JP7610854B2 - Industrial material sheets, tents made by connecting the sheets, waterproof sheets, and methods for using the waste materials - Google Patents

Description

The present invention relates to industrial material sheets (tarpaulin, synthetic canvas) for tent membrane structures and waterproof sheets, and tent membrane sewn products (pavilions, tent houses, sunshade tents, etc.) and waterproof sheet sewn products (truck hoods, loading platform covers, open-air storage sheets, floor sheets, etc.) made by connecting these industrial material sheets, and in particular to tent membrane sewn products (tent membrane structures with the metal frame removed) and waterproof sheet sewn products on which information such as origin, product number, and material is clearly and firmly engraved and which makes it easy to determine whether to recycle or discard, and also to the utilization of waste materials based on the engraved markings on these waste sewn products.

For tent membrane structures such as large tents (pavilions), circus tents, seat houses, membrane roofs (ceilings) for architectural spaces, and stadium sunshades, tarpaulins are used, which are made by laminating a thermoplastic resin film such as soft polyvinyl chloride resin to a fabric made from long-fiber polyester yarn, and light colors such as white and ivory are preferred for their hues, which blend well with other buildings and are visually appealing. On the other hand, for truck canopies, loading platform covers, seat warehouses, and open-air storage sheets, synthetic canvas is used, which is made by impregnating and covering a spun fabric made from short-fiber polyester yarn with a thermoplastic resin solution such as soft polyvinyl chloride resin, and then heating, drying, and solidifying it, and dark colors such as dark green, olive drab, and navy blue, which do not show dirt easily, are the mainstream. These industrial sheet materials, such as tarpaulins and synthetic canvas, are distributed in rolls of material that are 0.3-1.5 mm thick, 0.9-2.4 m wide, and 25-50 m long, and for the reasons mentioned above, there are multiple competing products in these markets that are of the same color scheme and specifications.

Since these industrial material sheets do not display information such as the manufacturer, brand, product number, and material on the sheet itself, wholesalers and sewing shops sometimes cannot distinguish the manufacturer and product number when the wrapping paper is removed. In particular, manufacturers have recently been developing a variety of products that comply with regulations, such as REACH (Registration, Evaluation, Authorization and Restriction of Chemicals in the European Union), RoHS2 (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment in the European Union), Minister of Land, Infrastructure, Transport and Tourism certified products, and products with durability guarantees (8 years, 10 years, 15 years), so strict product management is required at wholesalers and sewing shops. However, even if the sheets are used without mixing up, once they are released into the world as final products, after more than 10 years, when they are dismantled and disposed of, they are currently sent to landfills regardless of the manufacturer, product number, material, etc. The reason these are not recycled is that the materials that have deteriorated over time have no value. However, in light of recent environmental and resource issues, the disposal of tent membrane structures, waterproof sheets, and other waste requires a system that can correctly identify basic information such as manufacturer, product number, and material, but no such system has yet been established within the industry. Furthermore, the secondary use of this waste has not yet been considered.

The applicant previously proposed synthetic leather with a pearlescent luster, which has a design part consisting of a depressed part and a non-depressed part and has a specific depression height difference, as a synthetic leather for use in the fabric of portable goods, furniture, flooring, decorative parts, etc., and which has a rich three-dimensional and unexpected design display by embossing, and disclosed in Patent Document 1 a synthetic leather in which the letters "HIRAOKA" are engraved in a convex shape by embossing press, and the letters are designed in a concave shape, with a depression height difference of 0.2 mm between the depressed and non-depressed parts. This synthetic leather has a decoration in which gold and violet interfere with each other alternately depending on the observation angle, except for the letter part, but such interfering uneven letters are poorly identifiable when used outdoors, and are therefore unsuitable for imprinting information on industrial material sheets. Patent Document 2 discloses an invention in which a unique heat transfer label is formed by screen printing as a heat transfer label for general use on textile products such as blousons, training wear, and T-shirts, or bags and sports shoes, in which the information display section on the label surface is mainly composed of raised parts of an uneven pattern, and the raised parts of the uneven pattern constituting the background pattern are glossy surfaces and the recessed parts are matte surfaces. However, even if such a transfer label formed by screen printing is used to display information on industrial material sheets, the fine uneven pattern will wear out and become short-lived due to screen printing. Therefore, at present, there is a strong demand for industrial material sheets on which information such as manufacturer, product number, and material can be displayed stably for a long period of time, and for a way to effectively reuse waste materials from industrial material sheet structures.

JP 2014-163013 A JP 2003-094891 A

The present invention aims to provide industrial material sheets (tarpaulin, synthetic canvas) for tent membrane structures and waterproof sheets, and tent membrane sewn products (pavilions, tent houses, sunshade tents, etc.) and waterproof sheet sewn products (truck hoods, loading platform covers, open-air storage sheets, floor sheets, etc.) made by connecting these industrial material sheets, in particular tent membrane sewn products (tent membrane structures with the metal frame removed) and waterproof sheet sewn products that are clearly and robustly marked with markings such as origin, product number, and material even with a marking depth of about 0.3 mm, and that allow sorting judgment for recycling/disposal over time, and further to provide a method of utilizing waste materials based on the markings on these sewn products.

As a result of intensive research in consideration of the above points, the present invention provides a long sheet comprising a soft polyvinyl chloride resin coating layer on the front and back sides of a fabric, the soft polyvinyl chloride resin coating layer containing a crosslinked rubber, a rubber crosslink formed throughout the layer, the rubber crosslink containing one or more rubber structures selected from butadiene rubber, isoprene rubber, and farnesene rubber, the soft polyvinyl chloride resin coating layer on either side of the front or back side having an imprinting area A, the imprinting area A being periodically formed on one side end in the longitudinal direction of the long sheet, comprising an indicia and a background, and having a "mirror surface convex portion (indicia)/matt texture concave portion (background)" )”, “mirror concave (indication)/matt convex (background)”, “matt convex (indication)/mirror concave (background)”, and “matt concave (indication)/mirror convex (background)”, and the indication is a collection of one or more types of concave and/or convex portions selected from letters, numbers, symbols, and figures (marks), so that the appearance of the indication and background has a contrast effect of the mirror surface and matt texture, and even if the engraving depth is about 0.3 mm, the visibility of the indication is significantly improved, and an industrial material sheet (tarpaulin, synthetic canvas) for tent membrane structures and waterproof sheets can be obtained with a clear engraving area A. The inventors have found that, in applications for tent membrane sewn products (pavilions, tent houses, sunshade tents, etc.) and waterproof sheet sewn products (truck hoods, loading platform covers, open-air storage sheets, floor sheets, etc.) made by connecting these industrial material sheets, by clearly and firmly marking information such as the source, product number, and material as the marking area A in a specific portion of the industrial material sheet, it becomes possible to determine whether to recycle or discard the product, and further that, based on this marking, the tent membrane sewn products (tent membrane structures with the metal frame removed) and waste waterproof sheet sewn products can be used as weed control sheets, leading to the completion of the present invention. In other words, if the marking area A is unclear, it becomes unclear who is responsible for the construction and disposal of the weed control sheet, so when waste materials such as tent membrane sewn products and waterproof sheet sewn products are reused as weed control sheets, at least the information in the marking area A is required. For example, the engraved area A "PET &PVC" indicates that the material is polyester fiber fabric and polyvinyl chloride resin, and the clarity of the engraved area A is maintained for a long period of time, making it easier to separate the material for later recycling (weed control sheet) or disposal.

The industrial material sheet of the present invention preferably contains a crosslinked rubber in the soft polyvinyl chloride resin coating layer, rubber crosslinks are formed throughout this layer, and this rubber crosslink contains one or more rubber structures selected from butadiene rubber, isoprene rubber, and farnesene rubber. By forming a hybrid in which a crosslinked network of rubber crosslinks is entangled with the polyvinyl chloride resin main chain within this soft polyvinyl chloride resin coating layer, the engraving in the engraving area A has excellent abrasion and wear resistance, and the engraving is stably maintained even after a long period of time outdoors, making it possible to make a sorting decision for recycling or disposal.

The industrial material sheet of the present invention preferably has a display portion that is a collection of one or more recesses and/or protrusions selected from letters, numbers, symbols, and figures (marks).

The tent membrane sewn product of the present invention is a tent membrane sewn product in which the ends of the above-mentioned industrial material sheets are lapped and connected by a high-frequency welding machine (high-frequency welder) equipped with a mold bar , and it is preferable that an imprinted area B is provided at the lap connection part of the tent membrane sewn product , and this imprinted area B is stamped by pressing the mold bar during high-frequency welding . This imprinted area B is stamped by pressing the heated mold when sewing the tent membrane, and the imprinted area B reveals the sewing manufacturer information of the tent membrane sewn product. For example, the imprinted area B "HIRAOKA" indicates that the sewing manufacturer is Hiraoka Orisen Co., Ltd., and the clarity of this imprinted area B is maintained for a long period of time, making it possible to inquire with the manufacturer.

The waterproof sheet sewn product of the present invention is a waterproof sheet sewn product in which the ends of the above-mentioned industrial material sheets are lap- connected by a high-frequency welding machine (high-frequency welder) equipped with a mold bar , and it is preferable that an imprinted area B is provided at the lap connection part of this waterproof sheet sewn product , and this imprinted area B is stamped by pressing the mold bar during high-frequency welding . This imprinted area B is stamped by pressing the heated mold when sewing the waterproof sheet, and the sewing manufacturer information of the waterproof sheet sewn product is revealed by the imprinted area B.

In the method of utilizing the waste tent membrane sewn material of the present invention, it is preferable to repurpose the waste tent membrane sewn material into weed control sheets. In this way, the waste tent membrane sewn material is appropriately reused as weed control sheets according to the tent membrane profile (information display) before being disposed of in landfills, eliminating the need for new weed control sheets. By eliminating the need for new weed control sheets, the consumption of new petrochemical raw materials is reduced, which also leads to a reduction in future carbon dioxide emissions.

In the method of utilizing waste waterproof sheet sewn products of the present invention, it is preferable to repurpose the waste waterproof sheet sewn products into weed control sheets. In this way, the waste waterproof sheet sewn products are appropriately reused as weed control sheets according to the profile (information display) of the waterproof sheet before being disposed of in landfills, eliminating the need for new weed control sheets. By eliminating the need for new weed control sheets, the consumption of new petrochemical raw materials is reduced, which also leads to a reduction in future carbon dioxide emissions.

In the application of industrial material sheets such as tent membrane sewn products (pavilions, tent houses, sunshade tents, etc.) and waterproof sheet sewn products (truck hoods, loading platform covers, open-air storage sheets, floor sheets, etc.), the markings, particularly the origin, product number, material, etc., are clearly and robustly displayed in the marking area A even if the marking depth is about 0.3 mm, making it easy to sort and decide whether to recycle or discard over a long period of time. Furthermore, by reusing the waste materials of tent membrane sewn products (tent membrane structures with the metal frame removed) and waterproof sheet sewn products as weed control sheets based on this marking, the consumption of petrochemical raw materials is reduced by the amount that new weed control sheets are not needed, which also leads to a reduction in carbon dioxide emissions.

FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention. FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention. FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention. FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention.

The industrial material sheet of the present invention is a long sheet comprising a fabric and a soft polyvinyl chloride resin coating layer on either side thereof, the soft polyvinyl chloride resin coating layer on either side having an imprinted area A, the imprinted area A being periodically formed on one end of the long sheet in the longitudinal direction, the imprinted area A being made up of a display portion and a background, and being one or more patterns selected from "mirror-surface convex portion (display portion)/pear-skinned concave portion (background)", "mirror-surface concave portion (display portion)/pear-skinned convex portion (background)", "pear-skinned convex portion (display portion)/mirror-surface concave portion (background)", and "pear-skinned concave portion (display portion)/mirror-surface convex portion (background)". The soft polyvinyl chloride resin coating layer contains a crosslinked rubber, rubber crosslinks are formed throughout the layer, and the rubber crosslinks include one or more rubber structures selected from butadiene-based rubber, isoprene-based rubber, and farnesene-based rubber. For example, the engraved area A "PET & PVC" indicates that the material is polyester fiber fabric and polyvinyl chloride resin, and the clarity of the engraved area A is maintained for a long period of time, making it easier to separate for later recycling (weed control sheet) or disposal. In this invention, mirror surface means a glossy appearance with light reflection, and matte surface means a matte appearance with fine unevenness that diffuses light reflection.

The fabric used in the industrial material sheet of the present invention can be in any form, such as woven fabric, knitted fabric, or nonwoven fabric. Examples of woven fabric include plain weave fabrics (biaxial fabrics consisting of warp and weft threads, triaxial fabrics consisting of warp and bias threads, and tetraaxial fabrics consisting of warp, weft and bias threads), twill weave fabrics (regular twill weaves such as 2x2, 3x3, and 4x4, and irregular twill weaves such as 3x2, 4x2, 4x3, 5x3, 2x3, 2x4, 3x4, and 3x5), twill weaves (minimum structural unit using a minimum of three warp and weft threads: 3-ply twill, 4-ply twill, 5-ply twill, 6-ply twill, 7-ply twill, 8-ply twill, 9-ply twill, 10-ply twill, 11-ply twill, 12-ply twill, 13-ply twill, 14-ply twill, 15-ply twill, 16-ply twill, 17-ply twill, 18-ply twill, 19-ply twill, 20-ply twill, 21-ply twill, 22-ply twill, 23-ply twill, 24-ply twill, 25-ply twill, 26-ply twill, 27-ply twill, 28-ply twill, 29-ply twill, 21-ply twill, 22-ply twill, 23-ply twill, 24-ply twill, 25-ply t Examples of usable fabrics include plain weave fabrics and 2x2 twill weave fabrics, with excellent balance of warp and weft properties. Examples of usable fabrics include raschel knit fabrics, and nonwoven fabrics include fleeces made by the wet method, dry method, spunbond method, or meltblown method, which are fixed with heat or adhesive. The above woven fabrics, knitted fabrics, and nonwoven fabrics may be subjected to one or more of the known fiber treatment processes such as scouring, bleaching, dyeing, softening, water repellency, water absorption prevention, flame retardancy, singeing, calendaring, binder fixing, and adhesive application in order to improve the performance of the industrial material sheet of the present invention.

The yarns constituting the fabric may be any of synthetic fibers, natural fibers (cotton, kenaf), semi-synthetic fibers (rayon, acetate), inorganic fibers, or a mixture of two or more of these. However, synthetic fibers such as polypropylene fibers, polyethylene fibers, polyvinyl alcohol fibers, polyester (PET, recycled PET, biomass PET synthesized from plant-derived raw materials, PBT, PNT) fibers, fully aromatic polyester fibers, biomass fibers synthesized from plant-derived raw materials (polyethylene furanoate fibers, polypropylene furanoate fibers, polybutylene furanoate fibers, polytrimethylene furanoate fibers, furan-based polyamide fibers, etc.), nylon fibers, fully aromatic polyamide fibers, aromatic heterocyclic polymer (polybenzimidazole, polybenzoxazole, polybenzothiazole, etc.) fibers, acrylic fibers, polyurethane fibers, or a mixture of these fibers are preferred. The yarn forms include monofilament, multifilament, short fiber spun (spun), split, tape, etc., but multifilament or short fiber spun (spun) is preferred to ensure the flexibility and tear strength of the industrial material sheet. Inorganic multifilament yarns such as glass fiber, silica fiber, alumina fiber, silica alumina fiber, and carbon fiber can also be used, and these inorganic fibers are particularly suitable for non-combustible materials (tent structures) certified by the Minister of Land, Infrastructure, Transport and Tourism, with glass fiber multifilament yarns being particularly versatile.

The fabric used in the present invention is preferably a woven fabric made of multifilament yarn or a staple spun fabric (spun), the multifilament yarn being in the range of 250 to 3000 denier (277 to 3333 dtex), particularly 500 to 2000 denier (555 to 2222 dtex), and non-twisted yarn (with an elliptical or flat cross section) or twisted yarn can be used as necessary. The staple spun yarn is preferably in the range of 10 (591 dtex) to 60 (97 dtex), particularly 10 (591 dtex), 14 (422 dtex), 16 (370 dtex), 20 (295 dtex), 24 (246 dtex), 30 (197 dtex), etc., and a single yarn, a two-ply yarn (single-twisted yarn), a double-twisted yarn (multi-twisted yarn) made of two or more single yarns, etc. There is no limit to the weft density of the warp and weft yarns in the woven fabric, and any design can be made depending on the thickness (denier, count) of the yarns used, but a weft density that results in a void ratio (open stitches) of the fabric of 0 to 30% and a basis weight of 100 to 500 g/ ^m2 is suitable for the fabric of an industrial material sheet. The void ratio can be calculated by subtracting the area of the yarns in a unit area of the fabric as a percentage from 100. The method is suitable for manufacturing a fabric (void ratio 10 to 35%) woven from multifilament yarn by heat laminating a film of a soft vinyl chloride resin composition onto, preferably, both sides thereof, to form a soft vinyl chloride resin coating layer. In the case of staple fiber spun fabric (spun), the method is suitable for forming a soft vinyl chloride resin coating layer onto, preferably, both sides thereof, of a staple fiber spun fabric (spun) having a void ratio of 0 to 10%, by coating and heat treatment using a paste-like soft vinyl chloride resin composition, or by dipping and heat treatment.

The soft vinyl chloride resin coating layer is formed from a soft vinyl chloride resin composition (containing a plasticizer), and is preferably formed by coating or dipping using paste vinyl chloride resin (emulsion polymerization type) and then gelling heat treatment, or by forming a coating using a vinyl chloride resin film (sheet) that has been calendered or T-die extrusion molded using straight vinyl chloride resin (suspension polymerization type). Paste vinyl chloride resin is suitable for the coating layer of canvas, while straight vinyl chloride resin is suitable for the coating layer of tarpaulin. The vinyl chloride resin may be made from a plant-derived monomer to form a biomass-compatible industrial material sheet. The plasticizer may be one or more of adipic acid diester compounds, sebacic acid diester compounds, phthalic acid diester compounds, isophthalic acid diester compounds, terephthalic acid diester compounds, cyclohexane dicarboxylate diester compounds, cyclohexene dicarboxylate diester compounds, chlorinated paraffin compounds, polyester compounds, ethylene-vinyl acetate-carbon monoxide terpolymer resins, ethylene-(meth)acrylic acid ester-carbon monoxide terpolymer resins, etc., and may be used in an amount of about 35 to 150 parts by mass per 100 parts by mass of vinyl chloride resin. The plasticizer may be a plant-derived compound to make the industrial material sheet biomass-compatible. Examples of plant-derived plasticizers include polyglycerin fatty acid ester compounds and furandicarboxylic acid dialkyl ester compounds.

The soft polyvinyl chloride resin coating layer can be coated with a polyvinyl chloride resin stabilizer, such as calcium zinc complex, barium zinc complex, organotin laurate, organotin mercaptite, or epoxy stabilizer, either alone or in combination, to prevent thermal deterioration and discoloration during the manufacture of the industrial material sheet of the present invention, and to improve weather resistance during outdoor use. The industrial material sheet of the present invention can be freely pigmented and can be colored as desired using titanium oxide (white), carbon black (black), inorganic compound complexes, azo compounds (red), phthalocyanine compounds (blue to green), anthraquinone compounds (yellow to red), quinacridone compounds (yellow to purple), etc., but white (titanium oxide) and pastel colors (titanium oxide with an accent color) are in high demand for tent membrane structures, and dark green and olive drab are in high demand for truck hoods and waterproof sheets. In addition, the soft vinyl chloride resin coating layer can contain various known additives for vinyl chloride resins in arbitrary amounts. If necessary, flame retardants (antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, ammonium polyphosphate, melamine cyanurate, etc.), light resistance stabilizers (HALS), ultraviolet absorbers (benzotriazole-based, benzophenone-based, triazine-based, etc.), antioxidants (phenol-based), antistatic agents (quaternary ammonium cations, ionic liquids, etc.), curing agents (isocyanate-based, silane cuprates, etc.), etc. ring agents, etc.), insect repellents (pyrethroids, etc.), antifungal agents (imidazole compounds, thiazole compounds, isothiazolinone compounds, pyridine compounds, N-haloalkylthio compounds, phenoxyarsine compounds, etc.), antibacterial agents (silver zeolite), deodorants (silicon oxide/metal oxide composites, etc.), heat insulating fillers (hollow particles, coarse titanium oxide, etc.), fragrances, phosphorescent pigments (strontium aluminate, etc.), aluminum flake pigments, pearl pigments, inorganic fillers (calcium carbonate, barium sulfate, etc.), etc.

In particular, the soft polyvinyl chloride resin coating layer contains crosslinked rubber, and rubber crosslinks are formed throughout this layer, and this rubber crosslink contains one or more rubber structures selected from butadiene-based rubber, isoprene-based rubber, and farnesene-based rubber, and forms a hybrid in which the rubber crosslink network is entangled with the polyvinyl chloride resin main chain, improving the wear and abrasion resistance of the engraved markings in the engraved area A and the engraved area B, and stably retaining the engraved markings even after a long period of time outdoors, making it easier to determine whether to recycle or dispose of the product. Such a rubber crosslink network can be formed by blending 5 to 30 parts by mass of one or more liquid synthetic rubbers selected from butadiene-based liquid rubber, isoprene-based liquid rubber, and farnesene-based liquid rubber with 100 parts by mass of polyvinyl chloride resin, and crosslinking between the liquid synthetic rubbers in parallel with the thermal gelation of the polyvinyl chloride resin. In this pre-crosslinking state, the liquid synthetic rubber penetrates into the polyvinyl chloride resin fine particles together with the plasticizer and acts as a softener for the polyvinyl chloride resin. By heating and gelling the soft vinyl chloride resin composition in this state, a hybrid soft vinyl chloride resin coating layer is formed in which the rubber crosslinked network is entangled with the vinyl chloride resin main chain. In other words, a hybrid in which the rubber crosslinked network is entangled with the vinyl chloride resin main chain is formed throughout the entire soft vinyl chloride resin coating layer.

Butadiene liquid rubber that forms rubber crosslinks has either -COOH or -OH groups at the molecular end, which allows for three-dimensional crosslinking. The molecular weight Mn is 1000 to 5000, especially 1300 to 3500, and the viscosity is 50 to 1000 poise (25°C), especially 200 to 500 poise (25°C). Butadiene liquid rubber contains 5 to 25% by mass of styrene and/or acrylonitrile as block copolymerization components, and 10 to 50% by mass of isoprene or hydrogenated isoprene as copolymerization components. Butadiene liquid rubber with 75 to 80% 1,4-cis structure or 1,4-trans structure and 20 to 25% 1,2-vinyl structure has low viscosity and excellent rubber elasticity when rubberized. This production ratio is made possible by radical polymerization method. The isoprene-based liquid rubber forming the rubber crosslink is preferably one having either a -COOH group or a -OH group at (both) molecular terminals and having a molecular weight Mn in the range of 3000 to 25000. The isoprene-based liquid rubber is one containing 5 to 25 mass% of styrene and/or acrylonitrile as a block copolymerization component, and 10 to 50 mass% of butadiene or hydrogenated isoprene as a copolymerization component. Examples of the farnesene-based rubber forming the rubber crosslink include rubbers containing monomers such as α-farnesene ((3E,7E)-3,7,11-trimethyl-1,3,6,10-dodecatetraene) and β-farnesene (7,11-dimethyl-3-methylene-1,6,10-dodecatriene), copolymer rubbers of farnesene and styrene, and copolymer rubbers of farnesene and butadiene. The Funnelsen-based liquid rubber preferably has either a -COOH group or a -OH group at the molecular (both) terminals and has a molecular weight Mn in the range of 3000 to 50000. The three-dimensional crosslinking of these liquid synthetic rubbers is formed by dehydration condensation of the -COOH group and -OH group at the molecular (both) terminals, but can also be formed by addition reaction with crosslinking agents such as diamines, polyamines, diisocyanates, polyisocyanates, epoxy-amines, aziridines, and oxazolines, or condensation reaction with compounds such as diols, polyols, dicarboxylic acids, and polycarboxylic acids. Furthermore, organic-inorganic hybrid rubber crosslinking containing silica can be used as part of the rubber crosslinking.

For rubber crosslinking, organic-inorganic hybrid rubber crosslinking in which silica particles are interposed as part of the rubber crosslinking is preferred. Silica is used in combination with the liquid synthetic rubber in an amount of 1 to 25% by weight, and is made part of a three-dimensional crosslink by forming chemical bonds between the functional groups on the silica surface and the -COOH and -OH groups at the molecular ends (both) of the liquid synthetic rubber. This reaction is formed by dehydration condensation between the -COOH and -OH groups at the molecular ends (both) of the liquid synthetic rubber and the silanol groups on the silica surface, but it is preferable to bond the functional groups of the liquid synthetic rubber and the silanol groups of the silica particles by addition reaction with crosslinking agents such as diamines, polyamines, diisocyanates, polyisocyanates, epoxy-amines, aziridines, and oxazolines, or condensation reaction with compounds such as diols, polyols, dicarboxylic acids, and polycarboxylic acids. This rubber crosslinking is generated simultaneously with the gelation heat treatment of the soft polyvinyl chloride resin paste that forms the soft polyvinyl chloride resin coating layer, and a homogeneous rubber crosslinking network is formed throughout the soft polyvinyl chloride resin coating layer. The soft polyvinyl chloride resin paste composition preferably contains a silane coupling agent to assist in the chemical bonding between the liquid synthetic rubber and the silica. This strengthens the rubber crosslinking, making the markings in the marking areas A and B, which are marked on specific parts of the industrial material sheet, more durable, making it easier to determine whether to recycle or dispose of the product after a long period of time.

The silica is preferably synthetic amorphous silica having a BET specific surface area of 100 to 300 m ² /g or a secondary particle diameter of 1 to 40 μm. The synthetic amorphous silica may be either wet-process silica (precipitation method or gel method) or dry-process silica (fumed silica). The surface of the silica has silanol (Si-OH group), and the silanol group reacts with -COOH group, -OH group, etc. at (both) molecular ends of the liquid synthetic rubber, and the silica particle becomes a part of the rubber component, thereby strengthening the rubber crosslinking and improving the abrasion resistance, and also making the display part of the marking area A and the marking area B, which are marked and displayed in a specific part of the industrial material sheet, more durable. Functional groups such as amino groups, vinyl groups, epoxy groups, methacryl groups, acrylic groups, chlorine groups, mercapto groups, isocyanurate groups, and isocyanate groups may be introduced into the silica surface. The silica particles are preferably surface-modified particles treated with a silane coupling agent. Silane coupling agents are alkoxysilane compounds having two or more different reactive groups in the molecule represented by the general formula: XR-Si(Y) ₃ , where, for example, X=amino group (aminosilane), vinyl group (vinylsilane), epoxy group (epoxysilane), methacryl group (methacrylsilane), acrylic group (acrylicsilane), chlorine group (chlorsilane), mercapto group (mercaptosilane), isocyanurate group (isocyanuratesilane), isocyanate group (isocyanatesilane), etc. (R=alkyl chain), Y=methoxy group, ethoxy group, etc. Surface modification of silica is a modification of the silanol group of silica with -Si-R-Si(Y) ₃ , but it may also be a modification of the siloxane bond portion of silica with (-O) ₃ Si-RX.

The manufacturing method of the industrial material sheet of the present invention includes the steps of: 1) preparing a soft polyvinyl chloride resin composition containing at least three components: polyvinyl chloride resin, a plasticizer, and liquid synthetic rubber; 2) coating a fabric with the soft polyvinyl chloride resin composition or laminating a soft polyvinyl chloride resin film to form a soft polyvinyl chloride resin coating layer; 3) converting the liquid synthetic rubber into a crosslinked rubber to form rubber crosslinks over the entire soft polyvinyl chloride resin coating layer; and 4) applying surface decorative embossing to form an imprint area A. The soft vinyl chloride resin composition (paste sol) is applied to the fabric in 2) by dipping (immersion-impregnation-roll squeezing-heat treatment gelation of the paste sol) or by coating (impregnation coating-heat treatment gelation of the paste sol) such as gravure coating, comma coating, roll coating, reverse roll coating, bar coating, doctor knife coating, etc., to form a coating thickness in the range of 0.05 to 0.3 mm, and the industrial material sheet is produced to a thickness of about 0.35 to 1.0 mm. The soft vinyl chloride resin film is formed to a thickness of 0.1 to 0.3 mm by calendar rolling or T-die extrusion molding of the soft vinyl chloride resin composition (compound), and the industrial material sheet is produced to a thickness of about 0.35 to 1.0 mm. The liquid synthetic rubber in 3) can be converted into a rubber crosslinked network by a crosslinking agent such as diamine, triamine, tetramine, polyamine, diisocyanate (e.g., hexamethylene diisocyanate: HMDI), triisocyanate (e.g., isocyanurate by cyclic trimer of HMDI), polyisocyanate, epoxy-amine, aziridine, oxazoline, etc., particularly a crosslinking agent having three or four functional groups, to form a dense and complex rubber crosslinked network. The conversion of the liquid synthetic rubber into a rubber crosslinked network is carried out simultaneously with the gelation of the soft vinyl chloride resin composition, so that a homogeneous rubber crosslinked network is formed throughout the soft vinyl chloride resin coating layer. The reaction between the liquid synthetic rubber and the crosslinking agent is preferably an equimolar reaction, but excess liquid synthetic rubber may remain in the soft vinyl chloride resin coating layer. The remaining liquid synthetic rubber is compatible with the plasticizer and acts to lower the glass transition temperature of the soft vinyl chloride resin coating layer, that is, as a cold resistance imparting agent. The remaining liquid synthetic rubber is within 10 parts by mass per 100 parts by mass of polyvinyl chloride resin. 4) The formation of the engraved area A by surface decorative embossing is periodically formed in the longitudinal direction of the industrial material sheet, and is formed at one end of the sheet, and is distinguishable from similar products of other companies by using mirror embossing (gloss), matte embossing (matte), pattern embossing (design), character engraving (embossed with embossed manufacturer name, product name, etc.), and especially by engraving the manufacturer name, product name, etc.

In addition, by providing an antifouling layer (0.005 to 50 μm) on the industrial material sheet of the present invention, the soft polyvinyl chloride resin coating layer is protected and damage caused by dust adhesion, ultraviolet degradation, and abrasion is mitigated. The antifouling layer allows the industrial material sheet, i.e., the tent membrane sewn product and the waterproof sheet sewn product, to maintain a beautiful appearance even after long-term use, so that the tent membrane sewn product and the waterproof sheet sewn product that have outlived their usefulness can be reused as a weed control sheet. The antifouling layer is a transparent layer containing acrylic resin, fluorine-based copolymer resin, acrylic-silicone copolymer resin, acrylic-fluorine copolymer resin, acrylic-urethane copolymer resin, a blend of acrylic resin and fluorine-based copolymer resin, and these resins together with silica fine particles, colloidal silica, organosilicate, silane coupling agent, ultraviolet absorber (benzophenone tautomer, benzotriazole tautomer, triazine tautomer, etc.), etc. These antifouling layers are formed by applying these paints by gravure coating and drying them to form a coating film, or by laminating a fluorine-containing resin film or a multilayer film such as a fluorine-containing resin/acrylic resin layer with an adhesive or by thermal melting. In addition, a photocatalytic layer containing a photocatalytic inorganic material (e.g., photocatalytic titanium oxide, photocatalytic tungsten oxide, etc.) can also be provided on these antifouling layers.

In particular, the industrial material sheet of the present invention has an imprinted area A, which is periodically formed in the longitudinal direction of the long sheet and is formed at one end of the sheet. The imprinted area A is composed of a display portion and a background, and the combination of the mirror portion and the matte portion in one or more patterns selected from "mirror convex portion (display portion)/matte concave portion (background)", "mirror concave portion (display portion)/matte convex portion (background)", "matte convex portion (display portion)/mirror concave portion (background)", and "matte concave portion (display portion)/mirror convex portion (background)" improves the visual contrast effect, making the imprinted area A clear even with an imprint depth of about 0.3 mm. In the present invention, the mirror surface means a glossy appearance accompanied by light reflection, and the matte surface means a matte appearance with fine unevenness that reflects light diffusely. The display portion is a collection of one or more types of concave portions and/or convex portions selected from letters, numbers, symbols, and figures (marks), and specifically, the manufacturer's name, product name, product number, registration number, material indication, reading code, etc. The height of the convex portion (depth of the concave portion) is 0.03 mm to 0.2 mm. The shape of the marking area A is not particularly specified, and may be a rectangle, a square, a polygon, an ellipse, a circle, etc., but a rectangle or an ellipse is preferable. The size of the marking area A is a square, polygon, circle, etc., with a minimum of 3 cm high x 3 cm wide and a maximum of 15 cm high x 15 cm wide, and a rectangle, ellipse, etc., with a minimum of 3 cm high x 5 cm wide and a maximum of 10 cm high x 25 cm wide. If the size of the marking area A is too small, it becomes difficult to read the displayed content, and if it is too large, it affects the appearance of the tent membrane sewn product and the waterproof sheet sewn product. The marking area A is formed periodically in the longitudinal direction during the production of the industrial material sheet, and the position of its formation is the right end or left end in the width direction of the industrial material sheet. The tent membrane sewn product and waterproof sheet sewn product of the present invention are welded by overlapping the ends of the industrial material sheet by 3 to 10 cm, so it is preferable to form the marking area A on the right or left end excluding 3 to 10 cm from the end that becomes the lap part, and especially to form the marking area A on the back side. The marking area A is continuously formed at regular intervals by the embossing roll, and letters, numbers, symbols, and figures (marks) are designed in reverse on the embossing roll. For example, in the case of one marking on an embossing roll with a diameter of 30 inches, the marking area A is continuously formed at intervals of about 240 cm. The marking area A clarifies the manufacturer information of the industrial material sheet. The embossing is performed by pressing the embossing roll set at 100 to 180 ° C with a pair of rubber rolls, and the marking display is fixed by cooling (air-cooled and water-cooled rolls) after embossing. It is preferable that the marking area A is on the inside of the tent membrane sewn product and the waterproof sheet sewn product to protect it from damage such as soot, rain, and ultraviolet rays. For example, the marking in area A, "PET & PVC," indicates that the material is polyester fiber fabric and polyvinyl chloride resin, and the clarity of the marking in area A is maintained for a long period of time, making it easier to separate the material for later recycling (weed control sheet) or disposal.

In addition, the tent membrane sewn product and waterproof sheet sewn product of the present invention are welded by overlapping the ends of the industrial material sheets by 3 to 10 cm with a lap connection. This welding is performed by pressing with a heated mold, specifically, pressing for a welding time of 3 to 5 seconds with a high-frequency welding machine (high-frequency welder) equipped with a rectangular mold bar with a width of 3 to 10 cm and a length of 100 cm, molecular vibration of the vinyl chloride resin of the soft vinyl chloride resin coating layer is caused by the high frequency, the soft vinyl chloride resin coating layer is melted by the frictional heat, and the sheet ends are welded, and the sheets are fixed by pressing for a cooling time of 5 to 10 seconds. An imprinting area B is provided in the lap connection part of the tent membrane sewn product and waterproof sheet sewn product, and this imprinting area B is stamped by pressing with the mold bar during high-frequency welding. The imprinting area B is designed on the mold bar, and the height of the imprinting area B is 3 to 10 cm, the length is 3 to 15 cm, and it is designed in at least one place at the end or center of the mold bar with a length of 100 cm, for example. The marking area B is designed with information of the tent membrane sewing manufacturer or the waterproof sheet sewing manufacturer, specifically, the sewing manufacturer, the read code, the symbol mark, etc. The mold bar is flat, and the information display is cast in the same four patterns as the marking area A, which is cast with a convex mirror surface, a convex matte surface, a concave mirror surface, a concave matte surface, etc., or the information display is cast by excluding the convex parts in the stripes that are in the form of letters or figures, which are formed by forming equally spaced convex stripes on the entire surface of the mold bar. The marking area B is formed by the mold bar, and letters, numbers, symbols, figures (marks) are designed in reverse on the mold bar. The marking area B clarifies the sewing manufacturer information of the tent membrane sewing product or the waterproof sheet sewing product. It is preferable that the marking area B is provided at intervals of 1 to 3 m on the inside of the tent membrane sewing product or the waterproof sheet sewing product to protect it from damage such as soot, wind, rain, and ultraviolet rays. For example, the engraved area B "HIRAOKA" indicates that the garment manufacturer is Hiraoka Textile & Sen Co., Ltd., and the clarity of the engraved area B is maintained for a long period of time, making it possible to inquire about the manufacturer.

Currently, sewn tent membranes and sewn waterproof sheets that have been used for 5 to 10 years are dismantled and disposed of in landfills, but even sewn items that have been used no longer retain their waterproof and light-blocking properties as they did when they were first used, unless there are holes or other damage. Therefore, healthy waste sewn tent membranes and sewn waterproof sheets can be reused as weed control sheets for vacant lots, fallow land, solar power generation equipment installation areas, railway track slopes, etc., and the waterproof properties cut off the water supply to plants (especially weeds), while the light-blocking properties cut off the photosynthesis of plants (especially weeds), thereby contributing to the prevention of weed devastation. In other words, it is a durable material with a thickness of 0.35 to 1.0 mm that is suitable for preventing plant proliferation. To reuse as weed control sheets, sewn tent membranes and sewn waterproof sheets can be dismantled to any size, laid on the ground or slopes, and secured to the ground with anchor pins or the like, in the same way as conventional weed control sheets. For tent membrane structures, white and ivory are particularly easy to obtain, and for truck hoods and waterproof sheets, dark green and olive drab are particularly easy to obtain. This reuse does not require new waterproof sheets, and reduces the consumption of petrochemical raw materials for manufacturing waterproof sheets, which leads to a reduction in the possibility of future carbon dioxide emissions. However, when reusing as a weed control sheet, if the user blindly lays the weed control sheet without knowing the information on the materials such as the tent membrane sewing material and the waterproof sheet sewing material, it is the same as dumping waste materials. Therefore, by clarifying the basic information (stamped area B) of the tent membrane sewing material and the waterproof sheet sewing material, and the basic information (stamped area A) of the industrial material sheet that constitutes the tent membrane sewing material and the waterproof sheet sewing material, it is possible to reuse as a weed control sheet and fulfill the corporate (company) responsibility for disposal after reuse. If neither engraved area A nor engraved area B is known, it will be impossible to determine who is responsible for the construction and disposal of the weed control sheet, so in order to reuse waste materials such as sewn tent membranes and waterproof sheeting as weed control sheets, at least the information in engraved area A is required.

The present invention will now be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples.
The test methods used in the examples and comparative examples of the present invention are as follows.
(1) Scott type reciprocating bending abrasion test (JIS L1096 8.19.2 B method)
A test piece of 25 mm width x 120 mm length including the imprinted area A was taken from the industrial material sheet, and left to stand in a 25°C environment for 24 hours. Then, it was attached to a Scott type testing machine and subjected to reciprocal bending 1000 times and 2000 times with a load of 1 kgf in a constant temperature room at 25°C. After the test, the surface condition was observed and the dynamic cold resistance was judged as follows.
1: No significant wear or abrasion is observed on the marking part of the marking area A. 2: Significant wear is observed on the marking part of the marking area A, but it can be distinguished. 3: The marking part of the marking area A has been worn away and cannot be distinguished. (2) Abrasion resistance of the marking area A: JIS L1096 8.19.3 Method C) Taber method A disk with a diameter of 13 cm including the marking area A taken from an industrial material sheet was used as a test piece,
The specimen was attached to a Taber type abrasion tester (wearing wheel CS-10) and subjected to an abrasion load of 2.45 N for 1,000 and 2,000 revolutions on the engraved area A. The engraved area A was then observed with a magnifying glass to determine the discernibility of the markings in the engraved area A.
1: No significant wear or abrasion is observed on the marking part of the marking area A 2: Significant wear is observed on the marking part of the marking area A, but it can be distinguished 3: The marking part of the marking area A is worn away and cannot be distinguished (3) Formation of the marking area A 3-1) During the production of the industrial material sheet, the marking area A was continuously formed at the right end of the industrial material sheet, excluding the end 10 cm, at a speed of 8 m/min with a 30-inch diameter embossing roll at 240 cm intervals. The embossing roll was engraved with "PET &PVC" in reverse Gothic font (1 character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm), with a concave mirror surface (height difference 0.5 mm) and a matte convex background designed by the marking part, and was written horizontally along the longitudinal direction of the end of the industrial material sheet. The marking area A was formed by pressing the embossing roll set at 180°C with a pair of rubber rolls, and the marking was fixed by cooling (air-cooled and water-cooled rolls) after embossing. The resulting engraved area A is a matte-finished depression (background: height 3.5 cm x width 19 cm) containing a mirror-surface convex portion (indication portion). The rest of the embossing roll is a mirror surface.
3-2) As in 1) above, "PET &PVC" in inverted Gothic font (1 character: 2 cm x
2cm line width 5mm mirror surface: character spacing 5mm) Convex mirror surface (height difference 0.5mm)
The engraved area A obtained by using an embossing roll with a background designed with a matte textured depression is a matte textured convex area (background: height 3.5 cm x width 19 cm) including a mirror surface depression (indication area), and the area of this embossing roll other than the engraved area A is a mirror surface.
3-3) As in 1) above, "PET &PVC" in inverted Gothic font (1 character: 2 cm x
2cm line width 5mm matte finish: character spacing 5mm) Concave matte finish due to display (height difference 0.5mm),
The engraved area A obtained by using an embossing roll with a background designed with a mirror-surface convex portion is a mirror-surface concave portion (background: height 3.5 cm x width 19 cm) including a matte-finish convex portion (indication portion), and the area other than the engraved area A on this embossing roll is matte-finished.
3-4) As in 1) above, "PET &PVC" in inverted Gothic font (1 character: 2 cm x
2cm line width 5mm matte finish: character spacing 5mm) Convex matte finish due to display part (height difference 0.5mm),
The engraved area A obtained by using an embossing roll with a mirror-surface recessed design in the background is a mirror-surface convex area (background: height 3.5 cm x width 19 cm) including a matte-finished recessed area (indication area), and the area other than the engraved area A in this embossing roll is matte-finished.
(4) Formation of imprinting area B The ends of two industrial material sheets in the same direction were overlapped in a straight line with a width of 4 cm in parallel to provide a lap stitching section, and the lap stitching section was then sewn using a high-frequency welder (YTO-8A type, high-frequency output 8 kW, manufactured by Yamamoto Vinita Co., Ltd.) equipped with a weld bar (imprinting blade) with a width of 4 cm and a length of 30 cm.
The lap stitching was pressed against the weld bar with an anode current of 1.0 A, and the soft polyvinyl chloride resin coating layer was melted by high-frequency oscillation to obtain a sewn product. The weld bar was marked with the inverted Gothic font "HIRAOKA" (1.
Characters: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm) The marking area has a convex mirror surface (height difference 0.5 mm), and the background is designed with a matte recessed pattern in the engraved area B. In this weld bar, the area other than the engraved area B is a mirror surface.

Example 1
<Fabric (1)>
A No. 5 fabric was used, which was plain woven with a warp density of 54 threads/inch and a weft density of 46 threads/inch using 20-count two-ply polyester staple spun yarn (S twist 300 T/m) as the warp yarn and 10-count single-ply polyester staple spun yarn (S twist 400 T/m) as the weft yarn, and had a void ratio of 0 in appearance in terms of fluff and a mass of 240 g/ ^m2 .
The fabric was subjected to a water-repellent treatment (immersion, heat treatment) using an acrylate/vinyl chloride resin copolymer emulsion (solid content 5% by mass) having a perfluoroalkyl group having 6 or less carbon atoms to prevent rainwater penetration (water absorption) in the event that an abnormality occurs in the soft vinyl chloride resin coating layer. This was designated fabric (1).
<Soft polyvinyl chloride resin coating layer>
A processing liquid was prepared that mainly contained a vinyl chloride resin composition paste (containing at least three kinds of vinyl chloride resin, plasticizer, and liquid synthetic rubber) for forming a soft vinyl chloride resin coating layer of the following <Composition 1>. Next, the fabric (1) was dipped (immersed) in a liquid bath filled with this processing liquid, and the processing liquid of <Composition 1> was impregnated into the fabric (1) at normal pressure. The fabric (1) was then pulled out of the liquid bath and simultaneously squeezed with a rubber mangle roll to remove excess processing liquid, and a soft vinyl chloride resin coating layer was provisionally formed. Next, a gelation heat treatment was performed in a hot air oven at 180°C for 3 minutes to form a soft vinyl chloride resin coating layer of 290 g/ ^m2 on the entire surface of the fabric (1), and the imprint area A described in paragraph [0031] 3-1) was provided on the back surface, and a dark green waterproof canvas (1) with a mass of 530 g/ ^m2 was obtained. The waterproof canvas (1) was provided with an imprint area B described in paragraph (4) of (0031) on the back surface of the sewn portion.
The gelation heat treatment is a process in which the polyvinyl chloride resin composition paste is converted into soft polyvinyl chloride resin, and at the same time the liquid synthetic rubber is crosslinked and converted into a crosslinked rubber, thereby forming a hybrid in which a three-dimensional crosslinked network is entangled with the polyvinyl chloride resin main chain throughout the entire area of the resulting soft polyvinyl chloride resin coating layer.
<Formulation 1> Processing fluid for forming soft polyvinyl chloride resin coating layer Paste polyvinyl chloride resin (degree of polymerization 1700) 100 parts by weight Diisononyl phthalate (DINP plasticizer) 60 parts by weight Butadiene-based liquid rubber * 10 parts by weight Isocyanurate (HMDI * trimer: NCO crosslinking agent) 2 parts by weight Chlorinated paraffin (flame retardant and plasticizer) 5 parts by weight Epoxidized soybean oil (stabilizer and plasticizer) 4 parts by weight Antimony trioxide (flame retardant) 20 parts by weight Zinc stearate (stabilizer) 2 parts by weight UV absorber (triazine tautomer) 0.5 parts by weight Titanium oxide (white pigment) 1 part by weight Phthalocyanine green (green pigment) 3 parts by weight Carbon black (black pigment) 0.5 parts by weight Trichloroethylene (dilution solvent) 20 parts by weight *Butadiene-based liquid rubber: Contains 15% by mass of styrene as a block copolymer component.
It has an average molecular weight of 3000 and has -COOH groups at both ends of the molecule. *HMDI: Hexamethylene diisocyanate. HMDI trimer (isocyanurate) has three isocyanate groups.

Example 2
A dark green waterproof canvas (2) weighing 530 g/m2 was obtained in the same manner as in Example 1, except that the processing solution of <Composition 1> in Example 1 was changed to the processing solution of <Composition 2> and the marking area A described in paragraph [0031] 3-2 ⁾ was provided on the back surface. The marking area B described in paragraph [0031] (4) was provided on the back surface of the sewn part of the sewn product of this waterproof canvas (2).
The processing fluid of <Blend 2> is obtained by replacing 10 parts by mass of the butadiene-based liquid rubber of <Blend 1> with 10 parts by mass of isoprene-based liquid rubber. The isoprene-based liquid rubber contains 10% by mass of acrylonitrile as a block copolymer component, has -COOH groups at both molecular terminals, and has an average molecular weight of 2,500.

Example 3
A dark green waterproof canvas (3) weighing 530 g/m2 was obtained in the same manner as in Example 1, except that the processing solution of <Composition 1> in Example 1 was changed to the processing solution of <Composition 3> and the marking area A described in paragraph [0031] 3-3) was provided on the back surface. The marking area B described in paragraph [0031] ⁽ 4) was provided on the back surface of the sewn part of the sewn product of this waterproof canvas (3).
The processing fluid of <Blend 3> is obtained by replacing 10 parts by mass of the butadiene-based liquid rubber of <Blend 1> with 10 parts by mass of β-funnelsen-based liquid rubber. The β-funnelsen-based liquid rubber contains 10% by mass of butadiene as a block copolymer component, has -COOH groups at both molecular terminals, and has an average molecular weight of 5,000.

Example 4
A dark green waterproof canvas (4) weighing 530 g/m2 was obtained in the same manner as in Example 1, except that the processing solution of <Composition 1> in Example 1 was changed to the processing solution of < ^Composition 4> and the marking area A described in paragraph [0031] 3-4) was provided on the back surface. The marking area B described in paragraph [0031] (4) was provided on the back surface of the sewn part of the sewn product of this waterproof canvas (4).
The processing liquid of <Blend 4> is the processing liquid of <Blend 1> to which 2 parts by mass of surface-modified silica particles have been added.
The surface-modified silica particles are prepared by stirring dry silica (gel method: average particle size 2 μm, BET specific surface area 300 ^m2 /g) in a 5 mass% aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (silane coupling agent) at 24°C for 3 hours, separating and drying the particles; they contain a mixture of -Si-R-Si( _OCH3 ) ₃ modifications bonded to the silanol groups of the silica and (-O) _3Si -R- _NH2 modifications bonded to the siloxane moieties.

Example 5
<Fabric (2)>
A plain weave fabric was used, consisting of 1000 denier (1111 dtex) polyethylene terephthalate (PET) fibers (192 filaments) and S-twisted 50 T/m PET multifilament yarns for the warp and weft groups, with the warp group having a weave of 16 threads per inch, and the weft group having a weave of 16 threads per inch. The mass of this fabric was 150 g/ ^m2 , and the void ratio (total of open areas) was 14%.
This fabric was subjected to a water-repellent treatment (immersion, heat treatment) using an acrylate/vinyl chloride resin copolymer emulsion (solid content 5% by mass) having a perfluoroalkyl group having 6 or less carbon atoms to prevent rainwater from penetrating (preventing water absorption) through the cut cross section of the sewn tent membrane sheet. This was named fabric (2).
<Soft polyvinyl chloride resin coating layer>
A vinyl chloride resin composition compound (containing at least three kinds of vinyl chloride resin, plasticizer, and liquid synthetic rubber) for forming a soft vinyl chloride resin coating layer of the following <Formulation 5> was prepared. A fabric (2) was used as a substrate, and a 0.2 mm-thick calendar-molded film made of the vinyl chloride resin composition compound of [Formulation 5] was applied to both sides of the substrate as the soft vinyl chloride resin coating layers on the front and back, and melt-laminated by thermocompression bonding with a laminator. Further, the imprint area A described in 3-1) of paragraph [0031] was provided on the back, to obtain a white tent membrane tarpaulin (1) having a thickness of 0.7 mm and a mass of 830 g/m ^2. The imprint area B described in (4) of paragraph [0031] was provided on the back of the sewn part of the sewn product of this tent membrane tarpaulin (1).
[Formulation 5]: Soft vinyl chloride resin composition (compound)
Straight polyvinyl chloride resin (K value 71.5) 100 parts by weight Diisononyl phthalate (DINP plasticizer) 60 parts by weight Butadiene-based liquid rubber* 10 parts by weight Isocyanurate (HMDI* trimer: NCO crosslinking agent) 2 parts by weight Chlorinated paraffin (flame retardant and plasticizer) 5 parts by weight Epoxidized soybean oil (stabilizer and plasticizer) 4 parts by weight Antimony trioxide (flame retardant) 20 parts by weight Zinc stearate (stabilizer) 2 parts by weight UV absorber (triazine tautomer) 0.5 parts by weight Titanium oxide (white pigment) 3 parts by weight *Butadiene-based liquid rubber: Contains 15% by weight of styrene as a block copolymer component,
It has an average molecular weight of 3000 and has -COOH groups at both ends of the molecule. *HMDI: Hexamethylene diisocyanate. HMDI trimer (isocyanurate) has three isocyanate groups.

Example 6
A white tent tarpaulin (2) having a thickness of 0.7 mm and a mass of 830 g/m2 was obtained in the same manner as in Example 5, except that the compound of <Composition 5> in Example 5 was changed to the compound of <Composition ⁶ > and the imprinting area A described in paragraph [0031] 3-2) was provided on the back surface. The imprinting area B described in paragraph [0031] (4) was provided on the back surface of the sewn part of the sewn product of this tent tarpaulin (2).
The compound of <Mixture 6> is obtained by replacing 10 parts by mass of the butadiene-based liquid rubber of <Mixture 5> with 10 parts by mass of isoprene-based liquid rubber. The isoprene-based liquid rubber contains 10% by mass of acrylonitrile as a block copolymer component, has -COOH groups at both molecular terminals, and has an average molecular weight of 2500.

Example 7
A white tent tarpaulin (3) having a thickness of 0.7 mm and a mass of 830 g/m2 was obtained in the same manner as in Example 5, except that the compound of <Composition 5> in Example 5 was changed to the compound of <Composition ⁷ > and the imprinted area A described in paragraph [0031] 3-3) was provided on the back surface. The imprinted area B described in paragraph [0031] (4) was provided on the back surface of the sewn part of the sewn product of this tent tarpaulin (3).
The compound of <Mixture 7> is obtained by replacing 10 parts by mass of the butadiene-based liquid rubber of <Mixture 5> with 10 parts by mass of β-funnelsen-based liquid rubber. The β-funnelsen-based liquid rubber contains 10% by mass of butadiene as a block copolymer component, has -COOH groups at both molecular terminals, and has an average molecular weight of 5,000.

Example 8
A white tent tarpaulin (4) having a thickness of 0.7 mm and a mass of 830 g/m2 was obtained in the same manner as in Example 5, except that the compound of <Composition 5> in Example 5 was changed to the compound of <Composition ⁸ > and the imprinted area A described in paragraph [0031] 3-4) was provided on the back surface. The imprinted area B described in paragraph [0031] (4) was provided on the back surface of the sewn part of the sewn product of this tent tarpaulin (4).
The processing fluid of <Formulation 8> is obtained by adding 2 parts by mass of surface-modified silica particles to the compound of <Formulation 5>. The surface-modified silica particles are obtained by stirring dry silica (gel method: average particle size 2 μm, BET specific surface area 300 m ² /g) in a 5% by mass aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (silane coupling agent) at 24°C for 3 hours, separating and drying the resulting mixture, which contains a mixture of -Si-R-Si(OCH ₃ ) ₃ modifications bonded to the silanol groups of the silica and (-O) ₃ Si-R-NH ₂ modifications bonded to the siloxane moiety.

Example 9
Used waste sewn product of the waterproof canvas (1) of Example 1 (two pieces of waterproof canvas, each 203 cm wide x 10 m long, sewn together to a size of 402 cm wide x 10 m long) was laid out in a vacant lot where weeds had been cut, secured to the ground with anchor pins, and left for three months from June to August. As a result, no weeds were observed to grow under the used waste product, demonstrating that the used waste sewn product of the waterproof canvas (1) of Example 1 is suitable for use as a weed control sheet.

[Example 10]
Used waste of the sewn material of the tent membrane tarpaulin (1) of Example 5 (two tent membrane tarpaulins of width 203 cm x length 10 m sewn together to a width of 402 cm x length 10 m) was spread out in a vacant lot where weeds had been cut, fixed to the ground with anchor pins, and left for three months from June to August. As a result, no weeds were observed to grow under the used waste, demonstrating that the used waste of the sewn material of the tent membrane tarpaulin (1) of Example 5 is suitable for use as a weed control sheet.

The waterproof canvases (1) to (4) of Examples 1 to 4 and the tarpaulins for tent membranes (1) to (4) of Examples 5 to 8 all have an engraving area A consisting of a display area and a background, and the appearance of the display area and the background in all cases form a contrast between a mirror surface and a matte finish. This contrast configuration has the effect of significantly improving the visibility of the display area even when the engraving depth is about 0.3 mm.
In these examples, rubber crosslinks were formed in the soft vinyl chloride resin coating layer, and the formation of the rubber crosslinks was achieved by converting liquid synthetic rubber into crosslinked rubber to form a rubber crosslinked network throughout the entire soft vinyl chloride resin coating layer. In the soft vinyl chloride resin coating layer before conversion, liquid synthetic rubber molecules were present in a state of being entangled with the vinyl chloride resin main chain, and the crosslinking of this liquid synthetic rubber formed a hybrid in which the rubber crosslinked network covered the entire soft vinyl chloride resin coating layer, improving the wear resistance and abrasion resistance of the soft vinyl chloride resin coating layer, i.e., the marking area A. Therefore, it was demonstrated that even if the marking depth of the marking area A is about 0.3 mm, there is no need to worry about the marking area being easily worn or worn away, resulting in the marking area becoming unclear.
In addition, in the synthetic canvas (4) of Example 4 and the tarpaulin for tent membrane (4) of Example 8, the liquid synthetic rubber bonds (through a crosslinking agent) with the silanol groups (Si-OH groups) on the surface of the silica particles, and the rubber crosslinking structure contains silica (treated with a silane coupling agent) as a relay point, which further strengthens the rubber crosslinking and further improves the wear resistance and abrasion resistance of the soft polyvinyl chloride resin coating layer (imprinted area A). In particular, in order for the liquid synthetic rubber to bond with the silanol groups on the surface of the silica particles and to include silica as a relay point in the rubber crosslinking structure, the involvement of a silane coupling agent was effective in assisting the formation of the rubber crosslinking.
The marking area A "PET &PVC" on the waterproof canvas and tent membrane tarpaulin of Examples 1 to 8 indicates that the material is polyester fiber fabric and polyvinyl chloride resin, and the clarity of the marking area A is maintained for a long period of time, making it easy to separate for recycling (weed control sheet) or disposal later. Also, the marking area B "HIRAOKA" on the welded part of the waterproof canvas sewn product and tent membrane sewn product sewn by welding these together indicates that the sewing manufacturer is Hiraoka Orisen Co., Ltd., and the clarity of the marking area B is maintained for a long period of time, making it possible to check the decision at the time of recycling or disposal.
In Example 9, it was demonstrated that the used sewn product of the waterproof canvas (1) of Example 1 can be reused for use as a weed control sheet, and in Example 10, it was demonstrated that the used sewn product of the tarpaulin for tent membrane (1) of Example 5 can be reused for use as a weed control sheet. Therefore, it is also possible to reuse the waste materials of the waterproof canvases (2) to (4) of Examples 2 to 4 and the tarpaulins for tent membrane (2) to (4) of Examples 6 to 8 as weed control sheets. If the waste materials of the sewn products of the tent membrane and the sewn products of the waterproof sheets can be reused as weed control sheets, new weed control sheets will become unnecessary, the consumption of petrochemical raw materials will be suppressed, and this will lead to a reduction in carbon dioxide emissions.

[Comparative Example 1]
A waterproof canvas (5) was obtained in the same manner as in Example 1, except that in the design of the inverted Gothic font characters (1 character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm) in the engraved area A "PET &PVC" used in Example 1, which had a concave mirror surface (height difference 0.5 mm) and a matte background, the background was a mirror convex surface.

[Comparative Example 2]
A waterproof canvas (6) was obtained in the same manner as in Example 1, except that in the design consisting of a concave mirror surface (height difference 0.5 mm) with the marking area A of "PET &PVC" in inverted Gothic font (one character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm) used in Example 1 and a matte convex background, the marking area was made matte concave (height difference 0.5 mm).

[Comparative Example 3]
A tarpaulin for tent membranes (5) was obtained in the same manner as in Example 5, except that in the design of the inverted Gothic font characters (1 character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm) in the engraved area A "PET &PVC" displayed on a concave mirror surface (height difference 0.5 mm) and with a matte background, the background was a mirror surface convex portion.

[Comparative Example 4]
In Example 5, the engraved area A of the design used was a concave mirror surface (height difference 0.5 mm) with inverted Gothic font characters (one character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm) in the display area A, with a matte background and a concave matte background (height difference 0.5 mm). A tarpaulin for tent membranes (6) was obtained in the same manner as in Example 5, except that the display area was a matte background (height difference 0.5 mm).

[Comparative Example 5]
A dark green waterproof canvas (7) having a mass of 530 g/m2 was obtained in the same manner as in Example 1, except that 10 parts by mass of ^butadiene -based liquid rubber (having -COOH groups at both molecular terminals and an average molecular weight of 3,000) was omitted from the processing solution of <Composition 1> of Example 1.
No rubber cross-linked network was formed in the soft polyvinyl chloride resin coating layer of the waterproof canvas (7). Therefore, the marking area A formed in the soft polyvinyl chloride resin coating layer had poor wear resistance and abrasion resistance. As a result of the Scott type reciprocating flexural abrasion test and the Taber type abrasion test, the marking "PET &PVC" in the marking area A had become indistinguishable due to wear.

[Comparative Example 6]
A dark green waterproof canvas (8) having a mass of 530 g/m2 was obtained in the same manner as in Example 1, except that 10 parts by mass of butadiene-based liquid rubber (having -COOH groups at both molecular terminals and an average molecular weight of 3000) in the processing liquid of <Composition 1> in Example 1 was replaced with 10 parts by mass of butadiene-based liquid rubber having an average molecular weight of 3000 and no functional groups at ^both molecular terminals.
No rubber cross-linked network was formed in the soft polyvinyl chloride resin coating layer of the waterproof canvas (8). Therefore, the marking area A formed in the soft polyvinyl chloride resin coating layer had poor wear resistance and abrasion resistance. As a result of the Scott type reciprocating flexural abrasion test and the Taber type abrasion test, the marking "PET &PVC" in the marking area A had become indistinguishable due to wear.

[Comparative Example 7]
A dark green waterproof canvas (9) having a mass of 530 g/m2 was obtained in the same manner as in Example 1, except that 10 parts by mass of butadiene-based liquid rubber (having -COOH groups at both molecular terminals and an average molecular weight of 3000) in the processing liquid of <Composition 1 ^> in Example 1 was replaced with 10 parts by mass of butadiene rubber powder (registered trademark "Kane Ace" M-711: Kaneka Corporation).
No rubber cross-linked network was formed in the soft polyvinyl chloride resin coating layer of the waterproof canvas (9). Therefore, the marking area A formed in the soft polyvinyl chloride resin coating layer had poor wear resistance and abrasion resistance. As a result of the Scott type reciprocating flexural abrasion test and the Taber type abrasion test, the marking "PET &PVC" in the marking area A had become difficult to read due to wear.

As is clear from the above examples and comparative examples, according to the present invention, in the application of industrial material sheets such as tent membrane sewn products (pavilions, tent houses, sunshade tents, etc.) and waterproof sheet sewn products (truck hoods, loading platform covers, open-air storage sheets, floor sheets, etc.), even if the marking depth is shallow, such as 0.5 mm or less, the marking area A clearly and robustly displays the marking information, making it easy to determine whether to recycle or discard the product over a long period of time. Furthermore, by reusing the waste materials of tent membrane sewn products (tent membrane structures with the metal frame removed) and waterproof sheet sewn products as weed control sheets based on this marking information, the consumption of petrochemical raw materials is reduced by the amount of new weed control sheets that are not needed, which also leads to a reduction in carbon dioxide emissions.

1-1: Mirror convex part (display part)
1-2: Satin-finished surface (background)
2-1: Mirror recess (display area)
2-2: Satin-finished convex part (background)
3-1: Satin-finished convex part (display part)
3-2: Mirror concave surface (background)
4-1: Satin-finish depression (display area)
4-2: Mirror surface convex part (background)

Claims (5)

1. An industrial material sheet comprising a long sheet having soft polyvinyl chloride resin coating layers on the front and back sides of a fabric, the soft polyvinyl chloride resin coating layers containing crosslinked rubber, rubber crosslinks formed throughout the layer, the rubber crosslinks containing one or more rubber structures selected from the group consisting of butadiene rubber, isoprene rubber, and farnesene rubber, the industrial material sheet comprising an imprinting area A on one of the soft polyvinyl chloride resin coating layers on the front and back sides, the imprinting area A being periodically formed on one end of a longitudinal side of the long sheet, comprising an indicia and a background, and one or more patterns selected from "mirror-surface convex portion (indicia)/pearskin concave portion (background)", "mirror-surface concave portion (indicia)/pearskin convex portion (background)", "pearskin convex portion (indicia)/mirror concave portion (background)", and "pearskin concave portion (indicia)/mirror convex portion (background)", the indicia being a collection of one or more types of indicia and/or convex portions selected from the group consisting of letters, numbers, symbols, and figures (marks) . A tent membrane sewn product in which the ends of the industrial material sheets described in claim 1 are lap- connected by a high-frequency welding machine (high-frequency welder) equipped with a die bar , and an engraving area B is provided at the lap connection part of the tent membrane sewn product, and this engraving area B is stamped by pressing the die bar during high-frequency welding . A waterproof sheet sewn product in which the ends of the industrial material sheets described in claim 1 are lap- connected by a high-frequency welding machine (high-frequency welder) equipped with a mold bar , and an engraving area B is provided at the lap connection part of the waterproof sheet sewn product, and this engraving area B is stamped by pressing the mold bar during high-frequency welding . A method for utilizing the waste tent membrane sewn material according to claim 2 , which comprises converting the waste tent membrane sewn material into a weed control sheet. A method for utilizing waste waterproof sheet sewn products according to claim 3 , which comprises converting the waste waterproof sheet sewn products into weed control sheets.