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

Abstract

To provide industrial material sheets (producing method) that excel in the warp and woof balance of water penetration prevention from cross-sections of tarpaulin and canvas and have excellent durability, as well as to provide tent membrane structures (sewing method) that are excellent in preventing water penetration from joint cross-sections.SOLUTION: 1) Preparing a treatment solution that necessarily includes a non-fluorine-containing resin emulsion and a carbodiimide compound (with an ethylene oxide moiety) emulsion; 2) Impregnating the treatment solution into a fabric woven from entangled multifilament yarns by applying high-frequency vibration or vibro-water vibration to obtain a treatment solution-impregnated fabric; 3) Drying the treatment solution-impregnated fabric to obtain a treated fabric with 1 to 7.5% by mass of the dry substance adhering; 4) Forming a thermoplastic resin coating layer on both sides of the treated fabric to create an industrial material sheet, thereby preventing internal water penetration from the cross-sections of the multifilament yarns exposed on the cut surface of the industrial material sheet to exceed 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, and in particular to a tent membrane structure that has excellent balance in the longitudinal direction of the effect of preventing rainwater penetration from the cross section of the industrial material sheet that constitutes the tent membrane structure, and excellent durability of that effect, and a method for manufacturing the industrial material sheet that constitutes this tent membrane structure. [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 sheets face a unique problem: when tent fabrics are subjected to long-term stresses from the elements, such as flapping in the wind, the impact of raindrops, and snow loads, the bundles of multifilament yarns loosen over time, promoting capillary action, allowing rainwater to penetrate the interior of the sheet and resulting in the growth of mold and algae. Furthermore, the capillary action specific to multifilament yarns behaves differently in the warp and weft yarns of the fabric, with capillary action tending to be particularly pronounced in the weft yarns. This is due to the fact that, when industrial sheets are processed, the tension applied to the fabric is aligned with the warp yarns, and as the width is reduced, the weft yarn density increases, while the weft yarn density remains almost unchanged. Capillary action in the weft yarns, in particular, occurring within and between multifilament yarns, has long been a problem. Therefore, there is a demand for industrial material sheets and tent membrane structures that have a well-balanced and stable effect in preventing rainwater penetration from the cross section and damaged parts of the industrial material sheet in the warp and weft directions, and that have excellent mold and algae resistance and durability. [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 has an excellent balance in the warp and weft directions of its rainwater penetration prevention effect from the cross section of tarpaulin, canvas, etc., and an excellent durability of this effect, and to provide a tent membrane structure (a sewing method) that has an excellent balance in the warp and weft directions of its rainwater penetration prevention effect from the cross section of the joints in the tent membrane structure made by sewing these industrial material sheets.By solving this problem, it is possible to maintain the appearance of tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and sunshade tents for a long period of time by suppressing the growth of mold and algae. [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 treatment solution essentially containing a fluorine atom-free resin emulsion and a carbodiimide compound (having an ethylene oxide moiety) emulsion; 2) a step of immersing a fabric woven by entangling multifilament yarns in a bath of the treatment solution and impregnating the interior of the multifilament yarns with the treatment solution by applying high-frequency vibration or water vibration at 3000 to 6000 times / min to obtain a treatment-solution-impregnated fabric; 3) drying the treatment solution-impregnated fabric to obtain a treated fabric having 1 to 7.5 mass % of the dried treatment solution adhered thereto relative to the basis weight of the fabric; 4) forming a thermoplastic resin coating layer on both sides of the treated fabric to 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 multifilament 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 anti-mold and anti-algae effects and excellent durability. They have also discovered that by 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, the balance in the warp and weft directions of the rainwater penetration prevention effect from the cross section of the joints and its dynamic durability are excellent. This has led to the completion of the present invention.

[0008] In the method for producing an industrial material sheet of the present invention, the treatment solution preferably further contains an alkoxysilane compound, the content of which is 7.5 to 35% by 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.

[0009] 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. 2This 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.

[0010] 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.

[0011] The sewing method for a tent membrane structure of the present invention is a method for manufacturing a tent membrane structure using an industrial material sheet obtained by the manufacturing method described in any one of the above, 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 to form a large 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 canvas that have an excellent balance of the warp and weft directions in preventing rainwater penetration from the cross section of the sheet and that have long-lasting durability.Furthermore, it makes it possible to provide tent membrane structures made by sewing these industrial material sheets that have an excellent balance of the warp and weft directions in preventing rainwater penetration from the cross section of the joints and that have long-lasting durability.This makes it possible to use tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and sunshade tents for long-term use while suppressing the growth of mold and algae. 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 treatment solution essentially containing a fluorine atom-free resin emulsion and a carbodiimide compound (having an ethylene oxide moiety) emulsion; 2) immersing a fabric woven by entangling multifilament yarns in a bath of the treatment solution and impregnating the interior of the multifilament yarns with the treatment solution by high-frequency vibration or water vibration at 3000 to 6000 times / min to obtain a treatment-solution-impregnated fabric; 3) drying the treatment-solution-impregnated fabric to obtain a treated fabric having a dried treatment solution content of 1 to 7.5 mass% based on the basis weight of the fabric; and 4) forming thermoplastic resin coating layers on the front and back of the treated fabric to obtain an industrial material sheet, wherein the industrial material sheet is produced by preventing water penetration from the cross section of the multifilament yarns exposed on the cut surface (JIS K6404-3-16 A. Ink method) is stopped within 20 mm in length, the treatment solution further contains an alkoxysilane compound, the content of which is 7.5 to 35 mass% based on the dry matter, and in particular, the woven fabric is woven only with long fiber multifilament yarn or only with short fiber spun multifilament yarn, and has 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 2and 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 the steps of: 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 to form a number of connecting parts to obtain a tent membrane structure, wherein water penetration into the connecting parts from the yarns exposed on the cut cross section of the industrial material sheet (in accordance with JIS K6404-3-16 A. ink method) is stopped within a length of 20 mm.

[0014] The fabrics used for the industrial material sheets produced by the manufacturing method of the present invention include plain weave fabrics, basket weave fabrics, twill weave fabrics, satin weave fabrics, and imitation weave fabrics, but plain weave fabrics are 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 3.81 μm (B fiber), 3.82 to 5.08 μm (C fiber), 5.09 to 6.35 μm (D fiber), 5.66 to 6.98 μm (DE fiber), or 8.89 to 10.0 μm (G fiber), and are preferably multifilament single yarns or untwisted single 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 elastic modulus (GPa) among glasses, 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 treatment solution essentially consisting of a fluorine-free resin emulsion, a carbodiimide compound (having an ethylene oxide moiety) emulsion, and dilution water. The fluorine-free resin emulsion is one or more selected from urethane resins, acrylic resins, silicone resins, and paraffin compounds. The silicone resin is a silicone-based water repellent such as OH-containing polysiloxane, methylpolysiloxane resin, dimethylpolysiloxane, or methylhydrogenpolysiloxane. The paraffin compound is a complex of such a paraffin compound with zirconium, such as n-paraffin wax having 20 to 48 carbon atoms and a melting point of 50 to 70°C. These fluorine-free resin emulsions can also be used in combination with 1 to 20% by mass of alkylene urea compounds (octadecylethylene urea), aliphatic amide compounds (N-methylolstearylamide), polyvinylpyrrolidone, etc. The dried mixture can be obtained by evaporating the water by heating. A "urethane resin / polycarbodiimide having an ethylene oxide moiety" composite or an "acrylic resin / polycarbodiimide having an ethylene oxide moiety" composite is particularly preferred, with a dry matter adhesion amount of 1 to 7.5% by mass relative to the fabric weight. This adhesion amount is significantly affected by factors such as the specific gravity of the yarns constituting the fabric, the number of filaments constituting the yarns, the filament diameter, the twist of the yarns, and the type and amount of oil and sizing agent used in spinning, and therefore must be adjusted appropriately depending on the fabric. If the amount of dry matter attached is less than 1% by mass, the internal penetration of water (JIS K6404-3-16 A. Ink method) may exceed 20 mm in length, and if the amount of attachment exceeds 7.5% by mass, the spaces between the filaments may be filled with excess resin, reducing the bending flexibility of the yarn and making it hard, which may reduce the tear strength of the industrial material sheet.

[0017] The fluorine-free resin 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. The chain extender may include a polyamine derivative, a hydrazine derivative, etc. 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 surface 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 includes the steps of: 1) adjusting a treatment solution essentially consisting of the above-mentioned fluorine atom-free resin emulsion, a carbodiimide compound (having an ethylene oxide moiety) emulsion, and dilution water to a total solids concentration of 3 to 18% by mass, and then stirring the solution at room temperature; 2) immersing a woven fabric woven by entanglement of multifilament yarns in a bath of the treatment solution to impregnate the entire fabric with the treatment solution (emulsion composition); 2) further impregnating the multifilament yarn with the treatment solution to the interior thereof by using high-frequency vibration (paragraph

[0023] ) or water vibration at 3000 to 6000 times / min (paragraph

[0023] ) in a liquid bath, and then simultaneously pulling up the impregnated fabric and squeezing it between a pair of rubber rolls to remove excess treatment solution, thereby obtaining a treatment solution-impregnated fabric; and 3) drying the treatment solution-impregnated fabric by means of drying and solidifying it with hot air at 100°C or higher, thereby obtaining a treated fabric having 1 to 7.5% by mass of dried treatment solution adhered to it relative to the fabric basis weight. Step 1) can further include an alkoxysilane compound, if necessary, whose content is 7.5 to 35% by mass of the total amount of dried material. The step 2) may be a method in which the treatment solution (emulsion composition) is applied to the front and back of the woven fabric by gravure coating, roll coating, knife coating, or the like to impregnate the emulsion composition onto the surface of the multifilament yarn and between the filaments, and then the emulsion composition is dried and solidified with hot air at 100°C or higher.

[0023] The high-frequency generator may be located inside or outside the liquid tank, provided that the high-frequency vibrator is located within the liquid tank. High-frequency vibrations are generated by ultrasonic waves with a frequency of 1 to 60 kHz, such as those generated by an ultrasonic oscillator, to generate vibration waves in the treatment solution (emulsion composition), causing the vibration waves to impinge across the entire width of the fabric. Alternatively, the water vibration may be a vibro-wave at 3,000 to 6,000 times per minute. By using a mechanism that brings the fabric into contact with the outer periphery of the cylindrical basket of the vibro-wave device during the impingement of these waves, the emulsion composition can be effectively impregnated and filled between the filaments of the multifilament yarn. When this high-frequency ultrasonic vibration propagates through the treatment solution, the vibration waves impart excessive acceleration to the surface of the multifilament yarn. This acceleration removes the sizing agent present on the surface of the multifilament yarn, effectively impregnating and filling the spaces between the multifilament yarn with the treatment solution. The temperature of the treatment solution is preferably controlled to 15 to 35°C, particularly 20 to 25°C. If the temperature is below 15°C, the efficiency of effectively impregnating the spaces between the multifilament yarns with the treatment solution will be reduced, and if the temperature is above 35°C, problems such as thickening and coagulation of the treatment solution (emulsion composition) may occur. Furthermore, the speed of the fabric passing around the high-frequency vibrator or the outer periphery of the cylindrical basket is preferably 4 to 16 m / min, and more preferably 4 to 10 m / min. In particular, the vibro ultrasonic wave generator has a two-tank structure in which a cylindrical basket and a cylindrical runner are stacked on the same axis, with the cylindrical runner on the inside, as a vibro mechanism within the liquid tank, and the cylindrical basket has multiple holes formed on the entire periphery, and the cylindrical runner has a corrugated cross section with unevenness formed all around its periphery. In this vibro mechanism, the cylindrical runner rotates at high speed, causing a shearing effect between the irregularities on the periphery of the cylindrical runner and the perforations, which violently ejects and sucks the treatment solution inside and outside the cylindrical basket and sprays it out through the perforations in the cylindrical basket, and the vibrations of 3,000 to 6,000 times per minute caused by this jet of water impart waves to the fabric that runs along and contacts the outer periphery of the cylindrical basket, effectively impregnating the spaces between the multifilament yarns with the treatment solution. This vibration treatment solution (emulsion composition) goes back and forth between the multifilament yarns, resulting in sufficient impregnation and filling effects in a short period of time.These high-frequency vibration and ultra-vibration methods can also be used in conjunction with microbubbles, which penetrate and burst between the multifilament yarns, removing the sizing agent present on the surface of the multifilament yarn and effectively impregnating and filling the gaps between the multifilament yarns with the treatment solution. Sizing agents, such as starch or aqueous epoxy resins, are present at approximately 0.3–1.5% of the yarns. These agents are particularly necessary when spinning multifilament yarns made of glass, but are unnecessary after the yarns are woven. In particular, for glass fiber fabrics, high-frequency vibration in the same liquid bath simultaneously removes the sizing agent from the multifilament yarn and impregnates it with the treatment solution. This can lead to the accumulation and concentration of the removed sizing agent in the liquid bath, resulting in redepositing of the multifilament yarn along with the treatment solution. Therefore, for glass fiber fabrics, a two-tank continuous process is preferred, in which the sizing agent is washed away in the first liquid bath using high-frequency vibration or vibro-water vibration (water removal using a mangle roll), followed by impregnation with the treatment solution in the second liquid bath using high-frequency vibration or vibro-water vibration. In this process, it is preferable that the first tank is filled with wash water and wastewater containing dissolved sizing agent is circulated at the same time to create a clean washing environment, and that the second tank is filled with fresh treatment solution to maintain a constant treatment solution concentration. In particular, it is preferable that the sizing agent on the fabric is removed in a separate process.

[0024] In the industrial material sheet of the present invention, the thermoplastic resin 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 thermoplastic resin coating layers may be colored and light-blocking, colored and light-transmitting, or colorless and transparent, as described below. In the industrial material sheet of the present invention, it is particularly preferred that the thermoplastic resin coating layers be soft vinyl chloride resins (containing plasticizers) from the viewpoints 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.

[0025] The thermoplastic resin coating layer of industrial material sheets (tarpaulins) can be formed by hot-kneading a thermoplastic resin composition (preferably a soft vinyl chloride resin compound) and melt-rolling it using a calendar or T-die extrusion method to produce a film (sheet) with a thickness of 80 to 800 μm, particularly 150 to 300 μm. Furthermore, the thermoplastic resin coating layers on both sides of an open-mesh fabric coated with a "fluorine-free resin / polycarbodiimide having an ethylene oxide moiety" composite can be formed by hot-melt compression bonding in a single or two-pass process using a laminator equipped with one or two continuous heat roll / rubber roll compression 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 structure applications such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, and sunshade tents. On the other hand, the thermoplastic resin coating layer of industrial material sheets (canvas) can be formed by a single-pass dipping method, in which a woven fabric is immersed in a liquid 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 surfaces and spaces between the multifilament yarns constituting the fabric with the soft vinyl chloride resin paste sol. The soft vinyl chloride resin paste sol is then removed and gelled with hot air at 160-185°C to form a 50-300 μm, preferably 80-200 μm, thick thermoplastic resin coating layer. Alternatively, the soft vinyl chloride resin paste sol can be applied to both sides of the woven 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 50-300 μm, preferably 80-200 μm, thick thermoplastic resin coating layer. 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.

[0026] On one or more surfaces of the thermoplastic resin 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.

[0027] 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 made by joining multiple industrial sheet components together and sewing them together to expand their area. This seam is achieved by lap-bonding using heat fusion (the edges of the sheets are used as adhesive, and the thermoplastic resin coating is melted to bond the overlapping edges). The cross-section of the woven 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 having an ethylene oxide moiety" composite to the surface and between the filaments of the woven yarn in an 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.

[0028] 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) See 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 one 5cm edge of the 20cm warp stack was fused 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 amp for 5 seconds on (3 seconds off) to obtain an industrial material sheet assembly. Two 15cm (warp) x 20cm (weft) sheets (for weft yarn testing) were similarly fabricated. Five 20cm long x 3cm wide test pieces (for warp yarn testing, one set for weft yarn testing) were taken from these assemblies. These test pieces were immersed in a 3% red ink aqueous solution bath for 72 hours and evaluated in the same manner. Absorption of less than 20mm (average value for five test pieces) was determined to be effective in preventing penetration. The removal of the waterproof coating layer, red ink, and test method were as described above.

[0029] [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%. Treatment solution (1) of [Mixture 1] was prepared to a solids concentration of 6% by mass and stirred at room temperature for 10 minutes. This fabric (1) was immersed in a liquid bath filled with treatment solution (1) of [Mixture 1] below, so that the entire fabric (1) was impregnated with the treatment solution (1). Furthermore, in a 28°C liquid bath, 40 kHz vibro vibration was oscillated at a cloth speed of 4 m / min to impregnate the fabric (1) to the interior of the multifilament yarn (using a "VIBRO WASHER" device manufactured by Uenoyama Iron Works Co., Ltd.). The impregnated fabric was then pulled up and simultaneously squeezed between a pair of rubber rolls to remove excess treatment solution (1), yielding a treatment-solution-impregnated fabric. The treatment-solution-impregnated fabric was then dried by means of hot air at 120°C in an electric furnace, resulting in a mass of 155.5 g / m2 of the dried composite adhering to the filament surfaces and between the filaments of the yarn of the fabric. 2The fabric (1a) was obtained. The dry weight of the composite was 5.5 g / m 2 and 3.6% for textiles (1). [Formulation 1] Treatment 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 <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

[0030] [Example 2] The same procedure as in Example 1 was repeated except that the treatment solution (1) in [Blend 1] in Example 1 was changed to the treatment 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] Treatment 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

[0031] [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. 2The fabric (2) was used. This fabric (2) was immersed in a liquid bath filled with the treatment solution (1) of [Recipe 1], and the entire fabric (2) was impregnated with the treatment solution (1). Furthermore, in a liquid bath at 28 to 32°C, a 40 kHz vibro vibration was transmitted to the fabric (2) at a cloth speed of 4 m / min, and the treatment solution (1) was impregnated into the interior of the multifilament yarn (using a "VIBRO WASHER" device manufactured by Uenoyama Iron Works Co., Ltd.). Next, the impregnated fabric was pulled up and simultaneously squeezed between a pair of rubber rolls to remove excess treatment solution (1), thereby obtaining a treatment solution-impregnated fabric. Next, the treatment solution-impregnated fabric was dried by means of drying and solidifying with hot air 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 yarn of the 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

[0032] [Example 4] In the industrial material sheet (3) of Example 3, the treatment solution (1) to be impregnated into the woven fabric (2) was changed to the treatment 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 attached to the filament surfaces and between the filaments of the yarn in an amount of 4.3% relative to the woven fabric (2).

[0033] [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 an industrial material sheet (5) was obtained. The woven fabric (3a) included in the industrial material sheet (5) had a dried composite material attached to the filament surfaces and between the filaments of the yarn in an amount of 3.9% relative to the woven fabric (3). However, in Example 5, as a pre-processing step before immersing the woven fabric (3) in a liquid bath filled with the treatment solution (1) of [Blend 1], the woven fabric (3) was immersed in a warm water bath at 34 to 40°C, and vibratory vibrations of 40 kHz were applied to the woven fabric (3) at a cloth speed of 4 m / min to remove the aqueous epoxy resin sizing agent attached to the multifilament yarn. The washed woven fabric (3) was then immersed in a liquid bath filled with the treatment solution (1) of [Blend 1], and high-frequency vibrations of 40 kHz were applied to the woven fabric (3) at a cloth speed of 4 m / min to impregnate the treatment solution (1) up to the interior of the multifilament yarn (using a "VIBRO WASHER" device manufactured by Uenoyama Iron Works Co., Ltd.). <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.

[0034] [Example 6] The industrial material sheet (2) of Example 2 was the same as Example 2 and Example 5 except that the woven fabric (1) was changed to the woven fabric (3). 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).

[0035] [Example 7] In the industrial material sheet (5) of Example 5, the treatment solution (1) of [Blend 1] was changed to the treatment solution (3) of [Blend 5], and the same as in Example 5, the thickness was 0.74 mm, and the mass was 960 g / m 2 A tarpaulin for the industrial material sheet (7) was obtained. [Blend 5] Treatment solution (3) was used after stirring at 28-30°C 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 filament surfaces and between the filaments of the yarn, relative to the woven fabric (3). [Formulation 5] Treatment 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

[0036] [Example 8] The same procedure as in Example 7 was repeated except that the treatment solution (3) in [Blend 5] in Example 7 was changed to the treatment 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] Water absorption prevention treatment 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

[0037] [Table 1]

[0038] [Table 2]

[0039] The industrial material sheets of Examples 1 to 8 were subjected to an impregnation process in which a "fluorine atom-free resin / polycarbodiimide having ethylene oxide moieties" composite was applied to the surface of the filaments and between the filaments of the woven fabric through a 40 kHz vibro-vibration process (using a "VIBRO WASHER" device manufactured by Uenoyama Iron Works Co., Ltd.) at a fabric speed of 4 m / min, and a total amount of approximately 3.6 to 4.3 mass% of the fabric weight was adhered to the woven fabric. This successfully prevented water from penetrating into the industrial material sheets from the cross section of the yarn exposed on the cut surface within a length of 5 mm (JIS K6404-3-16 A. Ink method). Furthermore, even after applying a bending load to the industrial material sheets of Examples 1 to 8, creating gaps in the multifilaments and promoting capillary action, the internal water penetration length was stopped within 10 mm. This suggests that these industrial material sheets can be expected to prevent capillary action caused by stresses such as folding the sheets when sewing them to a tent membrane structure, stretching the sewn tent membrane structure when attaching it to a steel frame, and flapping in strong winds after the tent membrane structure is completed. Furthermore, the cross sections of the high-frequency joints were all stopped within 5 mm due to the dried "fluorine-free resin / polycarbodiimide having an ethylene oxide moiety" composite melting during heat and pressure bonding, refilling the gaps between the multifilaments created by bending during sewing. Therefore, it was clear that tent membrane structures sewn with the industrial material sheets of the present invention have excellent rainwater penetration prevention (preventing mold and algae growth) through these cross sections, and that this effect is also durable and sustainable. 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.

[0040] [Comparative Example 1] The industrial material sheet (1) of Example 1 was prepared in the same manner as in Example 1, except that the treatment solution (1) of [Blend 1] was changed to the treatment 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, by omitting the polycarbodiimide having an ethylene oxide moiety, the water penetration inside exceeded 40 mm in length and could not be stopped within 20 mm, and when rainwater penetrated, mold and algae would grow inside the industrial material sheet, damaging its appearance and highly likely causing a moldy odor. [Formula 7] Treatment 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

[0041] Comparative Example 2 In the industrial material sheet (2) of Example 2, the treatment solution (2) of [Blend 3] was changed to the treatment solution (6) of [Blend 8], and the same procedure as in Example 2 was repeated to obtain a sheet having a thickness of 0.7 mm and a mass of 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, by omitting the polycarbodiimide having an ethylene oxide moiety, water penetration into the interior exceeded 40 mm in length and could not be stopped within 20 mm, and when rainwater penetrated, mold and algae would grow inside the industrial material sheet, damaging its appearance and highly likely causing a moldy odor. [Formula 8] Treatment 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

[0042] Comparative Example 3 The industrial material sheet (1) of Example 1 was prepared in the same manner as in Example 1, except that the treatment solution (1) of [Blend 1] was changed to the treatment solution (7) of [Blend 9]. The thickness was 0.7 mm and the mass was 830 g / m. 2 A 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 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, and when rainwater penetrated, mold and algae would grow inside the industrial material sheet, damaging its appearance and highly likely causing a moldy odor. [Formula 9] Treatment 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

[0043] [Table 3]

[0044] Comparative Example 4 In the manufacturing process of the tarpaulin of the industrial material sheet (5) of Example 5, the same process as in Example 5 was carried out except that the vibro vibration device was turned off and the 40 kHz vibro vibration was omitted. The thickness was 0.74 mm and the mass was 960 g / m. 2The tarpaulin for industrial materials (12) was obtained. By omitting high-frequency vibration, the effect of suppressing capillary absorption in the weft direction (weft yarns), which originally had a pronounced tendency for capillary absorption, was reduced, and abnormal water absorption lengths (45 mm) were observed in several locations, making the product out of specification. Furthermore, after a bending test, the water absorption length of the weft yarns increased to 72 mm, also out of specification. Regarding the joints, the fluorine-free resin and carbodiimide compound (containing ethylene oxide moieties) adhesion effect caused the filaments of the multifilament yarn to adhere to each other, preventing the out-of-specification water absorption length.

[0045] Comparative Example 5 In the manufacturing process of the tarpaulin of the industrial material sheet (6) of Example 6, the same process as in Example 6 was carried out except that the vibro vibration device was turned off and the 40 kHz vibro vibration was omitted. The thickness was 0.74 mm and the mass was 960 g / m. 2 The tarpaulin for industrial materials (13) was obtained. By omitting high-frequency vibration, the effect of suppressing capillary absorption in the weft direction (weft yarns), which originally had a pronounced tendency for capillary absorption, was reduced, and abnormal water absorption lengths (48 mm) were observed in several locations, which were out of specification. Furthermore, after a bending test, the water absorption length of the weft yarns increased to 78 mm, which was also out of specification. Regarding the joints, the fluorine-free resin and carbodiimide compound (containing ethylene oxide moieties) adhesion effect caused the filaments of the multifilament yarn to adhere to each other, which prevented the out-of-specification water absorption length from occurring.

[0046] Comparative Example 6 In the manufacturing process of the tarpaulin of the industrial material sheet (7) of Example 7, the same process as in Example 7 was carried out except that the vibro vibration device was turned off and the 40 kHz vibro vibration was omitted. The thickness was 0.74 mm and the mass was 960 g / m. 2The tarpaulin for industrial materials (14) was obtained. By omitting high-frequency vibration, the effect of suppressing capillary absorption in the weft direction (weft yarns), which originally had a pronounced tendency for capillary absorption, was reduced, and abnormal water absorption lengths (32 mm) were observed in several locations, which were not within the specifications. Furthermore, after a bending test, the water absorption length of the weft yarns increased to 56 mm, which was also not within the specifications. Regarding the joints, the fluorine-free resin and carbodiimide compound (containing ethylene oxide moieties) adhesion effect caused by high-frequency welding resulted in the filaments of the multifilament yarns to adhere to each other, preventing the water absorption length from exceeding the specifications.

[0047] Comparative Example 7 In the manufacturing process of the tarpaulin of the industrial material sheet (8) of Example 8, the same process as in Example 8 was carried out except that the vibro vibration device was turned off and the 40 kHz vibro vibration was omitted. The thickness was 0.74 mm and the mass was 960 g / m. 2 The tarpaulin for industrial materials (15) was obtained. By omitting high-frequency vibration, the effect of suppressing capillary absorption in the weft direction (weft yarns), which originally had a pronounced tendency for capillary absorption, was reduced, and abnormal water absorption lengths (37 mm) were observed in several locations, which were not within the specifications. Furthermore, after a bending test, the water absorption length of the weft yarns increased to 61 mm, which was also not within the specifications. Regarding the joints, the fluorine-free resin and carbodiimide compound (containing ethylene oxide moieties) adhesion effect caused by high-frequency welding resulted in the filaments of the multifilament yarns to adhere to each other, preventing the water absorption length from exceeding the specifications.

[0048] [Table 4] [Industrial Applicability]

[0049] The present invention makes it possible to provide industrial material sheets such as tarpaulins and canvas that have an excellent balance of the warp and weft directions in preventing rainwater penetration from the cross section of the sheet and that have long-lasting durability.Furthermore, it makes it possible to provide tent membrane structures made by sewing these industrial material sheets that have an excellent balance of the warp and weft directions in preventing rainwater penetration from the cross section of the joints and that have long-lasting durability.This makes it possible to use tent membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and sunshade tents for long-term use while suppressing the growth of mold and algae.

Claims

1. 1) preparing a treatment solution essentially containing a fluorine atom-free resin emulsion and a carbodiimide compound (having an ethylene oxide moiety) emulsion; 2) a step of immersing a fabric woven by entangling multifilament yarns in a bath of the treatment solution and impregnating the interior of the multifilament yarns with the treatment solution by applying high-frequency vibration or water vibration at 3,000 to 6,000 times / min to obtain a treatment-solution-impregnated fabric; 3) drying the treatment solution-impregnated fabric to obtain a treated fabric having a dried product of the treatment solution adhered thereto in an amount of 1 to 7.5% by mass relative to the basis weight of the fabric; 4) forming a thermoplastic resin coating layer on both sides of the treated fabric to 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 multifilament yarn exposed on the cut surface of the industrial material sheet is stopped within a length of 20 mm.

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

3. 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 3. The method for producing an industrial material sheet according to claim 1, wherein the weight per unit area is 10 ...

4. 4. The method for producing an industrial material sheet according to claim 3, 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.

5. A method for manufacturing a tent membrane structure using an industrial material sheet obtained by the manufacturing method according to any one of claims 1 to 4, 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 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 threads 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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