JP6678037B2 - 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 an aqueous solution of a complex (Patent Document 3) have been proposed, and their long-term stability is ensured. However, the aqueous solution of the complex has poor compatibility with a soft-blended vinyl chloride resin containing a plasticizer and causes poor mixing. It is practically difficult to use. Accordingly, as a film material for producing a film material for a tent structure, a film material having a long-term stable and sustainable fungicidal and algae-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 situation, and as a result, based on a fiber woven fabric, a flexible sheet having a thermoplastic resin coating layer on at least one surface thereof, a thermoplastic resin coating layer, By containing a polyether metal complex and a fungicidal substance, as a film material for a tent structure, which has been difficult with the above prior art, a long-lasting fungicidal effect of minimizing mold and algae for a long period of time The inventors have found that the problem of improvement can be solved, and have completed the present invention.

  That is, the film material for a tent structure of the present invention is a flexible sheet having a fibrous fabric as a base material and having a thermoplastic resin coating layer on at least one surface thereof, wherein the thermoplastic resin coating layer is a cyclic polyether metal. It preferably contains a complex and an antifungal substance. Thereby, the cyclic polyether metal complex and the antifungal substance exhibit a synergistic effect, and in particular, the metal and metal ions supported on the cyclic polyether metal complex are stabilized, and are hardly discharged out of the system. 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.

  In the membrane material for a tent structure of the present invention, the cyclic polyether metal complex is at least one selected from the group consisting of cyclic polyethers such as crown ether, azacrown ether, thiacrown ether, azathiacrown ether, and cryptand. And a derivative group obtained by introducing a functional group and / or a substituent into the cyclic polyether group, and a polymer group having at least one selected from the group consisting of polymers having the cyclic polyether as a repeating unit. Is preferred. This stabilizes the metal and metal ions carried by the cyclic polyether metal complex, making them difficult to be discharged out of the system, making it suitable for tent structures that can effectively suppress the generation of mold and algae for a long period of time. Film material can be obtained.

  In the film material for a tent structure of the present invention, the cyclic polyether metal complex is at least one selected from a cyclic polyether silver complex, a cyclic polyether copper complex, a cyclic polyether zinc complex, and a cyclic polyether nickel complex. It is preferred that This stabilizes silver ions, copper ions, zinc ions, nickel ions, and the like carried on the cyclic polyether metal complex, and makes it difficult for them to be discharged out of the system. A film material suitable for a tent structure that can be suppressed can be obtained.

  In the membrane material for a tent structure of the present invention, the antifungal substance may be synthetic amorphous silica, mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, Silver ions and / or copper ions are contained in one or more inorganic porous particles selected from hydroxyapatite, silica alumina, calcium silicate, magnesium silicate aluminate, diatomaceous earth, and a silane coupling agent-treated product thereof. It is preferably carried. 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 substance may be 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 stably and effectively suppressing the generation of mold and algae.

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

  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 thermoplastic resin coating layer. It is preferably at least one selected from titanium oxide (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 at least one selected from a cyclic polyether silver complex, a cyclic polyether copper complex, a cyclic polyether zinc complex, and a cyclic polyether nickel complex. It is preferable to include a cyclic polyether metal complex of Effective self-cleaning of dust and dirt by the redox effect of the photocatalytic substance (washing by rainfall by making the antifouling layer hydrophilic with the photocatalyst, and decomposition of mold and algae by the photocatalyst), and cyclic polyether metal Due to the presence of the complex, it is possible to obtain a film material for a tent structure capable of suppressing the generation of mold and algae more effectively and for a longer period.

  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 fibrous fabric as a base material and having a thermoplastic resin coating layer on at least one surface thereof, wherein the thermoplastic resin coating layer has a cyclic polyether metal complex ( A silver complex, a copper complex, a zinc complex, and a nickel complex), and a fungicide, wherein the inorganic porous particles carry silver ions or copper ions as necessary. If necessary, imidazole compounds, thiazole compounds, isothiazoline compounds, pyridine compounds, triazine compounds, triazole compounds, N-haloalkylthio compounds, quaternary ammonium salts -Based compounds, organometallic compounds, etc., and if necessary, ones which support inorganic fungicide on inorganic porous particles. A photocatalytic substance-containing antifouling layer can be formed on the plastic resin coating layer, and a cyclic polyether metal complex (silver complex, copper complex, zinc complex, and nickel complex) can be formed on the photocatalytic substance containing antifouling layer, if necessary. ) Can be included.

  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 (PET, PBT, PNT) fiber, wholly aromatic polyester fiber, nylon fiber, wholly aromatic polyamide fiber, aromatic heterocyclic polymer (polybenzimidazole, polybenzoxazole, polybenzothiazole, etc.) fiber, acrylic fiber, polyurethane fiber Alternatively, synthetic fibers such as mixed fibers thereof can be used, and polyester (PET: polyethylene terephthalate) fibers are particularly 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 thermoplastic resin coating layer formed by heat laminating a thermoplastic resin film on both sides of a woven fabric (porosity 7.5 to 30%) preferably woven with multifilament yarns. In the case of a cloth (span), a short fiber spun cloth (span) having a porosity of 0 to 5% is preferably coated on both sides with a liquid thermoplastic resin to heat treatment, or depping to a thermoplastic resin coating layer by heat treatment. Suitable for forming.

The thermoplastic resin coating layer is formed of a thermoplastic resin composition containing a cyclic polyether metal complex as an essential component and a fungicidal substance in a thermoplastic resin. The paste vinyl chloride resin (emulsion polymerization type) ) -Forming by polyvinyl chloride resin paste sol-gelation heat treatment, or using a straight vinyl chloride resin (suspension polymerization type), calender rolling molding or T-die extrusion molding vinyl chloride resin film (sheet) Particularly preferred. 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 to use a mixture obtained by mixing a cyclic polyether metal complex in advance, and thereby to make the dispersibility of the cyclic polyether metal complex uniform, thereby ensuring the stability of the antifungal effect. As thermoplastic resins other than vinyl chloride resin, vinyl chloride elastomer, olefin resin (PE, PP), olefin elastomer, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin , Urethane-based elastomers, acrylic-based elastomers, styrene-based elastomers, polyester-based elastomers, fluorine-based elastomers, silicone-based elastomers and the like can be used alone or in combination with one another. The thermoplastic 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 cyclic polyether metal complex contained in the thermoplastic resin coating layer is at least one selected from a cyclic polyether silver complex, a cyclic polyether copper complex, a cyclic polyether zinc complex, and a cyclic polyether nickel complex. Polyether metal complex (metal ion) reacts with the SH group of the protein involved in cell permeability on the surface of the mold and inhibits enzymes and proteins required for vital activities. By cross-linking double-stranded DNA and inhibiting DNA replication, the growth of molds and algae is suppressed. 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 cyclic polyether metal complex is obtained by ion-bonding the metal salt of the ion source and the cyclic polyether through an appropriate solvent, and the dried and isolated product is used in the present invention.

  The cyclic polyether metal complex has at least one selected from the group consisting of cyclic polyethers such as crown ether, azacrown ether, thiacrown ether and azathiacrown ether, and a functional group and / or an alkyl group in the cyclic polyether group. A metal complex based on one or more cyclic polyethers selected from the group of the introduced derivatives and the group of polymers having a cyclic polyether as a repeating unit. Among them, crown ether is 9-crown-3, 12-crown-4,15-crown-5,18-crown-6,21-crown-7, 24-crown-8,27-crown-9,30-. [(9 + 3n) -crown- (3 + n)] such as crown-10,33-crown-11,36-crown-12, wherein n is a cyclic polyether represented by an integer of 1 or more; The number at the beginning indicates the total number of atoms, and the number at the end indicates the number of oxygen atoms. Further, as a benzocrown ether, at least one benzene ring is bonded to these crown ethers of the formula [(9 + 3n) -crown- (3 + n)] in such a manner as to share two carbon atoms of the crown ether. For example, taking 18-crown-6 as an example, benzo18-crown-6, dibenzo18-crown-6, tribenzo18-crown-6, and hexabenzo18-crown-6 can be exemplified. Further, as a cyclohexano crown ether, at least one cyclohexane ring is bonded to these crown ethers of the formula [(9 + 3n) -crown- (3 + n)] by sharing with two carbon atoms of the crown ether. For example, taking 18-crown-6 as an example, cyclohexano 18-crown-6, dicyclohexano 18-crown-6, tricyclohexano 18-crown-6, hexacyclohexano 18-crown-6 Can be exemplified. Aza crown ether, benzoaza crown ether, and cyclohexanoaza crown ether correspond to those obtained by substituting a part or all of the oxygen atoms of the above-mentioned crown ether group with a nitrogen atom (NH). Similarly, thiacrown ether, benzothiacrown ether, and cyclohexanothiacrown ether correspond to those in which part or all of the oxygen atoms of the above-mentioned crown ether group have been substituted with sulfur atoms (S). Similarly, azathia crown ethers, benzoazathia crown ethers, and cyclohexanoazathia crown ethers have substituted part or all of the oxygen atoms of the aforementioned crown ether group with nitrogen atoms (NH) and sulfur atoms (S). Things are equivalent.

The group of crown ether derivatives includes those obtained by introducing a functional group and / or a substituent into the crown ether described in paragraph [0023]. Examples of the functional group include a hydroxy group, a vinyl group, an acryloyl group, an acyl group, and an acetyl group. Group, carboxyl group, sulfonic acid group, carbonyl group, epoxy group, amino group, imino group, cyano group, azo group, isocyanate group, sulfo group, nitro group, thiol group and the like.Examples of the substituent include alkyl. Groups, vinyl groups, allyl groups, aryl groups, phenyl groups, naphthyl groups, araalkyl groups, benzyl groups, cycloalkyl groups, alkoxy groups, methoxy groups, ethoxy groups and the like. The terminal and / or the side chain of these substituents may have the above-mentioned functional group. Examples of the polymer group having a cyclic polyether as a repeating unit include dimers and trimers of a crown ether derivative group, a bicyclic cryptand [2.2] which is a three-dimensional structure of a plurality of crown ethers, and a tricyclic cryptand. [2.2.2], and a polymer or a dendrimer. In particular, the polymer is a known polymer of a monomer A having a cyclic polyether (crown ether) structure and a monomer B capable of undergoing an addition reaction with the monomer A. These are polyester resin (-COOH + -OH), polyamide resin (-COOH + -NH ₂ ), polyurethane resin (-NCO + -OH), polyketone resin (-COOH + dibenzo crown ether: free). Acrylic resin and vinyl resin by homopolymerization of monomer A) Monomers A having a cyclic polyether (crown ether) structure in the linear chain or side chain of the polymer, and particularly having a cyclic polyether (crown ether) structure, are already known as cyclic polyether silver complex and cyclic polyether copper. It is preferable to form any one of a complex, a cyclic polyether zinc complex, and a cyclic polyether nickel complex, and to carry out an addition reaction or homopolymerization in a state of the cyclic polyether metal complex. Depending on the type and degree of polymerization of the polymer, it may be difficult to carry out the treatment for supporting metal ions in the cyclic polyether (crown ether) structure, or the carrying efficiency may be deteriorated. The cyclic polyether metal complex used in the present invention has a form in which one metal atom (ion) is surrounded by a plurality of cyclic polyethers (crown ethers), and one metal atom (ion) has two cyclic polyethers. An embodiment sandwiched by ether (crown ether) is included.

  Further, a cyclic polyether metal complex such as a cyclic polyether silver complex, a cyclic polyether copper complex, a cyclic polyether zinc complex, and a cyclic polyether nickel complex is used in an amount of 0.05 to 5 mass per thermoplastic resin coating layer. %, Particularly preferably 0.1 to 2% by mass. The cyclic polyether metal complex is formed into a soft vinyl chloride resin coating layer using a composition (paste sol or compound) previously mixed in a plasticizer. By doing so, the uniform dispersibility of the cyclic polyether metal complex is improved, and the stability of the antifungal effect is secured. On the other hand, the cyclic polyether metal complex is present in a state of being supported on the inorganic porous particles (gap between the secondary particles which are aggregates of the primary particles), thereby improving the chelate complex to a stable sustained release property. Thereby, the long-term antifungal and anti-algal effects can be stably maintained. Specific examples of the inorganic porous particles include synthetic amorphous silica, mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, and calcium silicate. , Magnesium aluminate silicate, diatomaceous earth, and secondary particles of these silane coupling agent-treated products. A method of supporting a cyclic polyether metal complex in the gap between secondary particles (aggregates) of inorganic porous particles is performed by mixing and stirring the inorganic porous particles in a solvent at the time of producing the cyclic polyether metal complex, and stirring the mixture. A chelate complex adsorbed and supported on particles, which is dried and isolated is used in the present invention. The loading of the cyclic polyether metal complex by this method is a two-step process in which the cyclic polyether metal complex is adsorbed and supported on the inorganic porous particles after the formation of the cyclic polyether metal complex. Or any one-step process performed. The loading ratio of the cyclic polyether metal 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 fungicidal substance and the cyclic polyether metal complex can be simultaneously adsorbed and carried on the inorganic porous particles (gap between the secondary particles), whereby the amount of the inorganic porous particles can be concentrated. And The particle size of the inorganic porous particles (secondary particles) is not particularly limited, but is preferably 0.5 to 10 μm, particularly preferably 1 to 5 μm. The content of the inorganic porous particles contained in the thermoplastic resin coating layer is 0.5 to 25% by mass, preferably 1 to 15% by mass, based on the thermoplastic resin coating layer.

  On the other hand, the antifungal substance contained in the thermoplastic resin coating layer includes synthetic amorphous silica, mesoporous silica, zeolite (synthetic), titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, One or more inorganic porous particles selected from metal ion exchangers such as silica alumina, calcium silicate, magnesium silicate aluminate, and diatomaceous earth, metal ion adsorbents, and treated products of these silane coupling agents ( What carries silver ion and / or copper ion in primary particle) is especially preferable. The particle size of the inorganic porous particles (primary particles) is not particularly limited, but is preferably 0.1 to 3 μm, particularly preferably 0.5 to 2 μm. The content of these inorganic porous particles contained in the soft vinyl chloride resin coating layer is 0.5 to 25% by mass, preferably 1 to 15% by mass, based on the thermoplastic resin coating layer.

On the other hand, as the antifungal substance contained in the thermoplastic resin coating layer, it inhibits oxidative phosphorylation against cell walls, cell membranes, cytoplasm, and cell nuclei of molds, bacteria (gram-positive, gram-negative), fungi, etc. It is an organic compound that exerts effects such as transmission 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 antifungal substances contained in the thermoplastic resin coating layer is 0.05 to 5% by mass, preferably 0.1 to 2% by mass, based on the thermoplastic resin coating layer.

  Further, the above-mentioned fungicide is preferably present in an amount of 0.05 to 5% by mass, particularly 0.1 to 2% by mass, based on the thermoplastic resin coating layer. By forming a soft vinyl chloride resin coating layer using the mixture therein, the uniform dispersibility of the antifungal substance is improved, thereby ensuring the stability of the antifungal effect. On the other hand, in a use system in which the fungicide is supported on inorganic porous particles (gap between secondary particles which are aggregates of primary particles), the controlled release of the fungicide is stably controlled, This makes it possible to stably maintain the long-term antifungal and anti-algal effects. Specific examples of the inorganic porous particles include synthetic amorphous silica, mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, and calcium silicate. , Magnesium silicate aluminate, diatomaceous earth, and a silane coupling agent-treated product thereof. The method of supporting the fungicide in the gaps between the secondary particles (aggregates) of the inorganic porous particles is performed by dissolving the fungicide in a solvent containing the fungicide or dispersing the fungicide in the solvent. Mix and stir the porous particles to adsorb and carry the antifungal substance on the inorganic porous particles, and then dry-isolate it, sublimate the antifungal substance, or adsorb and carry it under hot melting. Those obtained are used in the present invention. At this time, the inorganic porous particles can simultaneously adsorb and carry the fungicidal substance and the cyclic polyether metal complex, thereby making it possible to consolidate the compounding amount of the inorganic porous particles. The loading rate of the fungicidal substance on the inorganic porous particles is not particularly limited, but is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. The particle size of the inorganic porous particles (secondary particles) is not particularly limited, but is preferably 0.5 to 10 μm, particularly preferably 1 to 5 μm. The content of the inorganic porous particles contained in the thermoplastic resin coating layer is 0.5 to 25% by mass, preferably 1 to 15% by mass, based on the thermoplastic resin coating layer.

  In addition, by incorporating a flame retardant into the thermoplastic resin coating layer, it is possible to ensure flame resistance conforming to the Fire Service Law, and to use a non-combustible material (non-combustible film material for tent structures) certified by the Minister of Land, Infrastructure, Transport and Tourism. preferable. Specifically, 10 to 100 parts by mass of a flame retardant such as a phosphorus-containing compound, a nitrogen-containing compound, or an inorganic compound may be blended with respect to 100 parts by mass of the thermoplastic resin. ) Phosphates, (metal) organic phosphates, ammonium polyphosphate, and the like. Examples of the nitrogen-containing compound include (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, and urea compounds. Compounds and derivatives thereof, and inorganic compounds include metal oxides (antimony trioxide, antimony pentoxide, etc.), metal hydroxides (aluminum hydroxide, magnesium hydroxide, etc.), and metal composite oxides (zirconium -Antimony composite oxide), metal composite hydroxide (zinc hydroxystannate, hydrotalcite, etc.). The flame retardancy can be improved by using two or more of these flame retardants.

  In particular, for the soft vinyl chloride resin coating layer, a stabilizer such as calcium zinc composite, barium zinc composite, organic tin laurate, organic tin mercaptite, or epoxy is used alone or in combination as a stabilizer for the soft vinyl chloride resin. The use suppresses thermal deterioration and discoloration during production of the film material for a tent structure of the present invention, and further improves weather resistance. 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, the thermoplastic resin coating layer may contain various optional amounts of known additives for thermoplastic resins. If necessary, light stabilizers (HALS), ultraviolet absorbers (benzotriazole, benzophenone, etc.) Systems), antioxidants (phenols), fluorescent whitening agents, antistatic agents, curing agents (isocyanates, etc.), insect repellents (pyrethroids, etc.), deodorants (silicon oxide / metal oxide composites, etc.) ), 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.) be able to.

  As one aspect of the film material for a tent structure of the present invention, it is preferable that a photocatalytic substance-containing antifouling layer is formed on at least one surface of the thermoplastic resin coating layer. 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 a photocatalyst), and effective and long-term generation of mold and algae It is possible to stably maintain the appearance of the tent structure by restraining the entire 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 selected from a cyclic polyether silver complex, a cyclic polyether copper complex, a cyclic polyether zinc complex, and a cyclic polyether nickel complex as the cyclic polyether metal complex effective for fungicidal and antialgae. (Same as those described in paragraphs [0022] to [0024].) The photocatalytic substance-containing antifouling layer comprises 10 to 70% by mass of a photocatalytic 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 having a thickness of 0.1 to 15 μm and containing an inorganic substance as a main component and having a composition of 1 to 20% by mass of siloxane, colloidal silica or silica) and 1 to 10% by mass of a chelate complex is preferred. In this case, an intermediate protective layer for protecting the thermoplastic resin coating layer from the oxidation-reduction action of the photocatalytic substance may be provided between the photocatalytic substance-containing antifouling layer and the soft vinyl chloride resin coating layer. 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 [mu] m, which is obtained by removing 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 magnesium, etc. A cyclic polyether metal 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 cyclic polyether metal complex contained in the photocatalytic substance-containing antifouling layer is supported on inorganic porous particles (gap between secondary particles that are aggregates of primary particles), and controls the sustained release of the cyclic polyether metal complex. By doing so, it is possible to stably maintain the long-term fungicidal and anti-algal effects. The same inorganic porous particles as those described in the paragraph [0025] can be used in the same manner, and the inorganic porous particles are obtained by simultaneously adsorbing and supporting a fungicidal substance and a cyclic polyether metal complex. Is also good.

  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 occurrence of mold (algae) is observed (trace). 3: Mold (algae) occurrence (trace) is observed partially (area within 9% of test sample). 4: Partial (10% of test sample). (II) Evaluation of antifungal properties (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 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
More than 1/3 of the total area <Test mold> (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

[Example 1]
A polyester fiber plain woven base fabric (warp 1111 dtex multifilament yarn: yarn density 30 / 2.54 cm × weft 1111 dtex multifilament yarn: yarn density 32 / 2.54 cm: void ratio 0%: mass 225 g / m ² ) As a base material, the following soft vinyl chloride resin paste composition (1) was knife-coated on both sides (adhesion amount per side: 220 to 240 g / m ² ), and heat-treated at 190 ° C. for 1 minute to obtain a soft vinyl chloride resin paste. The composition (1) was gelled and solidified to obtain a film material having a thickness of 0.65 mm and a mass of 700 g / m ² .
<Soft vinyl chloride resin paste composition (1)>
Vinyl chloride resin (degree of polymerization 1700) 100 parts by mass Diisononyl 1,2-cyclohexanedicarboxylate (plasticizer) 55 parts by mass * Trade name: Hexamol DINCH (manufactured by BASF)
18-monoazathia crown ether-5 silver (cyclic polyether metal complex)
1 part by weight _{※ - (CH 2 CH 2 S} ) 5 CH 2 that CH ₂ NH- were annularly carrying silver ions ※ cyclic polyethers metal complex previously plasticizer (1,2-cyclohexanedicarboxylic acid diisononyl) 55 Silver ion-supported synthetic zeolite (average particle size: 1 μm: fungicidal substance) used for blending in the procedure of uniformly dispersing in mass parts: 1 part by mass TBZ (4.5% by mass) -supported mesoporous silica (average particle size: 5 μm: protection) Moldy substance)
11 parts by mass * The antifungal substance is a plasticizer (diisononyl 1,2-cyclohexanedicarboxylate) in advance.
Chlorinated n-paraffin (flameproofing plasticizer) used for blending in the procedure of uniformly dispersing in 55 parts by mass 10 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Part Antimony trioxide (flame retardant) 10 parts by mass Rutile type titanium oxide (white pigment) 5 parts by mass Benzotriazole (ultraviolet absorber) 0.3 parts by mass
* Preparation of mesoporous silica carrying antifungal substance (TBZ) TBZ: To 100 ml of a water-ethanol solution containing 0.5 g of 2- (4-thiazolyl) -benzimidazole, add 10 g of mesoporous silica (average particle diameter 5 μm) to 100 ml of silane. The mixture was stirred at room temperature for 1 hour together with 1 g of a coupling agent (γ-glycidoxypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and then dried at 100 ° C. to obtain about 11 g of powder. The amount of TBZ carried by 11 g of this powder was 0.5 g (4.5% by mass).

[Example 2]
In the soft vinyl chloride resin composition (1) of Example 1, 1 part by mass of 18-monoazathia crown ether-5 silver (cyclic polyether metal complex) was added to decyl 18-crown ether-6 zinc (cyclic polyether metal). Complex) 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 substitution was performed with 1 part by mass.
* Decyl 18-crown ether-6 zinc:
_{- (CH 2 CH -C 10 H} 21) O (CH 2 CH 2 O) 5 - the carrying zinc ion those annularly

[Example 3]
In the soft vinyl chloride resin composition (1) of Example 1, 1 part by mass of 18-monoazathia crown ether-5 silver (cyclic polyether metal complex) was added to 18-diaza crown ether-4 copper (cyclic polyether). A metal 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 metal material was replaced by 1 part by mass.
* 18-diaza crown ether-4 copper:
-[(CH ₂ CH ₂ NH (CH ₂ CH ₂ O) ₂ ] _2- cyclically supports copper ions

[Example 4]
In the soft vinyl chloride resin composition (1) of Example 1, 1 part by mass of 18-monoazathia crown ether-5 silver (cyclic polyether metal complex) was added to synthetic amorphous silica (average secondary particle diameter: 9 μm: BET 140-170 m ² / g) 10 g of 18-monoazathia crown ether-5 silver (cyclic polyether metal complex) was replaced by 11 parts by mass of synthetic amorphous silica in which 1 g of silver was supported in the gap between secondary particles. 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 for the above.

[Examples 5 to 8]
Examples 5 to 8 were obtained by forming a photocatalytic substance-containing antifouling layer on the film materials of Examples 1 to 4.
* 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 mass%) 100 mass parts Methyl silicate solution (solid content 20 mass%) 8 mass parts γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 mass part

* 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 5 to 8 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 18-monoazathia crown ether-5 silver (cyclic polyether metal complex)
0.25 parts by mass

[Examples 9 to 12]
Examples 9 to 12 were formed by forming a photocatalyst substance-containing antifouling layer on the film materials of Examples 1 to 4.
* Formation of the intermediate protective layer The composition and the forming method are the same as in Examples 5 to 8.
* 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 of examples 9-12, 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%)
18-diaza crown ether-6 copper (cyclic polyether metal complex) 0.5 parts by mass

[Antifungal effect of Examples 1 to 12]
The membrane materials for tent structures of Examples 1 to 4 containing the cyclic polyether metal complex and the fungicidal substance in the soft vinyl chloride resin coating layer were all antifungal test (I): even after 36 months of outdoor extension exposure No molds or algae were found (traces), the initial surface condition was maintained, and the antifungal test (II): No hyphal growth was observed in the JIS Z2911 culture test. It became clear that a sufficient antifungal effect can be expected as a film material for tent structures. The superiority of the antifungal test (III) assuming long-term use is that the membrane material of Example 4 using the cyclic polyether metal complex supported on inorganic porous particles has the longest antifungal property. Had the nature. Further, the tent structure membrane materials of Examples 5 to 12 in which the photocatalytic substance-containing antifouling layer was formed on the tent structure membrane materials of Examples 1 to 4 were remarkable in accumulation of dust and rain streaks. The generation of tents was not observed for a long period of time, and the antifouling effect of rainfall self-cleaning by the photocatalytic substance-containing antifouling layer, the effect of decomposing organic substances such as fungi, and the synergistic effect of the cyclic polyether metal complex resulted in the tents of Examples 1 to 4. Compared with the membrane material for structures, the initial appearance was stable and sustainable for a long period of time (antifungal test (I) 48 months, antifungal test (III) 21 days).

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that 1 part by mass of 18-monoazathia crown ether-5 silver (cyclic polyether metal complex) was 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. In the film material of Comparative Example 1, the cyclic polyether metal complex was omitted, so that only the antifungal effect by the antifungal substance was exhibited. Although the initial antifungal effect was well exhibited, the antifungal test (I) was 36 months. Later, the occurrence of mold was partially observed (about 6% area of the test sample), and in the antifungal test (III), it was observed in the inoculated portion of the test piece due to the extraction of the antifungal substance (TBZ). Compared to the membrane material of Example 1, the long-term stability of the antifungal property was greatly impaired, for example, the area of the hyphal growth portion exceeded 1/3 of the total area.

[Comparative Example 2]
From the soft vinyl chloride resin composition (1) of Example 1, 1 part by mass of a synthetic zeolite supporting silver ions (antifungal substance) and 11 parts by weight of mesoporous silica supporting TBZ (4.5% by mass) (antifungal substance) 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 part was omitted. The film material of Comparative Example 2 had only the antifungal effect of the cyclic polyether metal complex due to the omission of the antifungal substance, and the initial antifungal effect was poor. After 24 months of the antifungal test (I), The occurrence of mold was partially observed (approximately 6% of the specimen). In the antifungal test (III), the area of the hyphal growth observed in the inoculated portion of the test piece was 1/3 of the total area. As compared with the film material of Example 1, the initial effect of the antifungal property was greatly impaired.

[Reference Example 1]
In the soft vinyl chloride resin composition (1) of Example 1, 1 part by mass of 18-monoazathia crown ether-5 silver (cyclic polyether metal complex) was mixed with the cyclic polyether metal complex in advance with a plasticizer (1). , 2-cyclohexanedicarboxylic acid diisononyl) in a procedure of uniformly dispersing it in 55 parts by mass, while using a soft vinyl chloride resin composition alone without dispersing the cyclic polyether metal complex in a plasticizer in advance. (1) It was blended and stirred sufficiently. Despite sufficient agitation, aggregation of the cyclic polyether metal complex caused the distribution of the cyclic polyether metal complex on the surface of the obtained membrane material to be nonuniform and inefficient. After 24 months from the test (I), the occurrence of mold was partially observed (about 6% area of the test sample).

  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 (5)

The fiber fabric as a substrate, a the flexible sheet having at least a thermoplastic resin coating layer on one surface, the thermoplastic resin coating layer, a cyclic polyether metal complexes, and the antifungal substance seen including, The cyclic polyether metal complex is at least one selected from a cyclic polyether silver complex, a cyclic polyether copper complex, a cyclic polyether zinc complex, and a cyclic polyether nickel complex, and the antifungal substance is imidazole. Compounds, thiazole compounds, isothiazoline compounds, pyridine compounds, triazine compounds, triazole compounds, N-haloalkylthio compounds, quaternary ammonium salt compounds, and at least one selected from organometallic compounds. A membrane material for a tent structure, which is characterized in that:   The cyclic polyether metal complex is at least one selected from the group consisting of cyclic polyethers such as crown ether, azacrown ether, thiacrown ether, azathiacrown ether, and cryptand, and the cyclic polyether group has a functional group and The film for a tent structure according to claim 1, wherein the metal complex is a metal complex having at least one selected from the group consisting of a derivative group into which a substituent is introduced and / or a polymer group having the cyclic polyether in a repeating unit. Wood. The antifungal substance may be synthetic amorphous silica, mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, silica The film material for a tent structure according to claim 1 , which is supported on at least one kind of inorganic porous particles selected from magnesium aluminate, 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 thermoplastic resin coating layer, and the photocatalytic substance contained in the photocatalytic substance-containing antifouling layer includes titanium oxide, titanium peroxide (peroxotitanic acid), zinc oxide, The tent structure film material according to any one of claims 1 to 3 , wherein the film material is at least one selected from tin oxide, strontium titanate, tungsten oxide, and bismuth oxide. The photocatalyst substance containing antifouling layer according to claim 4, including cyclic polyethers silver complex, cyclic polyethers copper complexes, one or more cyclic polyether metal complexes selected from cyclic polyethers zinc complex and cyclic polyethers nickel complexes 6. The film material for a tent structure according to item 5.