formation of intermediate protective layer A coating solution of the following silicon compound-containing resin is applied (wet) at 15 g / m ² with a coater having a gravure roll of 80 mesh and dried in a hot air oven at 100 ° C. for 1 minute to form an intermediate protective layer. Formed. (Solid content 3g / m ² )
<Silicon compound-containing resin layer coating liquid>
Acrylic-silicon 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 parts by mass Histidine silver (chelate complex) 0.5 parts by mass

* Formation of photocatalytic substance-containing antifouling layer 15 g / m ^{2 of a} coating solution for forming a photocatalyst substance-containing antifouling layer is applied in a coater having a gravure roll of 80 meshes in a hot air oven at 100 ° C. After drying for 5 minutes, the photocatalytic substance-containing antifouling layer was formed into a sol-gel (solids adhesion amount: 2 g / m ² ) to obtain a film material 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 photocatalytic 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 part by mass Histidine silver (chelate complex) 0.5 parts by mass

[ Reference Examples 16 to 18, 20 to 12, 14, and Examples 15, 19, 23 ]
The photocatalytic substance-containing antifouling layer was formed on the film material of Reference Examples 4 to 6, 8 to 10, 12 and Examples 3 , 7, and 11 , and Reference Examples 16 to 18, 20 to 12, 14, and Examples 15 , 19, and 23 .
* Formation of intermediate protective layer
The same composition and forming method as in Reference Examples 13 and 14 and Example 15 are used.
* Formation of photocatalytic substance-containing antifouling layer The following coating solution for forming a photocatalytic substance-containing antifouling layer is applied (wet) 25 g / m ² with a coater having a gravure roll of 80 meshes, and is coated in a hot air oven at 100 ° C. minutes dried form a photocatalyst substance containing antifouling layer (solid content adhesion quantity 7 g / ^{m 2),} to give each thickness 0.65mm examples 16-24, the film material of mass 707 g / ^{m 2.}
<Coating liquid for forming antifouling layer containing photocatalytic substance>
100 parts by mass of vinylidene fluoride resin solution (solid content: 15% by mass) 8 parts by mass of photocatalytic titanium oxide (average particle size: 1 μm) * Partial coating of hydroxyapatite with a surface coverage of 4 to 10%)
Mesoporous silica supporting copper glycine (chelate complex) and silver histidine (chelate complex)
10 parts by mass
* Preparation of mesoporous silica supporting glycine copper (chelate complex) / histidine silver (chelate complex) Mesoporous 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). 30 g of silica (average particle diameter 2.5 μm) was added, and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). The water-ethanol solvent was removed under reduced pressure, and then dried at 100 ° C. As a result, about 31 g of a powder was obtained. The amount of copper glycine (chelate complex) and the amount of silver histidine (chelate complex) supported by 31 g of this powder are each 0.5 g.

[Antifungal effect of Examples 3 , 7 , 11 ]
The film materials for tent structures of Examples 3 , 7 , and 11 in which the soft vinyl chloride resin coating layer contains a chelate complex and a fungicide-resistant organic compound are all prepared by using a chelate complex. No molds or algae were found (traces) after 36 months of spreading exposure, and the initial state was maintained. No fungal growth was observed in the antifungal test (II): JIS Z2911 culture test. Thus, it was revealed that a sufficient antifungal effect can be expected as a film material for a tent structure. The superiority in the antifungal test (III) assuming long-term use is that the membrane material of Example 11 in which a chelate complex and an antifungal organic compound are supported on inorganic porous particles is the most antifungal. The film material of Example 7 using the chelate complex supported on inorganic porous particles has a high long-term durability, and the film material of Example 3 has a somewhat longer duration in Examples. Although poor in sustainability, it is clear that it is superior to the conventional film material. Further, the tent structure membrane materials of Examples 15 , 19 , and 23 in which the photocatalytic substance-containing antifouling layer was formed on the tent structure film materials of Examples 3 , 7 , and 11 showed accumulation of dust and rain streaks. No remarkable occurrence was observed for a long period of time, and the antifouling effect of rainfall self-cleaning by the photocatalytic substance-containing antifouling layer and the effect of decomposing organic substances such as fungi caused the membranes for tent structures of Examples 3 , 7 , and 11. The material for the tent structure of Examples 19 and 23 has a longer duration than the material of the tent structure of Examples 11 and 15 , particularly in the film material for tent structure of Examples 19 and 23. It was excellent.

[ Reference Comparative Example 1]
Same as Reference Example 1 except that 0.5 parts by mass of glycine copper (chelate complex) and 0.5 parts by mass of histidine silver (chelate complex) were omitted from the soft vinyl chloride resin composition (1) of Reference Example 1. A film material having a thickness of 0.65 mm and a mass of 700 g / m ² was obtained. By omitting the chelate complex from the film material of Reference Comparative Example 1, only the antifungal effect of the antifungal organic compound was obtained, and the initial antifungal effect was well exhibited, but after 36 months of the antifungal test (I). Was found to be mildew due to factors such as bleeding of the antifungal organic compound, washing away due to rainfall, deterioration, etc., and the occurrence of fungi was partially observed (approximately 6% of the specimen). As a result of the extraction of the organic compound, the area of the growth portion of the hypha observed in the inoculated portion of the test piece exceeded one-third of the total area. Was greatly impaired.

[ Reference Comparative Example 2]
From the soft vinyl chloride resin composition (1) of Reference Example 1, 0.5 parts by mass of copper glycine (chelate complex) and 0.5 parts by mass of silver histidine (chelate complex) were omitted, and instead, zeolite 1 carrying silver ion was used. 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 Reference Example 1 except that the amount was changed to parts by mass. The membrane material of Reference Comparative Example 2 was able to exhibit a relatively long-term antifungal property by having a silver ion-supporting zeolite and an antifungal organic compound, but after 36 months of the antifungal test (I), The occurrence of mold was recognized due to factors such as bleeding of the antifungal organic compound, washing away due to rainfall, deterioration, etc. In the antifungal test (III), extraction of the antifungal organic compound resulted in the inoculation of the test piece on the inoculated portion. Although the area of the growing portion of the hyphae does not exceed 1/3 of the total area, it is better than Comparative Example 1, but is inferior to the membrane material of Example 1 in terms of long-term stability of the antifungal property. Was something.

[ Reference Comparative Example 3]
A soft vinyl chloride resin composition of Reference Example 1 (1), 10, 10 ^'- 0.15 part by weight oxy bisphenoxy sialic Shin (antifungal organic compound), and 2- (4-thiazolyl) - benzimidazole (proof (Moldy organic compound) 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 Reference Example 1 except that 0.15 parts by mass was omitted. The film material of Reference Comparative Example 3 had only the antifungal effect by the chelate complex by omitting the antifungal organic compound, and although the initial antifungal effect was well exhibited, the antifungal test (I) was 36 months. After that, the occurrence of mold was partially observed (about 6% of the specimen), and in the antifungal test (III), the area of the mycelial growth observed in the inoculated portion of the test piece was 1% of the total area. As a result, the long-term stability of the antifungal property was significantly impaired as compared with the film material of Example 1.

[ Reference Comparative Example 4]
When the soft vinyl chloride resin composition (1) of Reference Example 1 was changed to a calendar-molded type polyurethane resin composition (1) and subjected to calendar molding at 180 ° C., glycine copper (chelate complex) and histidine silver ( The chelate complex) was seized on a calender-molded heat roll, making it impossible to process the film and making it impossible to obtain a film material.
<Polyurethane resin composition (1)>
Polyurethane resin (ether type) 100 parts by mass Glycine copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by mass 10,10'-oxybisphenoxyarsine (antifungal organic compound) 0.15 Parts by mass 2- (4-thiazolyl) -benzimidazole (mold-resistant organic compound) 0.15 parts by mass ammonium polyphosphate (flame retardant) 10 parts by mass melamine cyanurate (flame retardant) 10 parts by mass rutile-type titanium oxide (white) Pigment) 5 parts by mass Benzotriazole (UV absorber) 0.3 parts by mass Montanic acid wax (lubricant) 0.5 parts by mass

[ Reference Comparative Example 5]
When the soft vinyl chloride resin composition (1) of Reference Example 1 was changed to a calender-molded type polyethylene resin composition (1) and subjected to calender molding at 150 ° C., glycine copper (chelate complex) and histidine silver ( The chelate complex) was seized on a calender-molded heat roll, making it impossible to process the film and making it impossible to obtain a film material.
<Polyethylene resin composition (1)>
Polyurethane resin (ether type) 100 parts by mass Glycine copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by mass 10,10'-oxybisphenoxyarsine (antifungal organic compound) 0.15 Parts by mass 2- (4-thiazolyl) -benzimidazole (mold-resistant organic compound) 0.15 parts by mass ammonium polyphosphate (flame retardant) 10 parts by mass melamine cyanurate (flame retardant) 10 parts by mass rutile-type titanium oxide (white) Pigment) 5 parts by mass Benzotriazole (UV absorber) 0.3 parts by mass Montanic acid wax (lubricant) 0.5 parts by mass

  As is clear from the above examples and comparative examples, according to the present invention, a film material capable of minimizing the occurrence of mold and algae is obtained. Large tent structures (stadium roof, dome stadium, retractable roof dome, pavilions, etc.), awning tent structures (public facilities monuments, station building home roofs, access passage roofs, arcade roofs, stores, residences, etc.), interior lighting The present invention can be widely used for tent structures (structures in which a waterproof fiber composite sheet is attached to a metal frame) such as a tent structure (eg, an electric sign, an image projection dome, and art molding).

Claims (8)

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, wherein the soft vinyl chloride resin coating layer has a silver ligand, a copper ligand, and a zinc ligand. , and with one or more chelate complex selected from nickel ligands, see contains an antifungal organic compound is a ligand of at least crown ethers and amino acids of the chelate complex and the chelating complex crown A membrane material for a tent structure, which is a combination of an ether complex and an amino acid complex, wherein the amino acid is at least one selected from glycine, histidine, and methionine . The membrane material for a tent structure according to claim 1, wherein the ligand of the chelate complex further includes at least one selected from ethylenediamine, triethylenetetramine, piperidine, ethyleneamineacetic acid, pyrithione, phenanthroline, and porphyrin. .   The chelate complex is mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium aluminate, diatomaceous earth, The film material for a tent structure according to claim 1 or 2, wherein the film material is supported on at least one kind of inorganic porous particles selected from the group consisting of:   The antifungal compound is 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 organic metal compound. The film material for a tent structure according to any one of claims 1 to 3, wherein the film material is at least one 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 film material for a tent structure according to claim 4, which is supported on at least one kind of inorganic porous particles selected from diatomaceous earth and a treated product 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 is titanium oxide, titanium peroxide (peroxotitanic acid), zinc oxide. The film material for a tent structure according to any one of claims 1 to 5, wherein the film material is at least one selected from a 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 includes at least one chelate complex 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 may be a mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate 8. The film material for a tent structure according to claim 7, wherein the film material is supported on at least one kind of inorganic porous particles selected from the group consisting of silica, magnesium aluminate, diatomaceous earth, and a treated product of these silane coupling agents.