JP2024035970A - Industrial material sheets, tent membrane sewn products made by connecting them, waterproof sheet sewn products, and methods for using their waste materials - Google Patents

Abstract

[Problem] To provide a sewn tent membrane product and a sewn waterproof sheet product that can be clearly and robustly displayed even if the depth of the stamp is shallow, and can be used to determine whether to recycle or dispose of the product over time. Providing a method for using waste materials based on markings on sewn products. [Solution] A long sheet is formed by providing a soft vinyl chloride resin coating layer on the front and back sides of a fabric, and a marking area is periodically placed on one end in the longitudinal direction. A is formed, and "mirror surface convex part (display part)/matte concave part (background)", "mirror concave part (display part)/matte finish convex part (background)", "matte finish convex part (display part)/mirror concave part (background)" )" and "matte concave part (display part)/mirror-finish convex part (background)" is an industrial material sheet having an imprint area A selected from Based on the information, this waste material will be reused for weed control sheets. [Selection diagram] Figure 1

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, awning tents, etc.) made by connecting these industrial material sheets. Information such as the source, part number, and material of waterproof sheet-sewn items (truck hoods, cargo bed covers, open storage sheets, floor sheets, etc.) is clearly and robustly engraved and displayed, making it easy to decide whether to recycle or dispose of them. The present invention relates to a sewn tent membrane (a tent membrane structure with a metal frame removed), a sewn waterproof sheet, and the use of waste materials based on markings on the waste materials of these sewn products.

Tent membrane structures such as large tents (pavilions), circus tents, seat houses, membrane roofs (ceilings) of architectural spaces, and stadium sunshade roofs use thermoplastic materials such as soft polyvinyl chloride resin in addition to fabrics made of long polyester fibers. Tarpaulins made of laminated resin films are used, and most of the colors are light colors such as white and ivory, which are aesthetically pleasing and harmonious with other buildings. On the other hand, for truck hoods, cargo bed covers, seat warehouses, open storage seats, etc., spun fabrics made of spun polyester short fibers are impregnated with a thermoplastic resin solution such as soft vinyl chloride resin, and then heated and dried to solidify. The most common colors are dark green, olive drab, and navy blue, which make stains less noticeable. These industrial material sheets such as tarpaulin and synthetic canvas are distributed in rolls with a thickness of 0.3 to 1.5 mm, a width of 0.9 to 2.4 m, and a length of 25 to 50 m, and in these markets, the above-mentioned For this reason, there are multiple competing products with the same color hue and the same specifications.

With these industrial material sheets, information such as the manufacturer, brand, product number, and material is not displayed on the sheet itself, so if the wrapping paper is removed at wholesalers or sewing shops, it may become impossible to identify the manufacturer or product number. there were. In particular, recently, manufacturers have begun to manufacture products that comply with REACH regulations (Regulations on the registration, evaluation, authorization, and restriction of chemical products in the European Union) and RoHS2 directive (Restrictions on the use of specific hazardous substances in electrical and electronic equipment in the European Union). Since we offer a variety of legally compliant products, including products certified by the Minister of Land, Infrastructure, Transport and Tourism, and products with guaranteed durability (8, 10, 15 years), strict product management is required at wholesalers and sewing shops. becomes. However, even if the sheets are used without mixing them up, once they are released into the world as final products, it will take more than 10 years to disassemble and dispose of them, regardless of the manufacturer, product number, material, etc. The current situation is that they are sent to landfills. The reason these materials are not recycled is because materials that have deteriorated over time have no use value. However, in light of recent environmental and resource issues, the disposal of tent membrane structures, tarpaulins, etc. requires a system that can correctly recognize basic information such as manufacturer, product number, and material, but there is still no system in the industry. Not built. Furthermore, the secondary use of these wastes has never been considered.

The applicant has previously used pearl dimmable glitter, which has been used for mobile goods fabrics, furniture fabrics, flooring fabrics, fabrics for decorative parts, etc., and can clearly display unexpected designs with a rich three-dimensional effect through embossing. As a synthetic leather, we proposed a synthetic leather that has a design part consisting of a depressed part and a non-concaved part, and has a specific difference in depression height, and one example of this is a gold plate with the letters "HIRAOKA" engraved in a convex shape. Patent Document 1 discloses a synthetic leather in which characters are designed into a concave shape by pressing with a mold, and the difference in depression height between a depressed part and a non-concave part is 0.2 mm. This synthetic leather is decorated with gold and violet colors that alternately interfere with each other depending on the viewing angle, except for the text part, but such interfering uneven text is inferior in distinguishability when used outdoors, so it is not suitable for use on industrial material sheets. It was inappropriate as an information stamp. In addition, as a heat transfer label commonly used for textile products such as blousons, training wear, T-shirts, bags, sports shoes, etc., on the label surface, the information display part mainly consists of convex parts with an uneven pattern, and the base pattern part Patent Document 2 discloses an invention in which a heat transfer label with a unique surface texture is formed by screen printing, in which the convex portions of the concavo-convex pattern constituting the label have a glossy surface and the concave portions have a matte surface. However, even if a transfer label formed by such screen printing is applied to display information on an industrial material sheet, the fine uneven patterns in screen printing will wear out and have a short lifespan. Therefore, there is currently a strong need for industrial material sheets that can stably display information such as manufacturer, product number, and material over a long period of time, and for effective secondary use of waste materials from industrial material sheet constructions. .

Japanese Patent Application Publication No. 2014-163013 Japanese Patent Application Publication No. 2003-094891

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, awning tents, etc.) made by connecting these industrial material sheets. In applications such as waterproof sheets and sewn products (truck hoods, cargo bed covers, open-air seats, floor seats, etc.), the markings such as origin, product number, material, etc. are clear and robust even when the stamp depth is about 0.3 mm. Providing sewn tent membrane products (with the metal frame removed from the tent membrane structure) and sewn waterproof sheets that can be displayed on the screen and sorted for recycling/disposal over time, as well as markings on these sewn products. The goal is to provide a method for using waste materials based on the following.

As a result of extensive research in consideration of these points, the present invention provides a long sheet comprising soft vinyl chloride resin coating layers on the front and back sides of a fabric, wherein either one of the soft vinyl chloride resin coating layers on the front and back sides The marking area A is periodically formed on one end of the long sheet in the longitudinal direction, and consists of a display area and a background, and includes a "mirror-finished convex part (display part)/matte-finish recessed part". (Background),” “Mirror-finished concave portion (display portion)/Near-skinned convex portion (background),” “Near-skinned concave portion (Display portion)/Mirror concave portion (Background),” and “Near-skinned concave portion (Display portion)/Mirror-finished convex portion ( By using one or more patterns selected from ``background)'', the appearance of the display part and background becomes a contrast effect of mirror and satin finish, and even if the engraving depth is about 0.3 mm, the visibility of the display part is improved. It is possible to obtain an industrial material sheet (tarpaulin, synthetic canvas) for tent membrane structures and waterproof sheets, which has a markedly improved engraved area A and a clear marking area A. In particular, in the use of tent membrane sewn products (pavilions, tent houses, sunshade tents, etc.) and waterproof sheet sewn products (truck hoods, cargo bed covers, open storage sheets, floor sheets, etc.) made by connecting these industrial material sheets, By clearly and robustly stamping information such as the source, part number, and material on a specific part of the industrial material sheet as stamp area A, it becomes possible to determine whether to recycle or dispose of the sheet. The present invention was completed based on the discovery that the waste materials of sewn tent membranes (the metal frame is removed from the tent membrane structure) and sewn waterproof sheets can be used as weed control sheets. In other words, if the marking area A is unknown, it will be difficult to determine who is responsible for constructing the weed control sheet and for its disposal. Information on the marking area A is required. For example, engraved area A "PET & PVC" indicates that the material is polyester fiber fabric and vinyl chloride resin, and by maintaining the clarity of this engraved area A for a long time, it is possible to later recycle (weed control sheet) / Facilitate waste separation.

The industrial material sheet of the present invention includes crosslinked rubber in the soft vinyl chloride resin coating layer, rubber crosslinks are formed throughout this layer, and the rubber crosslinks include butadiene rubber, isoprene rubber, farnesene rubber, It is preferable that the rubber structure contains one or more types of rubber structures selected from the following. In this soft vinyl chloride resin coating layer, a crosslinked network of rubber crosslinks forms a hybrid intertwined with the vinyl chloride resin main chain, resulting in excellent abrasion resistance and abrasion resistance of the engraved display in the engraved area A, which can be used outdoors for a long time. Even after the lapse of time, the stamped display remains stable, making it possible to determine whether to recycle or dispose of the product.

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

The sewn tent membrane product of the present invention is a sewn tent membrane product formed by connecting the end portions of the above-mentioned industrial material sheets by lap, and a stamped area B may be provided at the lap connection portion of the sewn tent membrane product. preferable. This stamped area B is stamped by the pressure of a heating die when the tent membrane is sewn, and the maker information of the sewn tent membrane becomes clear from the stamped area B. For example, engraved area B "HIRAOKA" indicates that the sewing manufacturer is Hiraoka Textile Co., Ltd., and by maintaining the clarity of this engraved area B for a long period of time, it is possible to make inquiries to the manufacturer.

The waterproof sheet sewn product of the present invention is a waterproof sheet sewn product formed by lap-connecting the ends of the above industrial material sheets, and it is preferable that a stamped area B is provided at the lap joint part of the waterproof sheet sewn product. . This stamped area B is stamped by the pressure of a heating die when the waterproof sheet is sewn, and the stamped area B reveals the sewing maker information of the waterproof sheet sewn product.

In the method of utilizing the waste material of sewn tent membranes of the present invention, it is preferable to divert the waste material of sewn tent membranes to a weed control sheet. As a result, the waste material of the sewn tent membrane can be appropriately reused as a weed control sheet according to the profile (information display) of the tent membrane before being disposed of in a landfill, thereby eliminating the need for a new weed control sheet. Since there is no need for new weed control sheets, the consumption of new petrochemical raw materials is suppressed, which further leads to a reduction in carbon dioxide emissions in the future.

In the method of utilizing the waste material of sewn waterproof sheets of the present invention, it is preferable to divert the waste materials of sewn waterproof sheets to weed control sheets. As a result, waste material from sewn tarpaulin sheets is appropriately reused as a weed control sheet according to the profile (information display) of the tarpaulin sheet before being disposed of in a landfill, thereby eliminating the need for a new weed control sheet. Since there is no need for new weed control sheets, the consumption of new petrochemical raw materials is suppressed, which further leads to a reduction in carbon dioxide emissions in the future.

According to the present invention, in the use of industrial material sheets such as tent membrane sewn products (pavilions, tent houses, sunshade tents, etc.) and waterproof sheet sewn products (truck hoods, cargo bed covers, open storage sheets, floor sheets, etc.), in particular, the source, Even if the stamping depth is about 0.3 mm, the markings such as the product number and material will be displayed clearly and robustly in the stamping area A, making it easier to determine whether to recycle or discard the product over a long period of time. Based on this engraved display, new weed control sheets can be made by reusing the waste materials of sewn tent membranes (the metal frame has been removed from the tent membrane structure) and sewn waterproof sheets as weed control sheets. Since it is no longer needed, the consumption of petrochemical raw materials is reduced, which further leads to a reduction in carbon dioxide emissions.

A sectional view showing one aspect of the stamping area A of the industrial material sheet of the present invention A sectional view showing one aspect of the stamping area A of the industrial material sheet of the present invention A sectional view showing one aspect of the stamping area A of the industrial material sheet of the present invention A sectional view showing one aspect of the stamping area A of the industrial material sheet of the present invention

The industrial material sheet of the present invention is a long sheet formed by providing a soft vinyl chloride resin coating layer on the front and back sides of a fabric, and has an engraved area A on either one of the soft vinyl chloride resin coating layers on the front and back sides. The marking area A is periodically formed on one end of the long sheet in the longitudinal direction and consists of a display part and a background, "mirror-finished convex part (display part)/matte-finish concave part (background)", From "Mirror concave part (display part) / Satin convex part (background)", "Painted concave part (display part) / Mirror concave part (background)", and "Near matte concave part (display part) / Mirror convex part (background)". One or more selected patterns, the soft vinyl chloride resin coating layer contains cross-linked rubber, rubber cross-links are formed throughout this layer, and the rubber cross-links are composed of butadiene-based rubber, isoprene-based rubber, farnesene-based rubber, This embodiment includes one or more types of rubber structure selected from the following. For example, engraved area A "PET & PVC" indicates that the material is polyester fiber fabric and vinyl chloride resin, and by maintaining the clarity of this engraved area A for a long time, it is possible to later recycle (weed control sheet) / Make it easy to separate waste. In the present invention, a mirror surface means a glossy appearance with light reflection, and a satin finish means a matte appearance with minute irregularities that diffusely reflect light.

The fabric used for 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 fabrics include plain woven fabrics (biaxial woven fabrics consisting of warp/weft, triaxial woven fabrics consisting of warp/bias yarns, four-axis woven fabrics consisting of warp/weft/bias yarns), and basket woven fabrics (e.g. 2×2, 3×2 woven fabrics). Regular thread weave such as ×3, 4 x 4, irregular thread weave such as 3 x 2, 4 x 2, 4 x 3, 5 x 3, 2 x 3, 2 x 4, 3 x 4, 3 x 5 woven fabric), twill woven fabric (having a minimum constituent unit of at least three warps and wefts: 3-ply diagonal, 4-ply diagonal, 5-ply diagonal, 6-ply diagonal, 8-ply diagonal, etc.), satin Fabrics (having a minimum constituent unit of at least five warps and wefts: regular satin fabrics with 2 skips, 3 skips, 4 skips, 5 skips, etc.), modified plain woven fabrics, modified twill woven fabrics, modified satin woven fabrics, etc. Honeycomb fabric, satin fabric, day and night satin fabric, twisted fabric (gauze fabric, gauze fabric), sewn fabric, double woven fabric, etc. can also be used, but plain fabric and 2×2 diagonal fabric are especially suitable. It is preferred due to its excellent balance of mechanical and mechanical properties. As the knitted fabric, a raschel knitted fabric can be used, and as the non-woven fabric, a fleece produced by a wet process, a dry process, a spunbond process, or a melt blow process and fixed with heat, adhesive, etc. can be used. The above-mentioned woven fabrics, knitted fabrics, and non-woven fabrics are subjected to known fiber treatments such as scouring, bleaching, dyeing, softening, water repellency, water absorption prevention, flame retardant, burning, calendering, binder fixation, and adhesive coating. In order to improve the performance of the industrial material sheet, one or more may be used.

The threads constituting the fabric can be synthetic fibers, natural fibers (cotton, kenaf), semi-synthetic fibers (rayon, acetate), inorganic fibers, or a mixture of two or more of these fibers, but polypropylene fibers , polyethylene fiber, polyvinyl alcohol fiber, polyester (PET, recycled PET, biomass PET, PBT, PNT synthesized from plant-derived raw materials) fiber, fully aromatic polyester fiber, biomass fiber synthesized from plant-derived raw material (polyethylene Furanoate fiber, polypropylene furanoate fiber, polybutylene furanoate fiber, polytrimethylene furanoate fiber, furan-based polyamide fiber, etc.), nylon fiber, fully aromatic polyamide fiber, aromatic heterocyclic polymer (polybenzimidazole, polybenzo Synthetic fibers such as oxazole, polybenzothiazole, etc.) fibers, acrylic fibers, polyurethane fibers, or mixed fibers thereof are preferred. The forms of these yarns include monofilament, multifilament, short fiber spun (spun), split, tape, etc., but in order to ensure the flexibility and tear strength of the industrial material sheet, multifilament or short fiber Spinning is preferred. 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 especially suitable for noncombustible materials (tent structures) certified by the Minister of Land, Infrastructure, Transport and Tourism. Glass fiber multifilament yarns are particularly suitable.

The fabric used in the present invention is preferably a fabric made of multifilament yarns or a short fiber spun fabric (spun), and the multifilament yarns are in the range of 250 to 3000 deniers (277 to 3333 dtex), particularly 500 deniers (277 to 3333 dtex). ~2000 denier (555~2222 dtex) is preferable, and untwisted yarn (having an elliptical or flat cross section) or twisted yarn can be used as required. In addition, short fiber spun yarns range from 10th (591 dtex) to 60th (97 dtex), especially 10th (591 dtex), 14th (422 dtex), 16th (370 dtex), 20th (295 dtex), and 24th ( 246 dtex), 30 count (197 dtex), single yarns of these, double yarns (single-twisted yarns), yarns twisted together with two or more single yarns (ply-twisted yarns), etc. are preferable. There is no limit to the implant density of the warp and weft of the fabric, and any design is possible depending on the thickness (denier, count) of the threads used, but the porosity (throughput) of the fabric is 0 to 30%. Fabrics with a density in the range of 100 to 500 g/m ² are suitable for industrial material sheets. The porosity can be determined by subtracting the area of the threads in the unit area of the fabric as a percentage from 100. Suitable for production in which a soft vinyl chloride resin composition film is thermally laminated on preferably both sides of a fabric woven with multifilament yarns (porosity 10 to 35%) to form a soft vinyl chloride resin coating layer, In the case of short fiber spun cloth (spun), preferably both sides of the short fiber spun cloth (spun) with a porosity of 0 to 10% are coated with a paste-like soft vinyl chloride resin composition, heat treated, or Suitable for forming a soft vinyl chloride resin coating layer 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 formed by coating or dipping with paste vinyl chloride resin (emulsion polymerization type) and gelation heat treatment. Alternatively, it is particularly preferable to form a coating using a vinyl chloride resin film (sheet) formed by calendar rolling or T-die extrusion using straight vinyl chloride resin (suspension polymerization type). Paste vinyl chloride resin is suitable for the coating layer of canvas, and straight vinyl chloride resin is suitable for the coating layer of tarpaulins. The vinyl chloride resin may be a biomass-compatible industrial material sheet using a vinyl chloride resin made of a plant-derived monomer. Plasticizers include adipic acid diester compounds, sebacic acid diester compounds, phthalic acid diester compounds, isophthalic acid diester compounds, terephthalic acid diester compounds, cyclohexanedicarboxylic acid diester compounds, cyclohexenedicarboxylic acid diester compounds, chlorinated paraffin compounds, and polyester compounds. , one or more of ethylene-vinyl acetate-carbon monoxide terpolymer resin, ethylene-(meth)acrylic ester-carbon monoxide terpolymer resin, etc., 100 parts by mass of vinyl chloride resin. Approximately 35 to 150 parts by mass can be used. The plasticizer may be a biomass-compatible industrial material sheet using a plasticizer made of a plant-derived compound. Examples of plant-derived plasticizers include polyglycerin fatty acid ester compounds and furandicarboxylic acid dialkyl ester compounds.

In the soft vinyl chloride resin coating layer, stabilizers such as calcium zinc composite system, barium zinc composite system, organic tin laurate, organic tin mercaptite, and epoxy system are used alone or in combination as stabilizers for vinyl chloride resin. The use of this material suppresses thermal deterioration and discoloration during production of the industrial material sheet of the present invention, and further improves weather resistance when used outdoors. In addition, the industrial material sheet of the present invention can be colored with pigments such as titanium oxide (white), carbon black (black), inorganic compound composites, azo compounds (red), phthalocyanine compounds (blue to green), and anthraquinone compounds. (yellow to red), quinacridone compounds (yellow to purple), etc. can be used to adjust the color arbitrarily, but white (titanium oxide) and pastel colors (colors added to titanium oxide) are in particular demand for tent membrane structures. Colors such as tall, dark green and olive drab are in high demand for truck hoods and tarpaulins. In addition, various arbitrary amounts of known additives for vinyl chloride resins can be blended into the soft vinyl chloride resin coating layer, and flame retardants (antimony trioxide, aluminum hydroxide, hydroxide magnesium, zinc borate, ammonium polyphosphate, melamine cyanurate, etc.), light 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 coupling agents, etc.), insect repellents (pyrethroid-based, etc.), fungicides (imidazole-based compounds, thiazole-based compounds, isothiazoline-based compounds, pyridine) type compounds, N-haloalkylthio compounds, phenoxyarsine compounds, etc.), antibacterial agents (silver zeolite type), deodorants (silicon oxide/metal oxide composite type, etc.), thermal barrier fillers (hollow particles, coarse titanium oxide, etc.) ), fragrances, phosphorescent pigments (such as strontium aluminate), aluminum flake pigments, pearl pigments, and inorganic fillers (such as calcium carbonate and barium sulfate).

In particular, the soft vinyl chloride resin coating layer contains crosslinked rubber, and rubber crosslinks are formed throughout this layer, and the rubber crosslinks are composed of one or more types selected from butadiene rubber, isoprene rubber, and farnesene rubber. By forming a hybrid that contains a rubber structure and a rubber crosslinked network intertwined with the vinyl chloride resin main chain, the wear resistance and abrasion resistance of the stamped display in stamped area A and stamped area B are improved, and it can be used outdoors for a long time. Even after the process is complete, the markings remain stable, making it easier to sort and recycle/discard. Such a rubber crosslinked network is made by adding 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 to 100 parts by weight of vinyl chloride resin. It can be formed by blending the vinyl chloride resin and crosslinking the liquid synthetic rubber at the same time as heating and gelling the vinyl chloride resin. In this state before crosslinking, the liquid synthetic rubber together with the plasticizer penetrates into the vinyl chloride resin fine particles and acts as a softener for the vinyl chloride resin. By heating and gelling the soft vinyl chloride resin composition in this state, a hybrid soft vinyl chloride resin coating layer in which the rubber crosslinked network is entangled with the vinyl chloride resin main chain is formed. That is, a hybrid in which the rubber crosslinked network is entangled with the vinyl chloride resin main chain is formed throughout the soft vinyl chloride resin coating layer.

The butadiene liquid rubber that forms rubber crosslinks enables three-dimensional crosslinking by having either a -COOH group or an -OH group at the molecular end. The molecular weight Mn is preferably in the range of 1,000 to 5,000, particularly 1,300 to 3,500, and the viscosity is in the range of 50 to 1,000 poise (25°C), particularly 200 to 500 poise (25°C). The butadiene-based liquid rubber contains 5 to 25% by mass of styrene and/or acrylonitrile as a block copolymerization component, and 10 to 50% by mass of isoprene or hydrogenated isoprene as a copolymerization component. Butadiene liquid rubber has a low viscosity when it has a 1,4-cis structure or a 1,4-trans structure of about 75 to 80% and a 1,2-vinyl structure of about 20 to 25%, and is difficult to rubberize. Excellent rubber elasticity. This production ratio is made possible by the radical polymerization method. The isoprene-based liquid rubber that forms the rubber crosslinks is preferably one having a molecular weight Mn of 3,000 to 25,000 and having either a --COOH group or --OH group at (both) ends of the molecule. Isoprene-based liquid rubber contains 5 to 25% by mass of styrene and/or acrylonitrile as a block copolymerization component, and 10 to 50% by mass of butadiene or hydrogenated isoprene as a copolymerization component. Farnesene rubbers that form rubber crosslinks include α-farnesene ((3E,7E)-3,7,11-trimethyl-1,3,6,10-dodecatetraene), β-farnesene (7,11-dimethyl Examples include rubbers containing monomers such as (-3-methylene-1,6,10-dodecatriene), copolymer rubbers of vanersene and styrene, and copolymer rubbers of vanersene and butadiene. The vanersene-based liquid rubber preferably has a molecular weight Mn of 3,000 to 50,000 and has either a --COOH group or --OH group at (both) ends of the molecule. The three-dimensional crosslinks of these liquid synthetic rubbers are formed by dehydration condensation of -COOH and -OH groups at the (both) ends of the molecule, and include diamines, polyamines, diisocyanates, polyisocyanates, epoxy-amines, aziridines, and oxazolines. It can be formed by an addition reaction with a crosslinking agent such as, or a condensation reaction with a compound such as a diol, polyol, dicarboxylic acid, or polycarboxylic acid. Further, as part of the rubber crosslinking, an organic-inorganic hybrid rubber crosslinking containing silica can be used.

The rubber crosslinking is preferably an organic-inorganic hybrid rubber crosslinking in which silica particles are present as a part of the rubber crosslinking. Silica is used in an amount of 1 to 25% by weight based on the liquid synthetic rubber, and chemical bonds are created between the functional groups on the silica surface and the -COOH and -OH groups at (both) molecular ends of the liquid synthetic rubber. It becomes part of the three-dimensional crosslinking by generating. This reaction is formed by dehydration condensation between the -COOH and -OH groups at (both) ends of the liquid synthetic rubber molecule and the silanol groups on the silica surface. by addition reaction with a crosslinking agent such as diamine, polyamine, diisocyanate, polyisocyanate, epoxy-amine, aziridine, oxazoline, or condensation reaction with a compound such as diol, polyol, dicarboxylic acid, polycarboxylic acid, etc. is preferred. The generation of this rubber crosslinking is performed simultaneously with the gelling heat treatment of the soft vinyl chloride resin paste forming the soft vinyl chloride resin coating layer, thereby forming a homogeneous rubber crosslinking network over the entire soft vinyl chloride resin coating layer. The soft vinyl chloride resin paste composition preferably contains a silane coupling agent to assist in chemical bonding between the liquid synthetic rubber and silica. This strengthens the rubber crosslinks and makes the stamped area A and stamped area B, which are stamped on specific parts of the industrial material sheet, tougher, making it clearer whether to recycle or discard after a long period of time. It can be done.

The silica is preferably synthetic amorphous silica with a BET specific surface area of 100 to 300 m ² /g or a secondary particle size of 1 to 40 μm. The synthetic amorphous silica may be either wet silica (precipitation method or gel method) or dry silica (fumed silica). The surface of silica has silanol (Si-OH group), and the silanol group reacts with the -COOH group and -OH group at both ends of the liquid synthetic rubber molecule, and the silica particles become part of the rubber component. As a result, the rubber crosslinks become tougher, improving abrasion resistance, and the marking areas A and B, which are stamped and displayed on specific parts of the industrial material sheet, are made more robust. Functional groups such as amino groups, vinyl groups, epoxy groups, methacrylic groups, acrylic groups, chloro groups, mercapto groups, isocyanurate groups, and isocyanate groups may be introduced onto the silica surface. The silica particles are preferably surface-modified particles treated with a silane coupling agent. A silane coupling agent is an alkoxysilane compound having _two or more different reactive groups in the molecule represented by the general formula: vinyl silane), epoxy group (epoxy silane), methacrylic group (methacrylic silane), acrylic group (acrylic silane), chloro group (chloro silane), mercapto group (mercapto silane), isocyanurate group (isocyanurate silane), isocyanate group (isocyanate) silane), etc. (R=alkyl chain), Y=methoxy group, ethoxy group, etc. The surface modification of silica is -Si-R-Si(Y) ₃ modification of the silanol group of silica, but may also be (-O) ₃ Si-RX modification of the siloxane bonding portion of silica.

The method for producing an industrial material sheet of the present invention includes 1) a step of preparing a soft vinyl chloride resin composition containing at least three types of vinyl chloride resin, a plasticizer, and a liquid synthetic rubber; 2) applying the soft vinyl chloride resin composition to a fabric. 3) Converting liquid synthetic rubber into crosslinked rubber to apply rubber to the entire area of the soft vinyl chloride resin coating layer. 4) a step of applying surface decoration embossing to form an engraved region A. The application of the soft vinyl chloride resin composition (paste sol) to the fabric in 2) can be carried out by dipping (immersion - impregnation - roll compression - heat treatment gelling of paste sol), gravure coating method, comma coating method, roll coating method. The film is formed in a thickness range of 0.05 to 0.3 mm by coating (impregnation coating to heat treatment gelling of paste sol) such as method, reverse roll coating method, bar coating method, doctor knife coating method, etc. The thickness is manufactured within the range of approximately 0.35 to 1.0 mm. In addition, the soft vinyl chloride resin film is formed to a thickness of 0.1 to 0.3 mm by calender rolling molding or T die extrusion molding of a soft vinyl chloride resin composition (compound), and the thickness of the industrial material sheet is Manufactured to a range of approximately 0.35 to 1.0 mm. 3) Conversion of liquid synthetic rubber into a rubber crosslinked network can be performed using diamines, triamines, tetramines, polyamines, diisocyanates (e.g. hexamethylene diisocyanate: HMDI), triisocyanates (e.g. isocyanurate by a cyclic trimer of HMDI), polyisocyanates, A dense and complex rubber crosslinked network can be obtained by using a crosslinking agent such as epoxy-amine, aziridine, or oxazoline, especially a crosslinking agent having 3 or 4 functional groups. By converting the liquid synthetic rubber into a rubber crosslinked network at the same time as gelling the soft vinyl chloride resin composition, a homogeneous rubber crosslinked network is formed over the entire soft vinyl chloride resin coating layer. The reaction between the liquid synthetic rubber and the crosslinking agent is preferably carried out in an equimolar ratio, 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 as a cold resistance imparting agent, which has the effect of lowering the glass transition temperature of the soft vinyl chloride resin coating layer. The remaining liquid synthetic rubber is within 10 parts by mass based on 100 parts by mass of the vinyl chloride resin. 4) The formation of the marking area A by the surface decoration embossing is performed periodically in the longitudinal direction of the industrial material sheet, and the formation position is at one end, and the marking area A is formed at one end of the industrial material sheet. ), pattern embossing (design), letter engraving (concave and convex stamping of manufacturer's name, product name, etc.), etc. In particular, the engraved display of manufacturer's name, product name, etc. can be used to differentiate products from similar products from other companies.

Furthermore, by providing an antifouling layer (0.005 to 50 μm) on the industrial material sheet of the present invention, the soft vinyl chloride resin coating layer is protected, and damage caused by sooty dust adhesion, ultraviolet deterioration, and abrasion is alleviated. The antifouling layer allows the appearance of industrial material sheets, that is, sewn tent membranes and sewn tarpaulins, to remain beautiful even after long-term use. Materials can be reused as weed control sheets. The antifouling layer is made of acrylic resin, fluorine copolymer resin, acrylic-silicone copolymer resin, acrylic-fluorine copolymer resin, acrylic-urethane copolymer resin, blend of acrylic resin and fluorine copolymer resin, and A transparent layer containing fine silica particles, colloidal silica, organosilicate, silane coupling agent, ultraviolet absorber (benzophenone tautomer, benzotriazole tautomer, triazine tautomer, etc.) in these resins. It is. These antifouling layers can be formed by gravure coating and drying to form a film, or by applying a fluorine-containing resin film or a multilayer film such as a fluorine-containing resin/acrylic resin layer with an adhesive. Alternatively, there is a method of laminating layers by thermal melting. Furthermore, a photocatalytic layer containing a photocatalytic inorganic material (for example, 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 engraved region A, which is formed periodically in the longitudinal direction of the long sheet, and whose formation position is at one end, and where the engraved region A is Consisting of a display area and a background, "mirror surface convex part (display part)/matte concave part (background)", "mirror concave part (display part)/matte convex part (background)", "matte finish convex part (display part)/mirror surface" By using one or more patterns selected from ``concave portion (background)'' and ``matte concave portion (display area)/mirrored convex portion (background),'' the visual contrast effect is improved by using a combination of a mirror surface portion and a matte surface portion. Even if the marking depth is about 0.3 mm, the marking area A becomes clear. In the present invention, a mirror surface means a glossy appearance with light reflection, and a satin finish means a matte appearance with minute irregularities that diffusely reflect light. In addition, the display part is a collection of one or more types of recesses and/or protrusions selected from letters, numbers, symbols, and figures (marks), and specifically includes the manufacturer's name, product name, product number, and registration number. , material display, 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 stamp area A is not particularly limited to a rectangle, square, polygon, oval, circle, etc., but rectangles and oval shapes are preferable. The size of the engraving area A is a square, polygon, circle, etc. with a minimum height of 3 cm x width 3 cm, and a maximum of 15 cm height x 15 cm width, and a minimum of 3 cm height x 5 cm width, and a maximum of 10 cm height x width. It can be a 25cm rectangle, an oval, etc. If the size of the stamp area A is too small, it will be difficult to read the displayed content, and if it is too large, the appearance of the tent membrane sewn product and the waterproof sheet sewn product will be affected. The stamped areas A are periodically formed in the longitudinal direction during manufacturing of the industrial material sheet, and are formed at the right or left end of the industrial material sheet in the width direction. The tent membrane sewn product and the waterproof sheet sewn product of the present invention are welded by lap connection in which the ends of industrial material sheets are overlapped by 3 to 10 cm, so the right end or It is preferable to form the engraved area A on the left end, and especially to form the engraved area A on the back surface. The marking area A is continuously shaped at regular intervals by an embossing roll, and letters, numbers, symbols, and figures (marks) are designed in reverse on the embossing roll. For example, in the case of marking one place on an embossing roll having a diameter of 30 inches, marking areas A are continuously formed at intervals of about 240 cm. The engraved area A clarifies the manufacturer information of the industrial material sheet. Embossing is performed by pressure bonding using an embossing roll set at 100 to 180°C and a pair of rubber rolls, and the engraved display is fixed by cooling (air-cooled and water-cooled rolls) after embossing. It is preferable that the stamped area A is on the inside of the tent membrane sewn product or the waterproof sheet sewn product to protect it from damage such as soot, wind and rain, and ultraviolet rays. For example, engraved area A "PET & PVC" indicates that the material is polyester fiber fabric and vinyl chloride resin, and by maintaining the clarity of this engraved area A for a long time, it is possible to later recycle (weed control sheet) / Make it easy to separate waste.

Further, the tent membrane sewn product and the waterproof sheet sewn product of the present invention are welded together by lap connection in which the ends of industrial material sheets are overlapped by 3 to 10 cm. This welding is performed by pressing a heated mold. Specifically, 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 is used to press the welding for 3 to 5 seconds. Molecular vibration of the vinyl chloride resin in the soft vinyl chloride resin coating layer is caused, and the resulting frictional heat melts the soft vinyl chloride resin coating layer, welding the sheet edges, and fixing by pressing for 5 to 10 seconds after cooling. let A stamped area B is provided at the lap connection portion of the tent membrane sewn product and the waterproof sheet sewn product, and this stamped area B is stamped by pressing a mold bar during high frequency welding. The marking area B is designed on the mold bar, and the height of the marking area B is 3 to 10 cm and the length is 3 to 15 cm. be done. The stamp area B is designed with information about the tent membrane sewing manufacturer or the tarpaulin sewing manufacturer, which specifically includes the sewing manufacturer, reading code, symbol mark, etc. The mold bar is flat, and these information displays are formed in the same four patterns as the marking area A, such as a mirror surface on the convex part, a matte finish on the convex part, a mirror surface on the concave part, a matte finish on the concave part, etc., or evenly spaced convex stripes are formed on the entire surface of the mold bar. , information display can be used by casting stripes in the form of letters or figures, excluding the convex parts. The marking area B is shaped by a mold bar, and letters, numbers, symbols, and figures (marks) are designed in reverse on the mold bar. The stamped area B clarifies the sewing maker information of the tent membrane sewn product or the waterproof sheet sewn product. The stamped areas B are preferably provided at intervals of 1 to 3 m on the inside of the tent membrane sewn product and the waterproof sheet sewn product to protect them from damage such as soot, wind and rain, and ultraviolet rays. For example, engraved area B "HIRAOKA" indicates that the sewing manufacturer is Hiraoka Textile Co., Ltd., and by maintaining the clarity of this engraved area B for a long period of time, it is possible to make inquiries to the manufacturer.

Currently, sewn tent membranes, sewn waterproof sheets, etc. that have been used for 5 to 10 years are dismantled and disposed of in landfills, but even sewn items that are no longer used tend to suffer from damage such as holes. Unless otherwise specified, it maintains waterproof and light-shielding properties comparable to those of the initial stage. Therefore, healthy waste materials from sewn tent membranes and sewn tarpaulins can be reused as weed control sheets for vacant lots, fallow fields, solar power generation equipment installation areas, railway track slopes, etc. In particular, it cuts off water supply to plants (especially weeds), and its light-blocking properties cut off photosynthesis in plants (especially weeds), 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 inhibiting the growth of plants. To reuse it as a weed control sheet, the sewn tent membrane and waterproof sheet are dismantled into any size, laid on the ground or slope, and used in the same way as conventional weed control sheets, which are secured to the ground with anchor pins, etc. can. For tent membrane structures in particular, white and ivory colors are easily available, and for truck hoods and tarpaulins in particular, dark green and olive drab colors are easily available. This reuse eliminates the need for new tarpaulins and reduces the consumption of petrochemical raw materials for manufacturing tarpaulins, leading to a reduction in future carbon dioxide emissions. By the way, when reusing weed control sheets, users who blindly lay down weed control sheets without knowing information about the materials of tent membranes, waterproof sheets, etc. are no different from dumping waste materials. becomes. Therefore, the basic information (engraved area B) of the tent membrane sewn product and the waterproof sheet sewn product, and the basic information (engraved area A) of the industrial material sheets that make up the tent membrane sewn product and the waterproof sheet sewn product are clarified. , it is possible to fulfill the company's responsibility for reusing it as a weed control sheet and disposing of it after reuse. If both stamped area A and stamped area B are unknown, it will be difficult to determine who is responsible for installing the weed control sheet and its disposal, so it is difficult to reuse waste materials such as sewn tent membranes and waterproof sheets for weed control sheets. requires at least information on the marking area A.

EXAMPLES Next, the present invention will 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 bending reciprocating wear test (JIS L1096 8.19.2 B method compliant)
A test piece of 25 mm width x 120 mm length, including the stamped area A, was taken from the industrial material sheet, left for 24 hours in a 25°C environment, then mounted on a Scott type tester, and tested 1,000 times and 2,000 times under a load of 1 kgf. The test pieces were bent back and forth twice in a constant temperature room at 25°C, the surface condition after the test was observed, and the dynamic cold resistance was judged as follows.
1: No noticeable wear or abrasion is observed on the display part of stamped area A. 2: Significant wear is observed on the display part of stamped area A, but it can be identified. 3: The display part of stamped area A is worn out and cannot be identified. (2) Abrasion resistance of stamped area A: JIS L1096 8.19.3 C method) Taber shape method A 13 cm diameter disk including stamped area A collected from an industrial material sheet was used as a test piece.
It was attached to a Taber type abrasion tester (wearing wheel CS-10), and after applying an abrasion load of 1000 rotations and 2000 rotations with a load of 2.45N to the marking area A, the marking area A was observed with a magnifying glass, and the marking area was The identifiability of the display section in area A was determined.
1: No noticeable wear or abrasion is observed on the display part of stamped area A. 2: Significant wear is observed on the display part of stamped area A, but it can be identified. 3: The display part of stamped area A is worn out and cannot be identified. (3) Formation of stamped area A 3-1) During production of the industrial material sheet, stamped area A is continuously formed on the right edge of the industrial material sheet except for the edge 10cm using a 30-inch diameter embossing roll at 240cm intervals at a speed of 8m/min. Shaped. The engraving on the emboss roll is "PET &PVC" inverted Gothic letters (1 character: 2cm x 2cm, line width 5mm, mirror surface: character spacing 5mm), a concave mirror surface due to the display (height difference 0.5mm), and the background is designed with a satin-finished convex part. The paper was written horizontally along the longitudinal direction of the edge of the industrial material sheet. The marking area A is crimped with an embossing roll set at 180°C and a pair of rubber rolls, and the marking is fixed by cooling (air-cooled and water-cooled rolls) after embossing. The resulting stamp area A is a satin-finished concave portion (background: height 3.5 cm x width 19 cm) including a mirror-finished convex portion (display portion). The embossing roll has a mirror surface other than the engraved area A.
3-2) Similar to 1) above, reverse Gothic letters of "PET&PVC" (1 character: 2cm x
2cm line width 5mm mirror surface: character spacing 5mm) Convex mirror surface due to display (height difference 0.5mm),
The engraving area A obtained by using an embossing roll with a satin-finished concave background design is a satin-finished convex part (background: height 3.5 cm x width 19 cm) including a mirror-finish concave part (display part), and this embossing roll The area other than the engraved area A is a mirror surface.
3-3) Similar to 1) above, reverse Gothic letters of "PET &PVC" (1 character: 2cm x
2cm line width 5mm satin finish: character spacing 5mm) concave satin finish due to display area (height difference 0.5mm),
The engraving area A obtained by using an embossing roll whose background is designed with a mirror-like convex part is a mirror-like concave part (background: height 3.5 cm x width 19 cm) including a matte finish convex part (display part). The boss roll has a satin finish other than the stamped area A.
3-4) Similar to 1) above, reverse Gothic letters of "PET &PVC" (1 character: 2cm x
2cm line width 5mm satin finish: character spacing 5mm) convex satin finish due to display area (height difference 0.5mm),
The engraving area A obtained by using an embossing roll whose background is designed with a mirror-like concave part is a mirror-like convex part (background: height 3.5 cm x width 19 cm) including a matte finish concave part (display part), and this embossing roll The areas other than the engraved area A are satin-finished.
(4) Formation of stamping area B The ends of two industrial material sheets in the same direction are overlapped in parallel in a straight line with a width of 4cm to form a lap sewing part, and a weld bar (engraved blade) with a width of 4cm and a length of 30cm is formed. ) equipped with a high frequency welder fusion machine (YTO-8A model manufactured by Yamamoto Vinita Co., Ltd.: high frequency output 8KW)
The lap sewing part was pressed against the weld bar by oscillation with an anode current of 1.0 A, and the soft vinyl chloride resin coating layer was melted by high frequency oscillation to obtain a sewn product. The weld bar is engraved with "HIRAOKA" in reverse Gothic letters (1) in the center of the weld bar.
Characters: 2cm x 2cm line width 5mm Mirror surface: Character spacing 5mm) Convex mirror surface (height difference 0.5mm) by the display part, Engraving area B with a satin-finished concave background design, and this weld bar other than the engraving area B is a mirror surface.

[Example 1]
<Fabric (1)>
Driving the warp threads using the 20th count double yarn polyester staple spun yarn (S twist 300T/m) as the warp yarn and the 10th count single yarn polyester short fiber spun yarn (S twist 400T/m) as the weft yarn. A No. 5 fabric having a porosity of 0 in appearance due to fluff and a mass of 240 g/m ² was used, which was plain weave woven at a density of 54 threads/inch and a weft density of 46 threads/inch.
The fabric was subjected to water repellency treatment (immersion, heat treatment) with an acrylate/vinyl chloride resin copolymer emulsion (solid content 5% by mass) having a perfluoroalkyl group with a carbon number of 6 or less, and abnormalities were detected in the soft vinyl chloride resin coating layer. This prevents rainwater from penetrating (water absorption) in the event that it occurs. This was designated as fabric (1).
<Soft vinyl chloride resin coating layer>
A processing liquid mainly consisting of a vinyl chloride resin composition paste (containing at least three types of vinyl chloride resin, plasticizer, and liquid synthetic rubber) for forming a soft vinyl chloride resin coating layer of <Formulation 1> below was prepared. Next, the fabric (1) is dipped (immersed) in a liquid bath filled with this processing liquid to impregnate the fabric (1) with the processing liquid of <Formulation 1> under normal pressure. At the same time as it was pulled up from the liquid bath, it was squeezed with a rubber mangle roll to remove excess processing liquid and temporarily form a soft vinyl chloride resin coating layer. Next, a soft vinyl chloride resin coating layer of 290 g/m ² was formed on the entire surface of the fabric (1) by performing a gelling heat treatment for 3 minutes in a hot air oven at 180°C, as described in paragraph [0031] 3-1). A dark green waterproof canvas (1) with a mass of 530 g/m ² was obtained by providing an engraved area A on the back surface. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this waterproof canvas (1).
Gelation heat treatment is performed by converting the vinyl chloride resin composition paste into a soft vinyl chloride resin and at the same time crosslinking the liquid synthetic rubber to convert it into a crosslinked rubber. This is a process of forming a hybrid in which the original crosslinked network is entangled with the vinyl chloride resin main chain.
<Formulation 1> Processing liquid for forming soft vinyl chloride resin coating layer Paste vinyl chloride resin (degree of polymerization 1700) 100 parts by mass Diisononyl phthalate (DINP plasticizer) 60 parts by mass Butadiene-based liquid rubber* 10 parts by mass Isocyanurate (HMDI* trimer (NCO crosslinking agent) 2 parts by mass Chlorinated paraffin (flame retardant and plasticizer) 5 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 4 parts by mass Antimony trioxide (flame retardant) 20 parts by mass Zinc stearate (stabilizer) 2 parts by mass Ultraviolet absorber (triazine tautomer) 0.5 parts by mass Titanium oxide (white pigment) 1 part by mass Phthalocyanine green (green pigment) 3 parts by mass Carbon black (black pigment) 0.5 parts by mass Trichlorethylene (diluent solvent) 20 parts by mass *Butadiene-based liquid rubber: Contains 15% by mass of styrene as a block copolymerization component,
Properties of average molecular weight 3000 with -COOH groups at both ends of the molecule *HMDI: Hexamethylene diisocyanate HMDI trimer (isocyanurate) has three isocyanate groups

[Example 2]
Example 1 except that the machining liquid of <Formulation 1> in Example 1 was changed to the machining liquid of <Formulation 2>, and the marking area A described in paragraph [0031] 3-2) was provided on the back side. Similarly, a dark green waterproof canvas (2) with a mass of 530 g/m ² was obtained. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this waterproof canvas (2).
The processing liquid of <Formulation 2> is obtained by substituting 10 parts by mass of the butadiene-based liquid rubber of <Formulation 1> with 10 parts by mass of isoprene-based liquid rubber, and the isoprene-based liquid rubber contains 10 parts by mass of acrylonitrile as a block copolymerization component. It contains -COOH groups at both ends of the molecule and has an average molecular weight of 2500.

[Example 3]
Example 1 except that the machining liquid of <Formulation 1> in Example 1 was changed to the machining liquid of <Formulation 3>, and the stamped area A described in paragraph [0031] 3-3) was provided on the back side. Similarly, a dark green waterproof canvas (3) with a mass of 530 g/m ² was obtained. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this waterproof canvas (3).
The processing liquid of <Formulation 3> is obtained by replacing 10 parts by mass of the butadiene-based liquid rubber of <Formulation 1> with 10 parts by mass of β-fanersene-based liquid rubber, and the β-phanersene-based liquid rubber is a block copolymer component. It contains 10% by mass of butadiene, has a -COOH group at both ends of the molecule, and has an average molecular weight of 5,000.

[Example 4]
Example 1 except that the machining fluid of <Formulation 1> in Example 1 was changed to the machining fluid of <Formulation 4>, and the stamped area A described in paragraph [0031] 3-4) was provided on the back side. Similarly, a dark green waterproof canvas (4) with a mass of 530 g/m ² was obtained. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this waterproof canvas (4).
The processing fluid of <Formulation 4> is the processing fluid of <Formulation 1> to which 2 parts by mass of surface-modified silica particles are added.
The surface-modified silica particles are made by combining dry silica (gel method: average particle diameter 2 μm, BET specific surface area 300 m ² /g) with N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (silane coupling agent). It was stirred in a 5% by mass aqueous solution at 24°C for 3 hours, separated and dried, and the -Si-R-Si(OCH ₃ ) ₃ modification that binds to the silanol group of silica and (that binds to the siloxane moiety) -O) ₃ Si-R-NH ₂ modification is mixed.

[Example 5]
<Fabric (2)>
PET multifilament yarn made of 1000 denier (1111 dtex) polyethylene teretalate (PET) fibers (192 filaments) and subjected to S twist of 50 T/m is used for the warp and weft groups, and the warp groups have a 1-inch interval. A plain woven fabric with 16 weaving lines and a weft group of 16 weaving lines per inch was used. The mass of this fabric was 150 g/m ² , and the porosity (total number of holes) was 14%.
This fabric was subjected to water repellency treatment (immersion, heat treatment) with an acrylate/vinyl chloride resin copolymer emulsion (solid content 5% by mass) having a perfluoroalkyl group having 6 or less carbon atoms, and a cut cross section of the sewn tent membrane sheet was prepared. This prevents rainwater from penetrating (water absorption). This was designated as fabric (2).
<Soft vinyl chloride resin coating layer>
A vinyl chloride resin composition compound (containing at least three types of vinyl chloride resin, plasticizer, and liquid synthetic rubber) for forming a soft vinyl chloride resin coating layer of <Formulation 5> below was prepared. Using the fabric (2) as a base material, a 0.2 mm thick calendar molded film made of the vinyl chloride resin composition compound of [Formulation 5] is applied to both sides as a soft vinyl chloride resin coating layer, and thermocompression bonded with a laminator. A white tarpaulin for tent membrane (1) with a thickness of 0.7 mm and a mass of 830 g/m ² was prepared by melt-laminating the tent membrane according to Obtained. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this tent membrane tarpaulin (1).
[Formulation 5]: Soft vinyl chloride resin composition (compound)
Straight vinyl chloride resin (K value 71.5) 100 parts by mass Diisononyl phthalate (DINP plasticizer) 60 parts by mass Butadiene liquid rubber* 10 parts by mass Isocyanurate (HMDI* trimer: NCO crosslinking agent) 2 parts by mass Chlorine Chlorinated paraffin (flame retardant and plasticizer) 5 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 4 parts by mass Antimony trioxide (flame retardant) 20 parts by mass Zinc stearate (stabilizer) 2 parts by mass Ultraviolet absorber (Triazine tautomer) 0.5 parts by mass Titanium oxide (white pigment) 3 parts by mass *Butadiene liquid rubber: Contains 15% by mass of styrene as a block copolymer component,
Properties of average molecular weight 3000 with -COOH groups at both ends of the molecule *HMDI: Hexamethylene diisocyanate HMDI trimer (isocyanurate) has three isocyanate groups

[Example 6]
Same as Example 5, except that the compound of <Blend 5> in Example 5 was changed to the compound of <Blend 6>, and the stamped area A described in paragraph [0031] 3-2) was provided on the back side. A white tent membrane tarpaulin (2) having a thickness of 0.7 mm and a mass of 830 g/m ² was obtained. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this tent membrane tarpaulin (2).
The compound of <Formulation 6> is obtained by substituting 10 parts by mass of the butadiene-based liquid rubber of <Formulation 5> with 10 parts by mass of isoprene-based liquid rubber, and the isoprene-based liquid rubber contains 10 parts by mass of acrylonitrile as a block copolymerization component. % and has -COOH groups at both ends of the molecule and has an average molecular weight of 2500.

[Example 7]
Same as Example 5, except that the compound of <Blend 5> in Example 5 was changed to the compound of <Blend 7>, and the stamped area A described in paragraph [0031] 3-3) was provided on the back side. A white tent membrane tarpaulin (3) with a thickness of 0.7 mm and a mass of 830 g/m ² was obtained. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this tent membrane tarpaulin (3).
The compound of <Blend 7> is obtained by substituting 10 parts by mass of the butadiene liquid rubber of <Blend 5> with 10 parts by mass of β-fanersene liquid rubber, and the β-phanersene liquid rubber is used as a block copolymerization component. It contains 10% by mass of butadiene, has -COOH groups at both ends of the molecule, and has an average molecular weight of 5,000.

[Example 8]
Same as Example 5, except that the compound of <Blend 5> in Example 5 was changed to the compound of <Blend 8>, and the stamped area A described in paragraph [0031] 3-4) was provided on the back side. A white tent membrane tarpaulin (4) with a thickness of 0.7 mm and a mass of 830 g/m ² was obtained. The stamped area B described in paragraph [0031] (4) was provided on the back side of the sewn part of the sewn product of this tent membrane tarpaulin (4).
The processing fluid of <Blend 8> is the compound of <Blend 5> to which 2 parts by mass of surface-modified silica particles are added. The surface-modified silica particles are made by combining dry silica (gel method: average particle diameter 2 μm, BET specific surface area 300 m ² /g) with N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (silane coupling agent). It was stirred in a 5% by mass aqueous solution at 24°C for 3 hours, separated and dried, and the -Si-R-Si(OCH ₃ ) ₃ modification that binds to the silanol group of silica and (that binds to the siloxane moiety) -O) ₃ Si-R-NH ₂ modification is mixed.

[Example 9]
The used waste of the waterproof canvas (1) sewn from Example 1 (two pieces of waterproof canvas 203 cm wide x 10 m long sewn to 402 cm wide x 10 m long) was spread on a vacant lot where weeds had been cut, and anchored. As a result of fixing it to the ground with pins and leaving it for three months from June to August, no weeds were observed to grow under the used waste, and the used waste of the waterproof canvas (1) sewn product of Example 1 was found. It was demonstrated that it is suitable for use as a weed control sheet.

[Example 10]
The used waste of the sewn tent membrane tarpaulin (1) of Example 5 (two tent membrane tarpaulins of width 203 cm x length 10 m sewn into width 402 cm x length 10 m) was taken from a vacant lot where weeds had been cut. As a result of fixing it to the ground with anchor pins and leaving it for three months from June to August, no weeds were observed to grow under the used waste, and the tarpaulin for tent membrane (1) of Example 5 was not observed. It has been demonstrated that used waste products from sewn products are suitable for use as weed control sheets.

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 each have an engraved area A consisting of a display part and a background. In both cases, the appearance of the display section and the background is a contrast between a mirror surface and a satin finish, and this contrast structure has the effect of significantly improving the visibility of the display section even if the engraving depth is about 0.3 mm. Obtained.
In these examples, rubber crosslinks are formed in the soft vinyl chloride resin coating layer, and this formation is achieved by converting liquid synthetic rubber into crosslinked rubber to form a rubber crosslinked network throughout the soft vinyl chloride resin coating layer. This is what I did. Liquid synthetic rubber molecules exist in the soft vinyl chloride resin coating layer before conversion in a state entangled with the vinyl chloride resin main chain, and as this liquid synthetic rubber is crosslinked, the entire area within the soft vinyl chloride resin coating layer is A hybrid covered by the rubber crosslinked network was formed, and the abrasion resistance and abrasion resistance of the soft vinyl chloride resin coating layer, that is, the stamped area A, were improved. Therefore, it has been demonstrated that even if the marking depth of the marking area A is about 0.3 mm, there is no fear that the display part will be easily abraded and abraded and the display part will become unclear.
In addition, in the synthetic canvas (4) of Example 4 and the tent membrane tarpaulin (4) of Example 8, liquid synthetic rubber is bonded to silanol groups (Si-OH groups) on the surface of silica particles (with the intervention of a crosslinking agent). By including silica (treated with a silane coupling agent) at the relay point in the rubber crosslinked structure, the rubber crosslinking is further strengthened, improving the abrasion resistance and abrasion resistance of the soft vinyl chloride resin coating layer (engraved area A). We were able to improve it further. Particularly, in order for the liquid synthetic rubber to bond with the silanol groups on the surface of the silica particles and to interpose silica as a relay point in the rubber crosslinked structure, the involvement of a silane coupling agent was effective in assisting the formation of rubber crosslinks.
The engraved area A "PET&PVC" provided on the waterproof canvas and tent membrane tarpaulin of Examples 1 to 8 indicates that the materials are polyester fiber fabric and vinyl chloride resin, and the clarity of this engraved area A By maintaining the material for a long period of time, it becomes easy to separate the materials for recycling (weed control sheets) and disposal later. In addition, the stamped area B "HIRAOKA" provided on the welded part of the waterproof canvas sewn product and the tent membrane sewn product, which are sewn by welding, indicates that the sewing manufacturer is Hiraoka Textile Co., Ltd., and this stamped area B By maintaining the clarity of the image for a long period of time, it becomes possible to refer to the decision at the time of recycling/disposal.
Example 9 demonstrated that the used waterproof canvas (1) sewn product of Example 1 could be reused as a weed control sheet, and Example 10 demonstrated that the used waterproof canvas (1) sewn product of Example 1 could be reused as a weed control sheet. It has been demonstrated that used sewn products can be reused as weed control sheets. Therefore, similar waterproof canvases (2) to (4) of Examples 2 to 4 and tarpaulins for tent membranes (2) to (4) of Examples 6 to 8 are also recycled into weed control sheets. It is possible to use it. If waste materials from sewn tent membranes and sewn tarpaulins can be reused as weed control sheets, new weed control sheets will no longer be needed, the consumption of petrochemical raw materials will be reduced, and this will further lead to a reduction in carbon dioxide emissions. .

[Comparative example 1]
Inverted Gothic letters in stamp area A "PET&PVC" used in Example 1 (1 character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm), concave mirror surface (height difference 0.5 mm) by display section, background is satin convex A waterproof canvas (5) was obtained in the same manner as in Example 1, except that in the design consisting of sections, the background was a mirror-finished convex section.

[Comparative example 2]
Inverted Gothic letters in stamp area A "PET&PVC" used in Example 1 (1 character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm), concave mirror surface (height difference 0.5 mm) by display section, background is satin convex A waterproof canvas (6) was obtained in the same manner as in Example 1, except that the display part had a concave satin finish (height difference: 0.5 mm).

[Comparative example 3]
Inverted Gothic letters in stamp area A "PET &PVC" used in Example 5 (1 character: 2 cm x 2 cm line width 5 mm mirror surface: character spacing 5 mm) concave mirror surface (height difference 0.5 mm) by display part, background is satin convex A tent membrane tarpaulin (5) was obtained in the same manner as in Example 5, except that in the design consisting of sections, the background was a mirror-finished convex section.

[Comparative example 4]
Inverted Gothic letters in stamp area A "PET &PVC" used in Example 5 (1 character: 2 cm x 2 cm line width 5 mm mirror surface: character spacing 5 mm) concave mirror surface (height difference 0.5 mm) by display part, background is satin convex A tarpaulin for a tent membrane (6) was obtained in the same manner as in Example 5, except that the display part had a concave matte finish (height difference: 0.5 mm).

[Comparative example 5]
The same as in Example 1 except that 10 parts by mass of butadiene-based liquid rubber (having a -COOH group at both ends of the molecule and an average molecular weight of 3000) was omitted from the processing fluid of <Formulation 1> of Example 1, and the mass was 530 g. A dark green waterproof canvas (7) with a size of /m ² was obtained.
A rubber crosslinked network is not formed in the soft vinyl chloride resin coating layer of the waterproof canvas (7), so the stamped area A formed in the soft vinyl chloride resin coating layer has poor abrasion resistance and abrasion resistance. As a result of the Scott type bending reciprocating abrasion test and the Taber type abrasion test, the marking area A "PET &PVC" was worn out and became unrecognizable.

[Comparative example 6]
10 parts by mass of the butadiene-based liquid rubber (having -COOH groups at both ends of the molecule and having an average molecular weight of 3000) of the processing fluid of <Formulation 1> of Example 1 was added to an average molecular weight of 3000 having no functional groups at both ends of the molecule. A dark green waterproof canvas (8) with a mass of 530 g/m ² was obtained in the same manner as in Example 1 except that 10 parts by mass of butadiene-based liquid rubber was substituted.
A rubber crosslinked network is not formed in the soft vinyl chloride resin coating layer of the waterproof canvas (8), so the stamped area A formed in the soft vinyl chloride resin coating layer has poor abrasion resistance and abrasion resistance. As a result of the Scott type bending reciprocating abrasion test and the Taber type abrasion test, the marking area A "PET &PVC" was worn out and became unrecognizable.

[Comparative Example 7]
10 parts by mass of the butadiene-based liquid rubber (average molecular weight 3000 with -COOH groups at both ends of the molecule) of the processing fluid of <Formulation 1> of Example 1 was added to butadiene rubber powder (registered trademark "Kane Ace" M-711: A dark green waterproof canvas (9) with a mass of 530 g/m ² was obtained in the same manner as in Example 1 except that 10 parts by mass (Kaneka Co., Ltd.) was substituted.
A rubber crosslinked network is not formed in the soft vinyl chloride resin coating layer of the waterproof canvas (9), so the stamped area A formed in the soft vinyl chloride resin coating layer has poor abrasion resistance and abrasion resistance. As a result of the Scott type bending reciprocating abrasion test and the Taber type abrasion test, the marking area A "PET &PVC" was difficult to distinguish due to wear.

As is clear from the above examples and comparative examples, according to the present invention, tent membrane sewn products (pavilions, tent houses, awning tents, etc.) and waterproof sheet sewn products (truck hoods, cargo bed covers, open storage sheets, In applications for industrial material sheets (such as floor sheets), in particular, stamps such as source, product number, material, etc. can be clearly and robustly displayed as stamp area A even if the stamp depth is as shallow as 0.5 mm or less. This makes it easier to sort and recycle/dispose of items over a long period of time.Furthermore, tent membrane sewn products (metal frame removed from the tent membrane structure) and waterproof sheet sewn products can be easily identified based on this marking. By reusing waste materials as weed control sheets, new weed control sheets are no longer required, which reduces the consumption of petrochemical raw materials, which in turn leads to a reduction in carbon dioxide emissions.

1-1: Mirror surface convex part (display part)
1-2: Satin recess (background)
2-1: Mirror recess (display part)
2-2: Satin convex part (background)
3-1: Satin convex part (display part)
3-2: Mirror surface recess (background)
4-1: Satin recess (display part)
4-2: Mirror surface convex part (background)

Claims (7)

A long sheet formed by providing a soft vinyl chloride resin coating layer on the front and back sides of a fabric, which has an engraved area A on either one of the front and back soft vinyl chloride resin coating layers, and this engraved area A is It is formed periodically on one end of the long sheet in the longitudinal direction and consists of a display part and a background, "mirror-finished convex part (display part)/matte-finish concave part (background)", "mirror-finished concave part (display part)/ The pattern is one or more selected from the following: ``Near-skinned convex portion (background)'', ``Near-skinned convex portion (display area)/mirror surface concave portion (background)'', and ``Near-skinned concave portion (display area)/mirror surface convex portion (background)''. An industrial material sheet characterized by: The soft vinyl chloride resin coating layer contains crosslinked rubber, and rubber crosslinks are formed throughout this layer, and the rubber crosslinks are made of one or more types selected from butadiene rubber, isoprene rubber, and farnesene rubber. The industrial material sheet according to claim 1, comprising a rubber structure. The industrial material sheet according to claim 1 or 2, wherein the display portion is a set of one or more types of concave portions and/or convex portions selected from letters, numbers, symbols, and figures (marks). A tent membrane sewn product formed by lap-connecting the ends of the industrial material sheet according to any one of claims 1 to 3, wherein a stamped area B is provided at the lap connection part of the tent membrane sewn product. Sewn tent membrane. A sewn waterproof sheet product formed by connecting the ends of the industrial material sheet according to any one of claims 1 to 3, wherein a stamped area B is provided at the lap connecting portion of the sewn waterproof sheet product. Sewn tarpaulin A method of utilizing sewn tent membrane waste material according to claim 4, wherein the waste material of the sewn tent membrane product is used as a weed control sheet. 6. A method of utilizing waste materials from sewn tarpaulin sheets as claimed in claim 5, wherein the waste material from sewn tarpaulin sheets is used as a weed control sheet.