Method for producing industrial material sheet, and sewing method of tent membrane structure

Abstract

To provide (a method for producing) an industrial material sheet excellent in permeation prevention effect of rain water from a cross section such as tarpaulin, sailcloth and so on, and mold prevention, and algae prevention effect, and durability thereof, and a tent membrane structure obtained by sewing these industrial material sheets (sewing method).SOLUTION: According to a method comprising: 1) a step of preparing a mixed solution that necessarily contains a fluorine atom-free resin emulsion, an emulsion of a carbodiimide compound (having an ethylene oxide moiety), and a specific dilution water (one or more selected from silver ion water, copper ion water, and water containing an organic antifungal agent); 2) a step of applying 1 to 7.5 mass% of the dried mixed solution onto the entire woven fabric made from entangled multifilament yarns; 3) a step of forming a waterproof coating layer of a thermoplastic resin composition on both sides of dry matter adhering fabric, thereby covering the dry matter adhering fabric to form an industrial material sheet, water penetration from the cross-section of yarns exposed at the cut ends of the industrial material sheet is stopped within a length of 20 mm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to industrial material sheets such as tarpaulins and canvas, and tent membrane structures using these. More specifically, the present invention relates to tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, and sunshade tents, which have excellent rainwater penetration prevention effects from the cross sections of the industrial material sheets that constitute the tent membrane structures, and excellent durability of their anti-fungal and anti-algae effects, and to the industrial material sheets that constitute the tent membrane structures. [Background technology]

[0002] Industrial material sheets used in tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, and sunshade tents are waterproof sheets such as tarpaulins and canvases, which are manufactured by forming a soft vinyl chloride resin layer on a polyester fiber yarn base material. These sheets are approximately 0.3 to 1.2 mm thick and 0.9 to 2.5 m wide. These tarpaulins and canvases are distributed in rolls slit to specified widths and lengths, with the cross section of the slits revealing the cross section of the base fabric (the cross section of the yarn). Tent membrane structures are made by joining multiple industrial material sheets together to expand their area. This sewing is done by lap-jointing using heat fusion (the edges of the sheets are used as glue tabs, and the soft vinyl chloride resin layer is melted and bonded with the overlapping edges), revealing the cross section of the yarn that makes up the fabric. These threads are made from bundles of many filaments, such as long-fiber multifilament threads and short-fiber spun multifilament threads. When the cross section of the threads is exposed, rainwater seeps deep into the threads due to capillary action. The dirty rainwater remains inside the sheet material, leading to problems with mold and algae growth. This rainwater seepage occurs not only at the joints, but also through wear, scratches, holes, and other damage to the industrial sheet. Mold and algae that form inside such industrial sheeting are difficult to remove, affecting the appearance of the interior and exterior of membrane structures, uneven light transmission, and causing unpleasant odors.

[0003] As a means for preventing such capillary penetration of rainwater, there are exemplified tent fabrics in which a vinyl chloride resin coating layer is provided on both sides of a fabric to which a fluororesin-based water repellent agent is applied (Patent Document 1), and membrane materials in which a thermoplastic resin is coated on at least one side of a base fabric to which a fluorine-based water repellent or silicone-based water repellent agent is applied (Patent Document 2).All of these means for making fabrics (woven or knitted fabrics) water repellent are effective in suppressing capillary action. Fluorine-based compounds, in particular, are widely used as water-repellent components that impart high water repellency to textile materials. However, the impurities PFOS (perfluorooctane sulfonic acid) and PFOA (perfluorooctanoic acid) contained in water repellents are persistent, highly bioaccumulative, and highly mobile over long distances. These impurities are accumulating in water, soil, air, and plants and animals on a global scale, potentially affecting the human body (liver dysfunction, carcinogenesis, etc.) and the habitat and growth of plants and animals. This has led to the elimination of PFOS and PFOA (Stockholm Convention on Persistent Organic Pollutants), and in Japan, their manufacture and import are generally prohibited. As a result, there has been a shift to C6-based fluorine-based compounds (Patent Document 3), which do not contain PFOS or PFOA. However, there is a recent global trend toward replacing these compounds with non-fluorine-based water repellents, such as silicon-based compounds and hydrocarbon compounds (Patent Documents 4 and 5), in order to eradicate the residue and accumulation of fluorine-based compounds in general. However, it is difficult to substitute non-fluorine-based water repellents with equivalent performance to fluorine-based water repellents in all aspects, including water repellency and durability of the water repellency effect (washability). Therefore, various attempts have been made to compensate for the performance balance by using crosslinkable organic compounds in combination with non-fluorine-based water repellents (Patent Documents 6 and 7).

[0004] However, these inventions primarily aim to waterproof and water-repellent clothing fabrics, and involve assessing the water repellency (SR) of fabrics by directly dripping water onto them, after 10 or 20 washes under specific washing conditions, and even after ironing at 180°C. In contrast, industrial sheets used outdoors are made of tarpaulin or canvas, which are woven fabrics treated with a resin (e.g., soft polyvinyl chloride resin), and therefore offer exceptional waterproofing. However, it is necessary to prevent rainwater from penetrating through the slightly exposed multifilament yarn at the cut edges (joints) of the sheet. This requires a technology to seal the capillary phenomenon specific to multifilament yarns and an appropriate evaluation method. This technology differs from the technology for imparting water repellency to clothing surfaces and the evaluation method disclosed in patent documents, and it is not easy to seal the capillary phenomenon specific to multifilament yarns by simply adapting the methods disclosed in patent documents. In particular, industrial material sheets have a problem specific to industrial material sheets: when tent membrane structures are subjected to natural stresses over a long period of time, such as flapping in the wind, collisions with raindrops, and snow loads, the bundles of multifilament yarns loosen over time, promoting capillary action and allowing rainwater to penetrate the interior of the sheet, resulting in the growth of mold and algae inside the sheet. Therefore, there is a demand for industrial material sheets for tent membrane structures that are effective in preventing rainwater penetration from the cross sections and damaged parts of the industrial material sheet, and that have excellent mold and algae prevention properties that are also durable. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-34093 [Patent Document 2] Japanese Patent Application Publication No. 9-183188 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-229593 [Patent Document 4] Japanese Patent Application Publication No. 2020-189980 [Patent Document 5] Japanese Patent Publication No. 2023-57061 [Patent Document 6] Special Publication No. 2018-506656 [Patent Document 7] Japanese Patent Application Publication No. 2019-533732 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide an industrial material sheet (a manufacturing method) that is effective in preventing rainwater penetration from the cross sections of tarpaulin, canvas, etc., and that has excellent anti-mold and anti-algae effects, and these effects are highly sustainable, and to provide a tent membrane structure (a sewing method) that is effective in preventing rainwater penetration from the cross sections of the joints in a tent membrane structure made by sewing these industrial material sheets, and that has excellent anti-mold and anti-algae effects, and that also has excellent dynamic durability and sustainability.By solving these problems, it will be possible to maintain a beautiful appearance for a long period of time in tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, and sunshade tents. [Means for solving the problem]

[0007] As a result of extensive investigations in consideration of the above points, the present invention provides a method for producing an industrial material sheet, which comprises the steps of: 1) a step of preparing a mixed solution essentially containing a fluorine atom-free resin emulsion, a carbodiimide compound (having an ethylene oxide moiety) emulsion, and dilution water (one or more selected from water containing 1 to 50 ppm silver ions, water containing 1 to 50 ppm copper ions, and water containing an organic antifungal agent at a concentration of 0.05 to 1% by mass); 2) a step of applying the dried mixture solution to the entire woven fabric obtained by entangling multifilament yarns in an amount of 1 to 7.5% by mass relative to the basis weight of the woven fabric; 3) forming a waterproof coating layer of a thermoplastic resin composition on the front and back of the dried material-attached fabric to conceal the dried material-attached fabric and produce an industrial material sheet; The inventors have discovered that by stopping the inward penetration of water (JIS K6404-3-16 A. ink method) from the cross section of the yarn exposed on the cut surface of the industrial material sheet within a length of 20 mm, an industrial material sheet can be obtained that is effective in preventing rainwater from penetrating from the cross section of the industrial material sheet, and that has excellent anti-mold and anti-algae effects, as well as long-lasting durability. They have also discovered that using these industrial material sheets in tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, and sunshade tents provides excellent effects in preventing rainwater from penetrating from the cross section of the joints, as well as excellent anti-mold and anti-algae effects, as well as long-lasting dynamic durability, which have led to the completion of the present invention.

[0008] In the method for producing an industrial material sheet of the present invention, the woven fabric is woven only from long fiber multifilament yarns or only from short fiber spun multifilament yarns having a yarn density of 50 to 400 g / m 2 or 50 to 400 g / m woven using a combination of the long fiber multifilament yarn and the short fiber spun multifilament yarn. 2 This allows the amount of dried matter adhering to the surface of the filaments and between the filaments to be specified, and prevents water from penetrating into the interior of the filaments (JIS K6404-3-16 A. Ink method) from the cross section of the yarn exposed on the cut surface of the industrial material sheet within a length of 20 mm.

[0009] In the method for producing an industrial material sheet of the present invention, the long-fiber multifilament yarn is preferably a bundle of organic long-fiber filaments having a diameter of 1.25 to 4 denier or a bundle of inorganic filaments having a diameter of 2.5 to 10.0 μm, and the short-fiber spun multifilament yarn is preferably a bundle of organic short-fiber filaments having a diameter of 1.25 to 4 denier. If the filament diameter is larger than this, the gaps between the filaments will increase proportionally, making it difficult to prevent water penetration by capillary action.

[0010] In the method for producing an industrial material sheet of the present invention, the mixed solution preferably further contains an alkoxysilane compound, the content of which is 7.5 to 35 mass% based on the dry matter, thereby improving the rainwater penetration prevention effect, mildew prevention effect, and algae prevention effect, as well as their durability, and is particularly effective for inorganic filaments such as glass filaments, silica filaments, alumina-silica filaments, and basalt filaments.

[0011] The sewing method for a tent membrane structure of the present invention is a manufacturing method for a tent membrane structure using an industrial material sheet obtained by the manufacturing method described in paragraph

[0007] , 1) A step of cutting the industrial material sheet to prepare a plurality of cut parts. 2) overlapping the ends of the cut pieces at a specific width and joining them by thermocompression or high-frequency welding to form a number of connecting parts to form a tent membrane structure; It is preferable that the penetration of water into the interior of the industrial material sheet from the threads exposed at the cut cross section of the connecting portion (based on JIS K6404-3-16 A. Ink Method) is stopped within a length of 20 mm, thereby improving the effect of preventing rainwater penetration from the cross section of the joint in the tent membrane structure, as well as the anti-mold and anti-algae effects and their durability. [Effects of the Invention]

[0012] The present invention makes it possible to provide industrial material sheets such as tarpaulins and canvases that have excellent durability and long-lasting effects, as well as the effect of preventing rainwater from penetrating through the cross sections of the industrial material sheets, as well as the effect of preventing mildew and algae, and further makes it possible to provide tent membrane structures made by sewing these industrial material sheets, that have excellent durability and long-lasting effects, as well as the effect of preventing rainwater from penetrating through the cross sections of the joints, as well as the effect of preventing mildew and algae, and thereby makes it possible to provide tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and sunshade tents, which can be used for a long period of time while maintaining a beautiful appearance. DETAILED DESCRIPTION OF THE INVENTION

[0013] The method for producing an industrial material sheet of the present invention includes the steps of: 1) preparing a mixed solution essentially containing a fluorine atom-free resin emulsion, a carbodiimide compound (having an ethylene oxide moiety) emulsion, and dilution water (one or more selected from water containing 1 to 50 ppm of silver ions, water containing 1 to 50 ppm of copper ions, and water containing an organic antifungal agent at a concentration of 0.05 to 1 mass %); 2) applying a dried product of the mixed solution to the entire woven fabric woven by entangling multifilament yarns in an amount of 1 to 7.5 mass % based on the basis weight of the fabric; and 3) forming waterproof coating layers of a thermoplastic resin composition on the front and back surfaces of the fabric to which the dried product has been applied, thereby concealing the fabric to which the dried product has been applied, to produce an industrial material sheet. A. Ink method) is stopped within 20 mm in length, especially when the woven fabric is woven with only long fiber multifilament yarn or only short fiber spun multifilament yarn of 50 to 400 g / m 2 or 50-400g / m woven with a combination of long fiber multifilament yarn and short fiber spun multifilament yarn 2 and the long-fiber multifilament yarn is a bundle of organic long-fiber filaments having a diameter of 1.25 to 4 denier or a bundle of inorganic filaments having a diameter of 2.5 to 10.0 μm, and the short-fiber spun multifilament yarn is a bundle of organic short-fiber filaments having a diameter of 1.25 to 4 denier. The method for producing a tent membrane structure includes: 1) cutting an industrial material sheet to prepare a plurality of cut parts; and 2) overlapping the ends of the cut parts at a specific width and joining them by thermocompression or high-frequency welding to form a number of connecting parts to obtain a tent membrane structure, wherein water penetration (in accordance with JIS K6404-3-16 A. ink method) from the yarns exposed on the cut cross section of the industrial material sheet contained in the connecting parts is stopped within a length of 20 mm.

[0014] The fabric used for the industrial material sheet of the present invention may be a plain weave fabric, a basket weave fabric, a twill weave fabric, a satin weave fabric, or a twill weave fabric, but a plain weave fabric is particularly preferred, and the basis weight is 50 to 400 g / m 2Suitable fabrics have a porosity of 5-35% for tarpaulin and 0-15% for canvas. These fabrics can be dyed, water-repellent, flame-retardant, or other conventional dyeing processes. Organic multifilament yarns made from vinylon, polyester (polyethylene terephthalate: PET, recycled PET, biomass PET, etc.), or polyamide (nylon, recycled nylon, biomass nylon, etc.) can be used as the yarns constituting the fabric. Polyester fibers, in particular, are preferred because they have terminal functional groups such as hydroxyl and carboxyl groups, while polyamide fibers, in particular, have terminal functional groups such as amino and carboxyl groups, which bond with the carbodiimide bond (-N=C=N-) of polycarbodiimide. Furthermore, for non-combustible materials certified by the Minister of Land, Infrastructure, Transport and Tourism, inorganic long-fiber multifilament yarns are suitable due to their excellent flame resistance and strength. The inorganic long fibers are preferably glass long fibers, melt-spun to filament diameters of 2.5 to 3.80 μm (B fiber), 3.81 to 5.08 μm (C fiber), 5.09 to 6.35 μm (D fiber), 5.66 to 6.98 μm (DE fiber), 6.35 to 7.62 μm (E fiber), or 8.89 to 10.0 μm (G fiber), and are preferably multifilament single yarns or untwisted yarns formed by bundling 50 to 1600 fibers of the same diameter. The glass raw material is preferably E glass (alkali-free glass), which has a high modulus of elasticity (GPa), and the filaments are preferably B fiber, which has excellent bending durability. If the filament diameter is larger than this, the gaps between the filaments increase proportionally, making it difficult to prevent water penetration by capillary action.

[0015] Multifilament yarns are long-fiber multifilament yarns or short-fiber spun multifilament yarns, and woven fabrics are made of only long-fiber multifilament yarns or only short-fiber spun multifilament yarns with a weight of 50 to 400 g / m 2 or 50-400g / m woven with a combination of long fiber multifilament yarn and short fiber spun multifilament yarn 2The weight is 125 to 2000 denier (139 to 2222 dtex). The long-fiber multifilament yarn is a long-fiber spun bundle (a bundle of 100 to 500 filaments of 1.25 to 4 denier) made by stretching a long-fiber spun yarn extruded from a spinneret and spun from polyester, nylon, etc., and either untwisted or twisted 1 to 200 times / m. If the filament denier is larger than this, the gaps between the filaments increase proportionally, making it difficult to prevent water penetration by capillary action. Staple spun multifilament yarn is made by extruding polyester, nylon, etc. through a spinneret and spinning a long fiber spun bundle (a bundle of 100 to 500 fibers of 1.25 to 4 denier) into staples approximately 3.8 to 5.8 mm long, which are then opened and kneaded to form a sliver into a roving (coarse yarn), which is then tow-spun into a specified count by drafting and twisting. If the filament denier is larger than this, the gaps between the filaments increase proportionally, making it difficult to prevent water penetration by capillary action. The count ranges from 10 count (591 dtex) to 60 count (97 dtex), particularly 10 count (591 dtex), 14 count (422 dtex), 16 count (370 dtex), 20 count (295 dtex), 24 count (246 dtex), and 30 count (197 dtex). These can be used as single yarns, two-ply yarns (single-twisted yarns), or ply-twisted yarns made from two or more single yarns. The number of twists in the twisted yarn is about 200 to 2,000 times per meter.

[0016] The dried material adhered to the surfaces of and between the filaments of a continuous multifilament yarn and to the surfaces of and between the filaments of a staple spun multifilament yarn is a solid obtained by drying a mixed solution essentially consisting of a fluorine-free resin emulsion, a carbodiimide compound (containing ethylene oxide moieties) emulsion, and dilution water (one or more selected from silver ion water, copper ion water, and water containing an organic antifungal agent). The fluorine-free resin emulsion is one or more selected from urethane resin, acrylic resin, and silicone resin (OH group-containing polysiloxane, methylhydrogenpolysiloxane). The dried material of the mixed emulsion is obtained by evaporating the water by heating. In particular, a "urethane resin / polycarbodiimide containing ethylene oxide moieties" composite or an "acrylic resin / polycarbodiimide containing ethylene oxide moieties" composite is preferred, and the dry material adhesion amount is preferably 1 to 7.5 mass% based on the basis weight of the fabric. This adhesion amount is greatly affected by factors such as the specific gravity of the yarns that make up the woven fabric, the number of filaments that make up the yarns, the filament diameter, the twist of the yarns, and the type and amount of oil and sizing agent used in spinning, so it must be adjusted appropriately depending on the woven fabric. If the adhesion amount of dry material is less than 1% by mass, the internal water penetration (JIS K6404-3-16 A. Ink method) may exceed 20 mm in length, and if the adhesion amount exceeds 7.5% by mass, the spaces between the filaments may be filled with excess resin, reducing the bending flexibility of the yarns and making them hard, which may reduce the tear strength of the industrial material sheet.

[0017] The fluorine-free resin in the "fluorine-free resin / polycarbodiimide having an ethylene oxide moiety" composite is a water-dispersible polyurethane resin obtained by reacting an isocyanate-terminated prepolymer with a chain extender in water. The isocyanate-terminated prepolymer contains an organic polyisocyanate compound, a high-molecular-weight polyol, a carboxyl group or carboxylate group, and a compound having two or more active hydrogen atoms as monomers, and may contain a chain extender such as a polyamine derivative or a hydrazine derivative. The organic polyisocyanate compound may be an aliphatic diisocyanate (e.g., hexamethylene diisocyanate), an alicyclic diisocyanate (e.g., isophorone diisocyanate), or an aromatic diisocyanate (e.g., 2,4-tolylene diisocyanate). Aliphatic diisocyanates and alicyclic diisocyanates are particularly preferred because they are less susceptible to yellowing due to ultraviolet light and nitrogen oxide gases. Two or more of these may be used in combination. Examples of high-molecular-weight polyols include polyester diols (e.g., polyethylene adipate diol), polyether diols (e.g., polyoxytetramethylene glycol), and polycarbonate diols (e.g., polyhexamethylene carbonate diol) with molecular weights of 300 to 10,000, preferably 500 to 5,000. Depending on the type of polyol used, polypolyurethanes containing ester bonds, polyurethanes containing ether bonds, polyurethanes containing carbonate bonds, and polyurethanes containing caprolactone bonds can be obtained. The NCO / OH molar ratio is 1.2 / 1.0 to 1.5 / 1.0. An isocyanate-terminated urethane prepolymer is emulsified and dispersed in water to form a reaction solution. A chain extender such as a water-soluble polyamine derivative or a hydrazine derivative, and optionally a crosslinker such as a triisocyanate (diisocyanate trimer), an aziridine compound, or an oxazoline compound, is added to the reaction solution, and a chain extension reaction is carried out in water to produce a polyurethane emulsion (e.g., solids content 20 to 60% by mass). The urethane resin body and terminals preferably have functional groups such as hydroxyl groups and carboxyl groups for reacting with polycarbodiimide having an ethylene oxide moiety.

[0018] On the other hand, the acrylic resin as a non-fluorine atom-containing resin is an acrylic copolymer resin mainly composed of a (meth)acrylic acid alkyl ester having an alkyl group containing 12 to 24 carbon atoms and containing 0.1 to 10 mass% of a carboxyl group-containing unsaturated monomer. The alkyl group may be branched but is preferably linear. Examples of linear alkyl groups include alkyl esters of acrylic acid or methacrylic acid, such as lauryl, hexadecyl, stearyl, isostearyl, and behenyl. The amount of (meth)acrylic acid alkyl ester is preferably 40 to 80 mass% or more. If the amount is less than 40 mass%, water penetration (JIS K6404-3-16 A. Ink Method) may exceed 20 mm. If the amount is more than 80 mass%, water penetration may exceed 20 mm over time due to bending of the yarn during long-term use. The carboxyl group-containing unsaturated monomer has a carboxyl group and a carbon-carbon unsaturated bond in the molecule, and examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crotonic acid. The amount of carboxyl group-containing monomer is 0.1 to 10% by mass. If the amount is less than 0.1% by mass, there will be insufficient cross-linking with polycarbodiimide, and internal water penetration (JIS K6404-3-16 A. Ink method) may exceed 20 mm in length. If the amount exceeds 10% by mass, the spaces between the filaments will be filled with excess cross-linked material, which will impair the bending flexibility of the yarn and make it hard, potentially reducing the tear strength of the industrial material sheet. The monomer to be copolymerized with the main component is a monomer having an aromatic ring having 6 to 12 carbon atoms, or an aromatic ring having a substituent, or a cycloalkane having 5 to 12 carbon atoms, or a cycloalkane having a substituent, and is preferably one or more selected from styrene, α-methylstyrene, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, naphthyl (meth)acrylate, 4-morpholinoethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetramethylpiperidinyl methacrylate, methyl cinnamate, ethyl cinnamate, etc., in a copolymerization ratio of 15 to 40 mass%.If the content is less than 15% by mass, water penetration may exceed 20 mm in length, while if it exceeds 40% by mass, the bending flexibility of the yarn may be impaired and the yarn may become hard, resulting in a decrease in the tear strength of the industrial material sheet. In particular, it is preferable to include 1 to 10% by mass of one or more monomers having a functional group selected from hydroxyl, carboxyl, amino, epoxy, blocked isocyanate, amide, N-methylol, and mercapto groups as the third copolymerization component, to serve as reaction points with polycarbodiimide having an ethylene oxide moiety. The acrylic resin body and terminals preferably have functional groups such as hydroxyl and carboxyl groups for reacting with polycarbodiimide having an ethylene oxide moiety. The obtained acrylic resin is preferably in the form of an emulsion (e.g., solids content 20 to 60% by mass) for ease of processing into textiles.

[0019] The polycarbodiimide having ethylene oxide moieties used in the "fluorine atom-free resin / polycarbodiimide having ethylene oxide moieties" composite is a copolymer obtained by reacting polycarbodiimide obtained by a condensation reaction involving the decarbonation of organic diisocyanate with polyethylene glycol, polyethylene glycol derivatives, etc., and is mainly composed of water-soluble polycarbodiimide having carbodiimide bonds (-N=C=N-) and ethylene oxide moieties (-CH2-CH2-O-). The carbodiimide bonds provide excellent adhesion to glass fibers, and the ethylene oxide moieties contribute to water solubility. These polycarbodiimides may have polyethylene glycol grafted to approximately 1 to 20% of the total carbodiimide bonds (-N=C=N-). The polycarbodiimide moiety has the chemical formula (R-[-N=C=N-R'] nIn the formula, R and R' are C1-C20 alkyl, C3-C10 cycloalkyl, or C1-C20 alkenyl groups, which may be cyclic or branched, or may contain a C8-C16 aromatic nucleus, and the aromatic nucleus may be substituted with a functional group. R' may be C1-C20 alkylene, C3-C10 cycloalkylene, etc. n is 2 to 50, preferably 5 to 20. The amount of water-soluble polycarbodiimide used is preferably 0.01 to 3 equivalents of carbodiimide bond per equivalent of carboxyl group of the carboxyl group-containing unsaturated monomer contained in the urethane resin or acrylic resin. If the amount used is less than 0.01 equivalents, the crosslinking reaction may be insufficient, resulting in water penetration exceeding 20 mm in length, while if the amount used is more than 3 equivalents, the texture may harden due to dimerization or trimerization between unreacted polycarbodiimides, or due to the influence of the ethylene oxide moiety contained in the polycarbodiimide, resulting in water penetration exceeding 20 mm in length. Examples of organic diisocyanates include hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate. Examples of organic compounds that form ethylene oxide moieties include polyethylene glycol derivatives such as monoalkyl ethers of polyethylene glycol, and monoalkyl ethers of polyethylene glycol-polypropylene glycol random copolymers or monoalkyl ethers of block copolymers.

[0020] Examples of the carbodiimide moiety of polycarbodiimide having an ethylene oxide moiety include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, 4,4'-dicyclohexylmethanecarbodiimide, tetramethylxylylenecarbodiimide, N,N-dimethylphenylcarbodiimide, and N,N'-bis(2,6-diisopropylphenyl)carbodiimide. Examples of suitable carbodiimides include 2,2',6,6'-tetraisopropyldiphenylcarbodiimide, 2,2',6,6'-tetraisopropyldiphenylcarbodiimide oligomer, 1,3,5-triisopropyl-2,4-diisocyanatobenzene polymer, 1,3,5-triisopropyl-2,4-diisocyanatobenzene polymer, and 2,6-diisopropylphenyl isocyanate. The N=C=N equivalent (formula weight per mole of carbodiimide groups) of these compounds is preferably 300 to 600. Approximately 1 to 20% of the total number of carbodiimide groups can be subjected to an addition reaction with a polyethylene glycol derivative, such as a monoalkyl ether of polyethylene glycol, a monoalkyl ether of a polyethylene glycol-polypropylene glycol random copolymer, or a monoalkyl ether of a block copolymer. The chemical formula is (R-[-N=C=N-R'] n In the formula (I), R' is 2,6-diisopropylbenzene, naphthalene, 3,5-diethyltoluene, 4,4'-methylenebis(2,6-diethylenephenyl), 4,4'-methylenebis(2-ethyl-6-methylphenyl), 4,4'-methylenebis(2,6-diisopropylphenyl), 4,4'-methylenebis(2-ethyl-5-methylcyclohexyl), 2,4,6-triisopropylphenyl, n-hexane, cyclohexane, dicyclohexylmethane, methylcyclohexane, and the like. Polycarbodiimides having ethylene oxide moieties are preferably in the form of emulsions (e.g., solid content of 20 to 60% by mass) for ease of application to textiles. The solid content ratio of urethane resin / polycarbodiimide having ethylene oxide moieties is 3:1 to 1:1, with a ratio of approximately 2:1 being particularly preferred. The same ratio is also true for acrylic resin / polycarbodiimide having ethylene oxide moieties.

[0021] In the above-mentioned "fluorine-free resin / polycarbodiimide having ethylene oxide moieties" composite, the terminal hydroxyl and carboxyl groups of the polyester fibers are bonded to carbodiimide bonds (-N=C=N-), thereby stopping water penetration (JIS K6404-3-16 A. ink method) through the cross section of the thread exposed on the cut surface of the polyester fiber woven industrial material sheet within a length of 20 mm, thereby preventing rainwater penetration through the cross section of the industrial material sheet (preventing the growth of mold and algae) and providing an industrial material sheet with excellent dynamic durability. Meanwhile, for fabrics woven with long glass fiber multifilament threads, the above-mentioned "fluorine-free resin / polycarbodiimide having ethylene oxide moieties" composite preferably contains a hydrolysis product of an alkoxysilane compound as an additional component, with the content of this product being 7.5 to 35 mass% of the composite. Examples of alkoxysilane compounds include one or more silane coupling agents selected from aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylsilane, chlorosilane, mercaptosilane, isocyanurate silane, and isocyanate silane. Alkoxysilane compounds have two or more different reactive groups in a molecule represented by the general formula: XR-Si(Y)3, where X = amino, vinyl, epoxy, methacryl, acryl, chloro, mercapto, isocyanurate, or isocyanate (R = alkyl chain), and Y = methoxy or ethoxy. Alkoxysilane compounds hydrolyze in aqueous solution to form compounds of the general formula: XR-Si(OH)3, and require a condensation product formed by the reaction of these hydrolyzates. Such condensates are particularly suitable when X = amino, epoxy, mercapto, or isocyanate, due to their high reactivity with carbodiimide bonds (-N=C=N-). On the other hand, by bonding to the surface of the glass filaments, Si(OH)3 stops the internal penetration of water from the cross section of the threads exposed on the cut surface of the glass fiber woven industrial material sheet (JIS K6404-3-16 A. Ink method) within a length of 20 mm, thereby preventing rainwater from penetrating from the cross section of the industrial material sheet (preventing the growth of mold and algae) and resulting in an industrial material sheet with excellent dynamic durability and sustainability.

[0022] The method for adhering the dried material to the surfaces of the filaments constituting the yarn and between the filaments in a total amount of 1 to 7.5% by mass relative to the basis weight of the woven fabric is as follows: 1) a mixed solution essentially consisting of the above-mentioned fluorine atom-free resin emulsion, a carbodiimide compound (having an ethylene oxide moiety) emulsion, and dilution water (one or more selected from silver ion water, copper ion water, and water containing an organic antifungal agent) is measured and diluted to adjust the total solid content to 10 to 25% by mass, and then stirring and preparing the mixed solution; 2) a woven fabric woven by entanglement of multifilament yarns is woven by entanglement of the mixed solution. This can be achieved by the steps of: immersing the woven fabric in a liquid bath filled with cellulose acetate to impregnate the entire fabric with the mixed solution (emulsion composition); lifting the woven fabric with the emulsion composition impregnated therein; simultaneously squeezing the woven fabric between a pair of rubber rolls; impregnating the surface of the multifilament yarn constituting the woven fabric with the emulsion composition and simultaneously removing excess emulsion composition; and then drying and solidifying the woven fabric with hot air at 100°C or higher to adhere the dried emulsion composition to the entire fabric in an amount of 1 to 7.5% by mass based on the basis weight of the woven fabric. Step 1) may further include an alkoxysilane compound, if necessary, whose content is 7.5 to 35% by mass based on the total amount of the dried emulsion. Step 2) may also be performed by gravure coating, roll coating, knife coating, or the like of the mixed solution (emulsion composition) to the front and back of the fabric to impregnate the surface of the multifilament yarn and between the filaments with the emulsion composition, followed by drying and solidifying the woven fabric with hot air at 100°C or higher. The water repellent that can be used in combination with the emulsion composition includes known silicone compounds and paraffin compounds, and the amount used in combination is 1 to 25% by mass based on the total dry matter.

[0023] The dilution water used to adjust the solids concentration of the emulsification composition is one or more selected from silver ion water containing 1 to 50 ppm silver ions, copper ion water containing 1 to 50 ppm copper ions, and organic antifungal agent-containing water containing an organic antifungal agent at a concentration of 0.05 to 1% by mass. A combination of silver ion water and organic antifungal agent-containing water in a mass ratio of 1:2 to 2:1, a combination of copper ion water and organic antifungal agent-containing water in a mass ratio of 1:2 to 2:1, or a combination of silver ion water, copper ion water, and organic antifungal agent-containing water in a mass ratio of 1:1:2 is particularly preferred. Silver ion water can be obtained by a known electrolysis method in which a DC voltage is applied between two pure silver electrodes placed in water to generate silver ions, or by a known chemical method in which a compound containing a gold ion component (e.g., silver bromide, silver chloride, silver citrate, silver iodide, silver lactate, silver nitrate, silver oxide, etc.) is dissolved in water, and the silver ion concentration is adjusted to 1 to 50 ppm before use. Copper ion water can be obtained by a known electrolysis method in which a DC voltage is applied between two pure copper electrodes placed in water to generate copper ions, or by a known chemical method in which a compound containing a copper ion component (e.g., copper nitrate) is dissolved in water, and used with the copper ion concentration adjusted to 1 to 50 ppm. Water containing an organic antifungal agent contains one or more compounds selected from imidazole compounds, thiazole compounds, isothiazolinone compounds, pyridine compounds, triazine compounds, triazole compounds, N-haloalkylthio compounds, quaternary ammonium salt compounds, and organometallic compounds, dissolved or dispersed in water to a concentration of 0.05 to 1% by mass. These organic antifungal agents are also algae inhibitors. The silver ions contained in the silver ion water, the copper ions contained in the copper ion water, and the organic antifungal agent contained in the organic antifungal agent-containing water remain in the dried fluorine-free resin / polycarbodiimide composite, and even if rainwater containing mold or algae spores penetrates into the interior through the cross section of the thread exposed at the cut surface of the industrial material sheet, they have effects such as inhibition of oxidative phosphorylation, electron transport chain inhibition, inhibition of -SH groups, inhibition of DNA synthesis, inhibition of cell epidermal function, inhibition of lipid metabolism, and chelate formation on the cell walls, cell membranes, cytoplasm, and cell nuclei of mold, bacteria (gram-positive and gram-negative), fungi, etc., thereby exhibiting the effect of suppressing the growth of mold and algae.Silver ion water, copper ion water, and water containing an organic antifungal agent have different antifungal and antialgae effects depending on the type of mold and algae, so it is necessary to prepare a composition that is appropriate for the type of mold and algae.

[0024] Imidazole compounds include 2-(4-thiazolyl)-benzimidazole (TBZ), 2-(carbomethoxyamino)benzimidazole (BCM), and 1-(butylcarbamoyl)-2-benzimidazolecarbamate methyl ester. Thiazole compounds include 2-n-octyl-4-isothiazolin-3-one, 2-mercaptobenzothiazole, 2-(4-thiocyanomethylthio)benzothiazole, and 2-(thiocyanomethylsulfonyl)benzothiazole. Isothiazolin compounds include 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazoline. -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-t-butylamino-6-cyclopropylamino-S-thiazine, etc. Pyridine compounds include bis(pyridine-2-thiol-1-oxide) zinc salt (abbreviated as ZPT), (2-pyridinethiol-1-oxide) sodium salt, 2,2 ′-dithio-bispyridine-1-oxide, 2-pyridylthio-1-oxide copper salt, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, etc. Triazine compounds include 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-6-(1,2-dimethylpropylamino)-S-triazine, etc. Triazole compounds include α-[2-(4-chlorophenyl)ethyl]-α N-haloalkylthio compounds include N-(fluorodichloromethylthio)phthalimide, N-trichloromethylthiotetrahydrophthalimide, N-(trichloromethylthio)-4-cyclohexane 1,2-dicarboximide, N,N-dimethyl-N-(4-chlorophenyl)-α-(1-cyclopropylethyl)-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-dioxolan-2-yl]methyl]-1H-1,2,4-triazole, and α-(4-chlorophenyl)-α-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol. ′ -(fluorodimethylthio)-N ′ -phenylsulfamide, N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide, etc.; quaternary ammonium salt compounds such as benzakonium chloride, benzethonium chloride, N-decyl-N-isononyl-N,N-dimethylammonium chloride, etc.; organometallic compounds such as 10,10 ′ Examples include 8-oxybisphenoxyarsine (abbreviated as OBPA), 8-oxyquinoline copper, and 2-ethylhexanoic acid nickel.

[0025] In the industrial material sheet of the present invention, the waterproof coating layers formed on the front and back of the woven fabric are formed from compositions primarily containing known thermoplastic resins, such as soft vinyl chloride resins (containing plasticizers), vinyl chloride copolymer resins, chlorinated vinyl chloride resins, olefin resins (PE, PP), olefin copolymer resins, ethylene-vinyl acetate copolymer resins (EVA), ethylene-(meth)acrylic acid (ester) copolymer resins, urethane resins, vinyl acetate copolymer resins, styrene copolymer resins, and polyester copolymer resins. The waterproof coating layers may be colored and light-blocking, colored and light-transmitting, or colorless and transparent, depending on the formulation examples below. In the industrial material sheet of the present invention, it is particularly preferred that the waterproof coating layers be soft vinyl chloride resins (containing plasticizers) from the standpoints of flexibility, flame retardancy, abrasion resistance, and weather resistance.Specifically, the flexible vinyl chloride resin composition comprises 100 parts by mass of vinyl chloride resin (emulsion polymerized or suspension polymerized) having a number average molecular weight of 800 to 2500, 40 to 100 parts by mass of a plasticizer (one or more selected from adipic acid diester compounds, phthalic acid diester compounds, cyclohexane dicarboxylic acid ester compounds, cyclohexene dicarboxylic acid ester compounds, phosphate ester compounds, chlorinated paraffin compounds, polyester oligomers, epoxidized soybean oil, etc.), 2 to 5 parts by mass of a stabilizer (one or more selected from barium-zinc complex systems, calcium-zinc complex systems, tin mercapto complex systems, etc.), 0 to 30 parts by mass of a flame retardant (one or more selected from antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, zinc borate, etc.), 0 to 30 parts by mass of a filler (one or more selected from calcium carbonate, barium sulfate, silica, talc, etc.), and a light resistance stabilizer (benzophenone-based compounds, benzotriazole, etc.). a compounded composition containing, in any desired amounts, 0.5 to 3 parts by mass of a crosslinking agent (one or more selected from polyfunctional isocyanate compounds, carbodiimide compounds, oxazoline compounds, (meth)acrylate compounds, silane coupling agents, etc.); 0 to 10 parts by mass of a crosslinking agent (one or more selected from imidazole compounds, thiazole compounds, isothiazolinone compounds, pyridine compounds, N-haloalkylthio compounds, phenoxyarsine compounds, etc.); 0 to 3 parts by mass of an antifungal agent (one or more selected from imidazole compounds, thiazole compounds, isothiazolinone compounds, pyridine compounds, N-haloalkylthio compounds, phenoxyarsine compounds, etc.); and 0 to 5 parts by mass of a pigment (one or more selected from titanium oxide, carbon black, inorganic compounds, azo compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, etc.). If necessary, known additives such as antistatic agents, lubricants, chemical foaming agents, insect repellents, deodorizers, and heat-shielding agents can be added.

[0026] The waterproof coating layer for industrial sheets (tarpaulins) can be a film (sheet) with a thickness of 80 to 800 μm, preferably 150 to 300 μm, formed by hot-kneading a thermoplastic resin composition (preferably a flexible polyvinyl chloride resin compound) and melt-rolling it using a calendar or T-die extrusion method. The waterproof coating layers on both sides of an open-mesh fabric coated with a "fluorine-free resin / polycarbodiimide containing ethylene oxide moieties" composite can be formed by hot-melt lamination in a single or two-pass process using a laminator equipped with one or two continuous heat roll / rubber roll bonding units, a cooling roll unit, and a winding unit, resulting in tarpaulins with a thickness of 0.4 to 1.5 mm and a mass of 500 to 2000 g / m. These tarpaulins are suitable for membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, and sunshade tents. On the other hand, waterproof coating layers for industrial material sheets (canvas) can be formed by a single-pass dipping method, in which a woven fabric is immersed in a bath of a paste-like thermoplastic resin composition (preferably a soft vinyl chloride resin paste sol), pulled out, and simultaneously squeezed between a pair of rubber rolls to impregnate the multifilament yarns constituting the fabric with the soft vinyl chloride resin paste sol on the surface and between the yarns while simultaneously removing excess soft vinyl chloride resin paste sol. The dipping method then gels the sol with hot air at 160-185°C to form a waterproof coating layer with a thickness of 50-300 μm, preferably 80-200 μm. Alternatively, the soft vinyl chloride resin paste sol can be applied to the front and back of the fabric by a coating method such as knife coating, clearance coating, or gravure coating, and then gelled with hot air at 160-185°C to form a waterproof coating layer with a thickness of 50-300 μm, preferably 80-200 μm. These methods can produce canvas with a thickness of 0.3 to 0.8 mm and a mass of 400 to 1000 g / m, which can be used for truck hoods, truck bed sheets, house tents, sheet houses, etc.

[0027] On one or more surfaces of the waterproof coating layer of the industrial material sheet (tarpaulin, canvas) of the present invention, an antifouling layer composed of a fluorine-free coating film such as an acrylic resin, a urethane resin, an acrylic / silicone copolymer resin, or a urethane / silicone graft copolymer resin may be formed. The application of such an antifouling layer to membrane structures such as large tents (pavilions), circus tents, tent warehouses, and membrane roofs (ceilings) for architectural spaces can dramatically improve durability during outdoor use. Furthermore, the surface of such an antifouling layer or the surface of the industrial material sheet (tarpaulin, canvas) may be provided with an antistatic antifouling layer composed of nanoparticles made from an inorganic colloidal substance with a primary particle diameter of 3 nm to 150 nm, supported by a binder component containing a hydrolysis condensate of a silane coupling agent. The inorganic colloidal substance is a metal oxide such as a photocatalytic titanium oxide sol, a photocatalytic zinc oxide sol, a photocatalytic tin oxide sol, a titanium oxide sol, a zinc oxide sol, a tin oxide sol, a silica sol, an aluminum oxide sol, a zirconium oxide sol, a cerium oxide sol, or a composite oxide (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol.

[0028] The industrial material sheet (tarpaulin, canvas) of the present invention is produced in a long roll with a thickness of approximately 0.3 to 1.2 mm and a width of approximately 0.9 to 2.5 m, for example, 1000 m per lot, which is then slit to the standard width and rewound into 50 m lengths for distribution as a product (tarpaulin raw roll, canvas raw roll).The cross section of the woven fabric (cross section of the yarn) is exposed at the cross sections of the left and right slits of this raw roll and at the end cross section of the 50 m roll. Tent membrane structures are constructed by joining multiple industrial sheet components together and sewing them together to expand their surface area. This is done by lap welding using heat fusion or high-frequency welding (the edges of the sheets are used as adhesive, and the waterproof coating is melted and bonded together with the adhesive overlapped). The cross-section of the fabric yarn is exposed at the joint, making it constantly exposed to rainwater during outdoor use. However, the present invention applies a "fluorine-free resin / polycarbodiimide with ethylene oxide moieties" composite to the surface and between the filaments of the fabric yarn in a total amount of 1 to 7.5% by weight of the fabric. This prevents water penetration (JIS K6404-3-16 A. Ink Method) through the exposed cross-section of the yarn on any cut surface of the industrial sheet within 20 mm. This prevents the intrusion of dirty rainwater, which can lead to mold and algae growth, thereby maintaining a beautiful membrane structure's appearance and good light transmission from the inside for a long period of time. This water absorption prevention effect is also effective in preventing problems caused by wear, scratches, holes, and other damage to industrial material sheets.

[0029] The present invention will be further explained by the following examples and comparative examples, but the embodiments of the present invention are not limited to the scope of these examples. Water penetration prevention effect from the cross section of the sheet material (initial stage) JIS K6404-3-16 A. Ink method 5mm of the tip of each rectangular specimen cut to 20cm (length) x 3cm (width) and 3cm (length) x 20cm (width) was immersed in a 3% red ink aqueous solution bath for 72 hours, then removed and dried. The waterproof coating was then peeled off and removed from these specimens using high-frequency welding, exposing the fabric and measuring the maximum amount of red ink absorbed. A absorption of 20mm or less (average value for 5 specimens) was deemed to be effective in preventing water penetration. The waterproof coating can be removed by forcibly separating a sheet of the same material as the specimen that has been welded together using a high-frequency welder. * Red ink: Pilot Corporation "Ink Red 350R" * Japan Membrane Structures Association test method standard "Membrane material quality and performance test method" (MSAJ / M-3-82003) Section 13 “Water absorption resistance method A” Water penetration prevention effect from the cross section of the sheet material (after mechanical bending damage) JIS K6404-3-16 A. Ink method compliant Sheet material cut into 12cm (length) x 2.5cm (width) and 2.5cm (length) x 12cm (width) pieces was mounted on a Scott Crush Resistance Friction Tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and subjected to a 1.0kgf pressure x 30 times flexing and creasing load according to JIS L1096 Abrasion Strength Method B (Scott type method). These specimens were then immersed in a 3% aqueous red ink bath for 72 hours and evaluated in the same manner. A penetration prevention effect was deemed to be present if the ink absorbed within 20mm (average value for 5 specimens). The waterproof coating layer removal, red ink, and test method were as described above. Water penetration prevention effect from the cross section of the joint between sheet materials (initial stage) JIS K6404-3-16 A. Ink method Two 20cm (warp) x 15cm (weft) sheets (for warp yarn testing) were completely overlapped, and 5cm of one end of the 20cm warp stack was high-frequency fusion-bonded using a high-frequency welder (Yamamoto Vinita Co., Ltd.) YTO-8A model (high-frequency output 8kW) equipped with a 5cm wide x 20cm long weld bar (flat blade) at an anode current of 1.0 ampere for 5 seconds on (3 seconds off), to obtain an industrial material sheet joint (tent membrane structure mockup). Two 15cm (warp) x 20cm (weft) sheets (for weft yarn testing) were similarly bonded to obtain a joint (tent membrane structure mockup). Two sets of five test pieces (one for warp thread testing, one for weft thread testing) measuring 20cm long and 3cm wide were taken from these joints, and these test pieces were immersed in a 3% red ink aqueous solution bath for 72 hours and evaluated in the same way. Those that absorbed within 20mm (average value of 5 test pieces) were judged to have a penetration prevention effect. The removal of the waterproof coating layer, red ink, and test method were as described above. Evaluation of antifungal properties of textiles (JIS Z2911 culture test) Spores of the test molds listed below were inoculated onto fabric (3 cm wide x 3 cm long) to which the dried emulsion composition had been attached, and the fabric was placed on potato dextrose agar medium. The mold growth was observed in a petri dish at 28°C for 7 and 14 days, and evaluated according to the following criteria. 1: No mycelial growth is observed in the inoculated part of the test piece. 2: The area of ​​the mycelium grown in the inoculated part of the test piece does not exceed 1 / 3 of the total area. 3: The area of ​​the mycelium grown in the inoculated part of the test piece exceeds one-third of the total area. <Test mold> Mixed mold of A+B+C A) Aspergillus niger NBRC 105649 (black mold) B) Penicillium citrinum NBRC 6352 (blue mold) C) Cladosporium cladosporioides NBRC 6348 (black mold)

[0030] [Example 1] <Textiles (1)> The fabric (1) used was a plain weave fabric with a warp and weft group consisting of 1000 denier (1111 dtex) polyester long fiber (192 filaments) and S-twisted PET multifilament yarn of 50 T / m. The warp group had a weave of 16 threads per inch, and the weft group had a weave of 16 threads per inch. The mass of this fabric (1) was 150 g / m. 2 The porosity (total of open areas) was 14%. A mixed solution (1) of [Blending 1] was prepared, and this woven fabric (1) was immersed in a liquid bath filled with the mixed solution (1) of [Blending 1] below, so that the entire woven fabric (1) was impregnated with the mixed solution (1), and the mixed solution (1) was impregnated on the filament surfaces and between the filaments of the yarns constituting the woven fabric. This impregnated woven fabric (1a) was pulled up and simultaneously squeezed between a pair of rubber rolls, and immediately thereafter subjected to hot air drying at 120°C in an electric furnace, so that the dried composite material adhered to the filament surfaces and between the filaments of the yarns of the woven fabric, with a mass of 155.5 g / m 2 The fabric (1a) was obtained. The dry weight of the composite was 5.5 g / m 2 and 3.6% for textiles (1). [Formulation 1] Mixed solution (1) Solid content 6% by mass Fluorine atom-free resin (urethane resin) emulsion (solid content 40% by mass) Product name: Mayshield Z-1 (Meisei Chemical Industry Co., Ltd.) *Paragraph

[0017] *Having carboxyl groups 10 parts by mass Polycarbodiimide emulsion containing ethylene oxide moieties Product name: Carbodilite V-02 (Nisshinbo Chemical Inc.: solid content 40% by mass) *Paragraph

[0019]

[0020] 5 parts by mass Dilution water 85 parts by mass * 84.2 parts by mass of silver ion water with a concentration of 5 ppm by electrolysis, Dilute the aqueous solution in which 0.8 parts by mass of TBZ powder is dispersed. This was used as a dilution solution. <Industrial Material Sheet (1): Tarpaulin> The woven fabric (1a) was used as a substrate, and a 0.2 mm thick calendar-molded film made of the soft vinyl chloride resin composition of [Recipe 2] below was melt-laminated on both sides of the substrate by thermocompression bonding with a laminator to form a waterproof coating layer on both sides, resulting in a thickness of 0.7 mm and a mass of 830 g / m. 2 A tarpaulin of the industrial material sheet (1) was obtained. The woven fabric (1a) contained in the industrial material sheet (1) had the composite attached to the filament surfaces and between the filaments of the yarn in an amount of 3.6% relative to the woven fabric (1). [Formulation 2]: Soft vinyl chloride resin composition (compound) Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass Diisononyl phthalate (plasticizer DINP: MW419) 55 parts by mass Tricresyl phosphate (flame retardant 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 (flame retardant) 10 parts by mass Rutile titanium dioxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass

[0031] [Example 2] The same procedure as in Example 1 was repeated except that the mixed solution (1) in [Blend 1] in Example 1 was changed to the mixed solution (2) in [Blend 3]. The thickness was 0.7 mm and the mass was 830 g / m 2 A tarpaulin of the industrial material sheet (2) was obtained. The woven fabric (1b) contained in the industrial material sheet (2) has the dried composite material adhered to the filament surfaces and between the filaments of the yarn in an amount of 3.6% relative to the woven fabric (1). [Formulation 3] Mixed solution (2) Solid content 6% by mass Fluorine atom-free resin (acrylic resin) emulsion (solid content 40% by mass) Product name: Palladium SEF-1 (Ohara Palladium Chemical Co., Ltd.) *Paragraph

[0018] *Having carboxyl groups 10 parts by mass Polycarbodiimide emulsion containing ethylene oxide moieties Product name: Carbodilite V-02 (Nisshinbo Chemical Inc.: solid content 40% by mass) *Paragraph

[0019]

[0020] 5 parts by mass Dilution water 85 parts by mass * 84.2 parts by mass of copper ion water with a concentration of 5 ppm obtained by electrolysis, ′ -O An aqueous solution in which 0.8 parts by mass of bisphenoxyarsine (OBPA) powder was dispersed was This was used as a diluted solution.

[0032] [Example 3] <Textiles (2)> The warp yarn is a 20-count two-ply polyester staple fiber spun yarn (approximately 5 cm long PET staple fiber: S-twist 300T / m) with two strands per unit, and the weft yarn is a 10-count single-ply polyester staple fiber spun yarn (approximately 5 cm long PET staple fiber: S-twist 400T / m) with two strands per unit, and the weft is a plain weave with a density of 23 strands per inch. The void ratio is 0 in appearance and the mass is 240g / m. 2 A woven fabric (2) of [Recipe 1] was used. This woven fabric (2) was immersed in a liquid bath filled with the mixed solution (1) of [Recipe 1], and the entire woven fabric (2) was impregnated with the mixed solution (1), and the mixed solution (1) was impregnated on the filament surfaces and between the filaments of the yarns constituting the woven fabric. This impregnated woven fabric (2a) was pulled up and simultaneously squeezed between a pair of rubber rolls, and immediately thereafter subjected to hot air drying at 120°C in an electric furnace, and a mass of 250.4 g / m2 of the dried composite material adhering to the filament surfaces and between the filaments of the yarns of the woven fabric was obtained. 2 The fabric (2a) was obtained. The dry weight of the composite was 10.4 g / m 2 and 4.3% for textiles (2). <Industrial Material Sheet (3): Canvas> The woven fabric (2) is dipped (immersed) in a liquid bath filled with the soft vinyl chloride resin composition (paste) of [Blend 4], and the woven fabric (2) is impregnated with the processing solution of [Blend 4]. After that, the woven fabric (2a) is pulled out of the liquid bath and simultaneously squeezed with a rubber mangle roll to remove excess processing solution. After that, a gelling treatment is carried out in a hot air oven at 180°C for 3 minutes, thereby forming a waterproof coating layer that is impregnated and coated over the entire woven fabric (2a), with a thickness of 0.47 mm and a mass of 580 g / m. 2 The canvas of the industrial material sheet (3) was obtained. The woven fabric (2a) contained in the industrial material sheet (3) had the dried composite material adhered to the filament surfaces and between the filaments of the yarn in an amount of 4.3% relative to the woven fabric (2). [Formula 4] Soft vinyl chloride resin paste composition Paste: vinyl chloride resin (degree of polymerization 1700) 100 parts by mass Diisononyl phthalate (plasticizer DINP: MW419 55 parts by mass Tricresyl phosphate (flame retardant 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 (flame retardant) 15 parts by mass Rutile titanium dioxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Dilution solvent (trichloroethylene) 20 parts by mass

[0033] [Example 4] In the industrial material sheet (3) of Example 3, the mixed solution (1) to be impregnated into the woven fabric (2) was changed to the mixed solution (2), and the same as in Example 3, the thickness was 0.47 mm and the mass was 580 g / m 2 The canvas of the industrial material sheet (4) was obtained. The woven fabric (2b) contained in the industrial material sheet (4) has the dried composite material adhered to the filament surfaces and between the filaments of the yarn in an amount of 4.3% relative to the woven fabric (2).

[0034] [Example 5] In the industrial material sheet (1) of Example 1, the woven fabric (1) was changed to the woven fabric (3), and the thickness was 0.74 mm and the mass was 960 g / m. 2 A tarpaulin for the industrial material sheet (5) was obtained. The woven fabric (3a) contained in the industrial material sheet (5) had the dried composite material adhered to the filament surfaces and between the filaments of the yarn in an amount of 3.9% relative to the woven fabric (3). <Textiles (3)> E-glass long fiber multifilament yarn (filament diameter 6 μm, filament count 400: 75 dtex flat yarn) was used as the warp and weft yarns, and the warp yarn pick density was 44 / inch, the weft yarn pick density was 40 / inch, the void ratio was 5%, and the mass was 285 g / m 2 , woven fabric (3) was used.

[0035] [Example 6] In the industrial material sheet (2) of Example 2, the woven fabric (1) was changed to the woven fabric (3), and the same as in Example 2, the thickness was 0.74 mm and the mass was 960 g / m 2 Thus, a tarpaulin for an industrial material sheet (6) was obtained. The woven fabric (3b) contained in the industrial material sheet (6) had the dried composite material adhered to the filament surfaces and between the filaments of the yarn in an amount of 3.9% relative to the woven fabric (3).

[0036] [Example 7] In the industrial material sheet (5) of Example 5, the mixed solution (1) of [blending 1] was changed to the mixed solution (3) of [blending 5], and the same as in Example 5, the thickness was 0.74 mm, the mass was 960 g / m 2 A tarpaulin for the industrial material sheet (7) was obtained. [Blend 5] The mixed solution (3) was used after stirring at room temperature for 1 hour. The woven fabric (3a) contained in the industrial material sheet (7) has 3.9% of the dried composite material attached to the surface of the filaments of the yarn and between the filaments, relative to the woven fabric (3). [Formulation 5] Mixed solution (3) Solid content 6% by mass Fluorine atom-free resin (urethane resin) emulsion (solid content 40% by mass) Product name: Mayshield Z-100 (Meisei Chemical Industry Co., Ltd.) *Paragraph

[0017] 10 parts by mass Polycarbodiimide emulsion containing ethylene oxide moieties Product name: Carbodilite V-04 (Nisshinbo Chemical Inc.: solid content 40% by mass) *Paragraphs

[0019]

[0020] *Contains carboxyl groups 5 parts by mass N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane Hydrochloride (active ingredient 40% by mass / methanol solution: alkoxysilane compound) 5 parts by mass Dilution water 80 parts by mass * 79.2 parts by mass of copper ion water with a concentration of 5 ppm obtained by electrolysis, Dilute the aqueous solution in which 0.8 parts by mass of TBZ powder is dispersed. This was used as a dilution solution.

[0037] [Example 8] The same procedure as in Example 7 was repeated except that the mixed solution (3) in [Blend 5] in Example 7 was changed to the mixed solution (4) in [Blend 6]. The thickness was 0.74 mm and the mass was 960 g / m 2 Thus, a tarpaulin for an industrial material sheet (8) was obtained. The woven fabric (3b) contained in the industrial material sheet (8) had the dried composite material adhered to the filament surfaces and between the filaments of the yarn in an amount of 3.9% relative to the woven fabric (3). [Formulation 6] Mixed solution (4) Solid content 6% by mass Fluorine atom-free resin (acrylic resin) emulsion (solid content 40% by mass) Product name: Palladium SEF-8 (Ohara Palladium Chemical Co., Ltd.) *Paragraph

[0018] *Having carboxyl groups 10 parts by mass Polycarbodiimide emulsion containing ethylene oxide moieties Product name: Carbodilite V-04 (Nisshinbo Chemical Inc.: solid content 40% by mass) *Paragraph

[0019]

[0020] 5 parts by mass 3-Isocyanatepropyltriethoxysilane (alkoxysilane compound) 2 parts by mass Dilution water 83 parts by mass * 82.2 parts by mass of silver ion water with a concentration of 5 ppm by electrolysis, 10,10 ′ -Oki Dilute the aqueous solution in which 0.8 parts by mass of bisphenoxyarsine (OBPA) powder is dispersed. This was used as a dilution solution.

[0038] [Table 1]

[0039] [Table 2]

[0040] The industrial material sheets of Examples 1 to 8 were fabricated by attaching a dried "fluorine-free resin / polycarbodiimide having an ethylene oxide moiety" composite to the surface of the filaments and between the filaments in a total amount of about 3.6 to 4.3 mass% based on the fabric weight. This allowed water penetration (JIS K6404-3-16 A. Ink method) from the cross section of the yarn exposed on the cut surface of the industrial material sheet to be stopped within a length of 5 mm. Furthermore, even after applying a bending load to the industrial material sheets of Examples 1 to 8, which created gaps in the multifilaments and caused stress to promote capillary action, water penetration was stopped within a length of 10 mm. This suggests that these industrial material sheets are effective in preventing capillary action caused by stresses such as folding the sheet when sewing it to a tent membrane structure, stretching the tent membrane structure fabric when attaching it to a steel frame, and flapping in strong winds after the tent membrane structure is completed. Furthermore, in the cross sections of the industrial material sheets (1) to (8), especially those of the same sheets joined together by high frequency, the dried "fluorine atom-free resin / polycarbodiimide having an ethylene oxide moiety" composite melts during heat and pressure bonding, refilling the gaps between the multifilaments that had occurred due to bending during sewing, and this has the effect of stopping water penetration within a length of 5 mm. Therefore, it has become clear that a tent membrane structure made by sewing industrial material sheets according to the present invention has an excellent effect of preventing rainwater penetration from these cross sections (preventing the growth of mold and algae), and that this effect is also excellent in durability. Furthermore, comparing Examples 5 and 7, and Examples 6 and 8, it was found that in Examples 7 and 8, which contained 25% by mass of an alkoxysilane compound in the elements constituting the composite, the silanol groups Si(OH)3 formed by hydrolysis of the alkoxysilane compound bonded to the surface of the glass filaments, while the alkoxy groups bonded to the carbodiimide groups, resulting in a robust yarn that is less likely to develop gaps in the glass multifilaments when a bending load is applied to the industrial material sheet, and that this robustness makes it possible to effectively suppress capillary action in glass fiber fabrics.Furthermore, in the industrial material sheets of Examples 1 to 8, a dried composite of "fluorine atom-free resin / polycarbodiimide having ethylene oxide moieties" was attached to the surface of the filaments and between the filaments in a total amount of about 3.6 to 4.3 mass% based on the basis weight of the fabric, and silver ions, copper ions, organic antifungal agents, etc. remained in the dried composite, giving the fabric itself sufficient antifungal properties, and antifungal properties were guaranteed even within the allowable length of rainwater penetration of 20 mm or less according to JIS K6404-3-16 A. Ink method.

[0041] [Comparative Example 1] The industrial material sheet (1) of Example 1 was prepared in the same manner as in Example 1, except that the mixed solution (1) of [Blend 1] was changed to the solution (5) of [Blend 7]. The thickness was 0.7 mm and the mass was 830 g / m. 2 A tarpaulin for the industrial material sheet (9) was obtained. The woven fabric (1a) contained in the industrial material sheet (9) had resin attached to the filament surfaces and between the filaments of the yarn in an amount of 3.6% relative to the woven fabric (1), similar to that of Example 1. However, due to the omission of the polycarbodiimide having an ethylene oxide moiety, the internal penetration of water exceeded 40 mm in length and could not be stopped within 20 mm. When rainwater penetrated, mold and algae would grow within the industrial material sheet, damaging its appearance and causing a moldy odor. Furthermore, since the dried material did not contain silver ions, copper ions, organic fungicides, etc., the woven fabric itself did not have antifungal properties, and when rainwater penetrated, mold and algae would grow within the industrial material sheet, damaging its appearance and causing a moldy odor. [Formulation 7] Solution (5) Solid content 6% by mass Fluorine atom-free resin (urethane resin) emulsion (solid content 40% by mass) Product name: Mayshield Z-1 (Meisei Chemical Industry Co., Ltd.) 15 parts by mass Dilution water 85 parts by mass

[0042] Comparative Example 2 In the industrial material sheet (2) of Example 2, the mixed solution (2) of [Blend 3] was changed to the solution (6) of [Blend 8], and the same as in Example 2, the thickness was 0.7 mm and the mass was 830 g / m 2 A tarpaulin for an industrial material sheet (10) was obtained. The woven fabric (1b) contained in the industrial material sheet (10) had resin attached to the filament surfaces and between the filaments of the yarn in an amount of 3.6% relative to the woven fabric (1), similar to Example 2. However, due to the omission of the polycarbodiimide having an ethylene oxide moiety, the internal penetration of water exceeded 40 mm in length and could not be stopped within 20 mm. When rainwater penetrated, mold and algae would grow within the industrial material sheet, damaging its appearance and causing a moldy odor. Furthermore, since the dried material did not contain silver ions, copper ions, organic fungicides, etc., the woven fabric itself did not have antifungal properties, and when rainwater penetrated, mold and algae would grow within the industrial material sheet, damaging its appearance and causing a moldy odor. [Formulation 8] Solution (6) Solid content 6% by mass Fluorine atom-free resin (acrylic resin) emulsion (solid content 40% by mass) Product name: Palladium SEF-1 (Ohara Palladium Chemical Co., Ltd.) 15 parts by mass Dilution water 85 parts by mass

[0043] Comparative Example 3 The industrial material sheet (1) of Example 1 was prepared in the same manner as in Example 1, except that the mixed solution (1) of [Blend 1] was changed to the solution (7) of [Blend 9]. The thickness was 0.7 mm and the mass was 830 g / m. 2A tarpaulin for an industrial material sheet (11) was obtained. The woven fabric (1a) contained in the industrial material sheet (11) had resin attached to the filament surfaces and between the filaments of the yarn in an amount of 3.6% relative to the woven fabric (1), similar to that of Example 1. However, due to the omission of the fluorine-atom-free resin, water penetration into the interior exceeded 60 mm in length and could not be stopped within 20 mm. When rainwater penetrated, mold and algae would grow within the industrial material sheet, damaging its appearance and causing a moldy odor. Furthermore, since the dried product did not contain silver ions, copper ions, organic fungicides, etc., the woven fabric itself did not have antifungal properties, and when rainwater penetrated, mold and algae would grow within the industrial material sheet, damaging its appearance and causing a moldy odor. [Formulation 9] Solution (7) Solid content 6% by mass Polycarbodiimide emulsion containing ethylene oxide moieties (solid content 40% by mass) Product name: Carbodilite V-02 (Nisshinbo Chemical Co., Ltd.) 15 parts by mass Dilution water 85 parts by mass

[0044] [Table 3] [Industrial Applicability]

[0045] The present invention makes it possible to provide industrial material sheets such as tarpaulins and canvases that have excellent durability and long-lasting effects, as well as the effect of preventing rainwater from penetrating through the cross sections of the industrial material sheets, as well as the effect of preventing mildew and algae, and further makes it possible to provide tent membrane structures made by sewing these industrial material sheets, that have excellent durability and long-lasting effects, as well as the effect of preventing rainwater from penetrating through the cross sections of the joints, as well as the effect of preventing mildew and algae, and thereby makes it possible to provide tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and sunshade tents, which can be used for a long period of time while maintaining a beautiful appearance.

Claims

1. 1) preparing a mixed solution essentially containing a fluorine atom-free resin emulsion, a carbodiimide compound (having an ethylene oxide moiety) emulsion, and dilution water (one or more selected from water containing 1 to 50 ppm silver ions, water containing 1 to 50 ppm copper ions, and water containing an organic antifungal agent at a concentration of 0.05 to 1% by mass); 2) a step of applying the dried mixture solution to the entire woven fabric obtained by entangling multifilament yarns in an amount of 1 to 7.5% by mass relative to the basis weight of the woven fabric; 3) forming a waterproof coating layer of a thermoplastic resin composition on the front and back of the dried material-attached fabric to conceal the dried material-attached fabric and produce an industrial material sheet; A method for producing an industrial material sheet, characterized in that water penetration (JIS K6404-3-16 A. Ink method) from the cross section of the yarn exposed on the cut surface of the industrial material sheet is stopped within a length of 20 mm.

2. The woven fabric is woven from only long fiber multifilament yarns or only short fiber spun multifilament yarns, and has a fiber weight of 50 to 400 g / m ２ or a fabric having a basis weight of 50 to 400 g / m woven using a combination of the long fiber multifilament yarn and the short fiber spun multifilament yarn. ２ 2. The method for producing an industrial material sheet according to claim 1, wherein the weight per unit area is 10 ...

3. 3. The method for producing an industrial material sheet according to claim 2, wherein the long-fiber multifilament yarn is an aggregate bundle of organic long-fiber filaments having a diameter of 1.25 to 4 denier or an aggregate bundle of inorganic filaments having a diameter of 2.5 to 10.0 μm, and the short-fiber spun multifilament yarn is an aggregate bundle of organic short-fiber filaments having a diameter of 1.25 to 4 denier.

4. 4. The method for producing an industrial material sheet according to claim 1, wherein the mixed solution further contains an alkoxysilane compound, the content of which is 7.5 to 35% by mass based on the dry matter.

5. A method for manufacturing a tent membrane structure using an industrial material sheet obtained by the manufacturing method according to claim 1, 1) A step of cutting the industrial material sheet to prepare a plurality of cut parts. 2) overlapping the ends of the cut pieces at a specific width and joining them by thermocompression or high-frequency welding to form a large number of connecting parts to form a tent membrane structure; A sewing method for a tent membrane structure, characterized in that water penetration (in accordance with JIS K6404-3-16 A. Ink Method) from the thread exposed on the cut cross section of the industrial material sheet included in the connecting portion is stopped within a length of 20 mm.

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