Industrial material sheets, and sewn tent membranes and waterproof sheeting products made by connecting the sheets, and methods for utilizing the waste materials

Abstract

To provide a tent membrane sewn product and a waterproof sheet sewn product that can be clearly and robustly displayed even if a depth of an engraved stamp in stamp marking is shallow and can be used to determine whether to recycle or dispose the product over time, and to provide a method for using waste materials based on stamp markings on these sewn products.SOLUTION: On a long sheet formed by providing a soft vinyl chloride resin coating layer on front and back sides of a fabric, a stamped area A is periodically formed at one end in a longitudinal direction, to provide an industrial material sheet with the stamped area A selected from "mirror convex part (display part) / satin concave part (background)", "mirror concave part (display part) / satin concave part (background)", "satin convex part (display part) / mirror concave part (background)" and "satin concave part (display part) / mirror convex part (background)", and this is sewn into a tent membrane sewn product or the like, and this waste material is reused as a weed control sheet based on information on the stamped area A.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] 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 frames 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 sort and determine whether to recycle or discard, and to the utilization of waste materials based on the engraved markings on these waste sewn products. [Background technology]

[0002] Tarpaulins made by laminating a thermoplastic resin film such as soft polyvinyl chloride resin to a fabric made of polyester long fiber yarn are used for tent membrane structures such as large tents (pavilions), circus tents, seat houses, membrane roofs (ceilings) for architectural spaces, and stadium sunshades, and light colors such as white and ivory are preferred for their hues, which are aesthetically pleasing and blend well with other buildings. On the other hand, synthetic canvas made by impregnating and covering a spun fabric made of polyester short fiber yarn with a thermoplastic resin solution such as soft polyvinyl chloride resin, and then drying and solidifying it by heating is used for truck hoods, loading platform covers, sheet warehouses, and open-air storage sheets, and dark colors such as dark green, olive drab, and navy blue, which are less noticeable when dirty, are the mainstream for most of these colors. These industrial material sheets such as tarpaulins and synthetic canvas are distributed in rolls of raw material that are 0.3 to 1.5 mm thick, 0.9 to 2.4 m wide, and 25 to 50 m long, and for the reasons mentioned above, in these markets, there are multiple competing products of the same color and specifications mixed together.

[0003] These industrial material sheets do not display information such as the manufacturer, brand, product number, and material on the sheet itself, so 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) compliant products, RoHS2 (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment) compliant products, products certified by the Minister of Land, Infrastructure, Transport and Tourism, 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, a system that can correctly identify basic information such as manufacturer, product number, and material is necessary for the disposal of tent membrane structures, waterproof sheets, etc., but such a system has not yet been established within the industry.In addition, the secondary use of these waste materials has not been considered until now.

[0004] The applicant previously proposed synthetic leather with a pearlescent luster having a design part consisting of a depressed part and a non-depressed part and a specific depression height difference as a synthetic leather used for the fabric of portable goods, furniture, flooring material, fabric for decorative parts, etc., and capable of clearly and freely displaying a richly three-dimensional and unexpected design 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, the letters are designed in a concave shape, and the depression height difference between the depressed part and the non-depressed part is 0.2 mm. This synthetic leather has a decoration in which gold and violet alternately interfere with each other 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 part on the label surface is mainly composed of convex parts of an uneven pattern, and the convex parts of the uneven pattern constituting the background pattern are glossy surfaces and the concave parts are matte surfaces. However, even if such a transfer label formed by screen printing is applied to display information on industrial material sheets, the fine uneven pattern will wear out and become short-lived in 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. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-163013 A [Patent Document 2] JP 2003-094891 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides 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 frames removed) and waterproof sheet sewn products that can be clearly and robustly marked with markings such as origin, product number, material, etc. even with a marking depth of about 0.3 mm, and that enable sorting judgment for recycling / disposal over time, and further provides a method of utilizing waste materials based on the markings on these sewn products. [Means for solving the problem]

[0007] As a result of intensive research in consideration of the above points, the present invention provides a long sheet having a soft vinyl chloride resin coating layer on both sides of a fabric, The soft vinyl chloride resin coating layer contains a crosslinked rubber, and a rubber crosslink is formed throughout the layer, and the rubber crosslink contains one or more rubber structures selected from a butadiene rubber, an isoprene rubber, and a farnesene rubber, The sheet has an imprinted area A on either one of the soft vinyl chloride resin coating layers on the front or back, and the imprinted area A is periodically formed on one end of the long sheet in the longitudinal direction, and is composed of an indicia and a background, and has one or more patterns selected from "mirror-surface convex portion (indicia) / matt-finish concave portion (background)", "mirror-surface concave portion (indicia) / matt-finish convex portion (background)", "matt-finish convex portion (indicia) / mirror-surface concave portion (background)", and "matt-finish concave portion (indicia) / mirror-surface convex portion (background)". The display portion is a set of one or more recesses and / or protrusions selected from the group consisting of letters, numbers, symbols, and figures (marks).As a result, the appearance of the display part and the background has a contrast effect between a mirror surface and a matte finish, and even if the marking depth is about 0.3 mm, the visibility of the display part is significantly improved, and it is possible to obtain an industrial material sheet (tarpaulin, synthetic canvas) for tent membrane structures and waterproof sheets with a clear marking area A. 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, it has been found that by clearly and firmly marking and indicating information such as the source, product number, and material as the marking area A in a specific part of the industrial material sheet, it is possible to determine whether to recycle or discard, and further, it has been found that the tent membrane sewn products (tent membrane structures with the metal frame removed) and waste materials of the waterproof sheet sewn products can be used as weed control sheets based on this marking, and this invention has been completed. In other words, if the engraved area A is unclear, it will be impossible to determine who is responsible for the construction and disposal of the weed control sheet, so when recycling waste materials such as sewn tent membranes or waterproof sheeting into weed control sheets, it is necessary to have at least the information in the engraved area A. For example, engraved area A "PET&PVC" indicates that the materials are 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 materials for later recycling (weed control sheet) or disposal.

[0008] 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 the layer, and the rubber crosslinks contain one or more rubber structures selected from butadiene rubber, isoprene rubber, and farnesene rubber. A hybrid is formed in the soft polyvinyl chloride resin coating layer, in which a crosslinked network of the rubber crosslinks is entangled with the polyvinyl chloride resin main chain, and this hybrid provides excellent wear and abrasion resistance to the engraved markings in the engraved area A, and the engraved markings are stably maintained even after a long period of time outdoors, making it possible to determine whether to recycle or discard the product.

[0009] In the industrial material sheet of the present invention, the indicia are preferably a collection of recesses and / or protrusions of one or more types selected from letters, numbers, symbols and figures (marks).

[0010] The tent membrane sewn product of the present invention is the above-mentioned industrial material sheet Peer End of but , By using a high-frequency welding machine (high-frequency welder) equipped with a mold bar Wrap connection was done A tent membrane sewn product, in which an imprinted area B is provided at a lap connection portion of the tent membrane sewn product. The marking area B is stamped by the pressure of the die bar during high frequency welding. It is preferable that the marking area B is stamped by pressing a heated mold when sewing the tent membrane, and the marking area B reveals the sewing manufacturer information of the sewn tent membrane product. For example, the marking area B "HIRAOKA" 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 inquire with the manufacturer.

[0011] The waterproof sheet sewn product of the present invention is the above-mentioned industrial material sheet Peer End of but , By using a high-frequency welding machine (high-frequency welder) equipped with a mold bar Wrap connection was done A waterproof sheet sewn product, in which an imprinted area B is provided at the lap connection portion of the waterproof sheet sewn product. The marking area B is stamped by the pressure of the die bar during high frequency welding. This marking area B is stamped by pressing with a heated mold when sewing the waterproof sheet, and the marking area B reveals sewing manufacturer information of the sewn waterproof sheet product.

[0012] The method of utilizing the waste tent membrane sewn material of the present invention preferably involves converting the waste tent membrane sewn material into a weed control sheet. This allows the waste tent membrane sewn material to be appropriately reused as a weed control sheet according to the tent membrane profile (information display) before being disposed of in a landfill, eliminating the need for a new weed control sheet. The elimination of the need for a new weed control sheet reduces the consumption of new petrochemical raw materials, which in turn leads to a reduction in future carbon dioxide emissions.

[0013] The method of utilizing waste waterproof sheet sewn products of the present invention preferably involves converting the waste waterproof sheet sewn products into weed control sheets. This allows the waste waterproof sheet sewn products to be 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. Effect of the Invention

[0014] 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.), 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 after 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 since new weed control sheets are not required, which also leads to a reduction in carbon dioxide emissions. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention. [Diagram 2] FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention. [Diagram 3] FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention. [Figure 4] FIG. 1 is a cross-sectional view showing one embodiment of the imprint area A of the industrial material sheet of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The industrial material sheet of the present invention is a long sheet comprising a fabric and soft polyvinyl chloride resin coating layers on the front and back sides, the soft polyvinyl chloride resin coating layers on either side of the fabric having an imprinted area A, the imprinted area A being periodically formed on one end of the long sheet in the longitudinal direction and consisting of a display area and a background, the display area A being at least one pattern selected from "mirror-like convex area (display area) / matt-like concave area (background)", "mirror-like concave area (display area) / matt-like convex area (background)", "matt-like convex area (display area) / mirror-like concave area (background)", and "matt-like concave area (display area) / mirror-like convex area (background)". The soft polyvinyl chloride resin coating layer contains a crosslinked rubber, rubber crosslinks are formed throughout the layer, and the rubber crosslinks contain at least one rubber structure selected from butadiene-based rubber, isoprene-based rubber, and farnesene-based rubber. For example, the marking area A "PET&PVC" 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 time, making it easy to separate for recycling (weed control sheet) or disposal later. In this invention, the mirror surface means a glossy appearance accompanied by light reflection, and the matte surface means a matte appearance with fine unevenness that diffuses light reflection.

[0017] The fabric used in the industrial material sheet of the present invention can be in any form, such as woven fabric, knitted fabric, nonwoven fabric, etc. Woven fabrics include plain weave fabrics (biaxial fabrics made of warp / weft, triaxial fabrics made of warp / bias, and tetraaxial fabrics made of warp / weft / bias), twill weave fabrics (regular twill weaves such as 2×2, 3×3, and 4×4, and irregular twill weaves such as 3×2, 4×2, 4×3, 5×3, 2×3, 2×4, 3×4, and 3×5), twill weaves (minimum unit of 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 twill, 26-ply Twill, 8-ply twill, etc.), satin weave (minimum unit of warp and weft threads of at least 5 each: regular satin with 2-step, 3-step, 4-step, 5-step, etc.), and variation plain weave, variation twill, variation satin weave, etc., as well as honeycomb weave, pear ground weave, broken twill, day and night satin weave, twisted weave (shawl, ro), stitched weave, double weave, etc. can be used, but plain weave and 2 x 2 twill weave are particularly preferred as they have an excellent balance of warp and weft properties. As knitted fabrics, Russell knitted fabrics can be used, and as nonwoven fabrics, fleeces made by the wet method, dry method, spunbond method, or meltblown method fixed with heat or adhesive can be used. The above-mentioned woven fabrics, knitted fabrics and nonwoven fabrics may be subjected to one or more of known fiber treatments 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.

[0018] The yarns constituting the fabric may be any of synthetic fibers, natural fibers (cotton, kenaf), semi-synthetic fibers (rayon, acetate), inorganic fibers, or mixed fibers consisting 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, wholly 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, wholly aromatic polyamide fibers, aromatic heterocyclic polymer (polybenzimidazole, polybenzoxazole, polybenzothiazole, etc.) fibers, acrylic fibers, polyurethane fibers, or mixed fibers of these fibers are preferred. The form of these yarns may be 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 spun (spun) 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 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.

[0019] The fabric used in the present invention is preferably a woven fabric made of multifilament yarn or a staple spun fabric (spun), and the multifilament yarn is preferably 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 oval or flat cross section) or twisted yarn can be used as necessary. The staple spun yarn is preferably in the range of 10 count (591 dtex) to 60 count (97 dtex), particularly 10 count (591 dtex), 14 count (422 dtex), 16 count (370 dtex), 20 count (295 dtex), 24 count (246 dtex), 30 count (197 dtex), etc., and is preferably a single yarn, a two-ply yarn (single-twisted yarn), or a double-twisted yarn (multi-twisted yarn) made of two or more single yarns. There is no limit to the weft density of the warp and weft yarns in the woven fabric, and any design can be made according to the thickness (denier, count) of the yarns used. However, the weft density should be such that the void ratio (open stitches) of the woven fabric is in the range of 0-30% and the weight is 100-500g / m 2 The above-mentioned woven fabric is suitable for the fabric of the industrial material sheet. The porosity can be calculated by subtracting the area of ​​the yarn in the unit area of ​​the fabric as a percentage from 100. The woven fabric is suitable for manufacturing in which a soft vinyl chloride resin composition film is thermally laminated on preferably both sides of a woven fabric (void ratio 10 to 35%) made of multifilament yarn to form a soft vinyl chloride resin coating layer, and in the case of a staple fiber spun fabric (spun), the woven fabric is suitable for forming a soft vinyl chloride resin coating layer on preferably both sides of a staple fiber spun fabric (spun) with a void ratio of 0 to 10% by coating and heat treatment using a paste-like soft vinyl chloride resin composition, or dipping and heat treatment.

[0020] The soft vinyl chloride resin coating layer is formed from a soft vinyl chloride resin composition (containing a plasticizer), and is particularly preferably formed by coating or dipping using a paste vinyl chloride resin (emulsion polymerization type) and forming a coating by gelation heat treatment, or by forming a coating using a vinyl chloride resin film (sheet) by calendar rolling or T-die extrusion molding using a 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 tarpaulin. The vinyl chloride resin may be made of a plant-derived monomer to form an industrial material sheet compatible with biomass. 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 compounds, cyclohexene dicarboxylate 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 sheet of industrial materials compatible with biomass. Examples of plant-derived plasticizers include polyglycerin fatty acid ester compounds and furandicarboxylic acid dialkyl ester compounds.

[0021] The soft vinyl chloride resin coating layer is provided with a stabilizer for vinyl chloride resin, such as calcium zinc complex, barium zinc complex, organotin laurate, organotin mercaptite, epoxy stabilizer, or the like, 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 complex, azo compound (red), phthalocyanine compound (blue to green), anthraquinone compound (yellow to red), quinacridone compound (yellow to purple), etc., and 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 any amount, and 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 cations, etc.), etc. It may contain additives such as antibacterial agents, 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.).

[0022] 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 rubber, isoprene rubber, and farnesene rubber, and forms a hybrid in which the rubber crosslink network is entangled with the polyvinyl chloride resin main chain, thereby improving the wear and abrasion resistance of the markings in the marking area A and the marking area B, and stably retaining the markings even after a long period of time outdoors, making it easier to sort for recycling / disposal. 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 liquid rubber, isoprene liquid rubber, and farnesene 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 heat-gelling the soft vinyl chloride resin composition in this state, a hybrid soft vinyl chloride resin coating layer is formed in which a crosslinked rubber network is entangled with the vinyl chloride resin main chain. That is, a hybrid in which a crosslinked rubber network is entangled with the vinyl chloride resin main chain is formed throughout the entire soft vinyl chloride resin coating layer.

[0023] Butadiene liquid rubber that forms rubber crosslinks has either -COOH or -OH groups at the molecular end, which allows three-dimensional crosslinking. The molecular weight Mn is 1000 to 5000, particularly 1300 to 3500, and the viscosity is preferably in the range of 50 to 1000 poise (25°C), particularly 200 to 500 poise (25°C). Butadiene 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 that has about 75 to 80% of 1,4-cis structure or 1,4-trans structure and about 20 to 25% of 1,2-vinyl structure has low viscosity and excellent rubber elasticity when rubberized. This generation ratio is possible by radical polymerization method. The isoprene liquid rubber forming the rubber crosslink is preferably one having either -COOH group or -OH group at (both) molecular terminals and having a molecular weight Mn in the range of 3000 to 25000. The isoprene liquid rubber is one containing 5 to 25 mass% of styrene and / or acrylonitrile as a block copolymerization component, and one containing 10 to 50 mass% of butadiene or hydrogenated isoprene as a copolymerization component. Examples of the farnesene rubber forming the rubber crosslink include rubbers containing α-farnesene ((3E,7E)-3,7,11-trimethyl-1,3,6,10-dodecatetraene), β-farnesene (7,11-dimethyl-3-methylene-1,6,10-dodecatriene) as a monomer, copolymer rubber of farnesene and styrene, and copolymer rubber 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 the -OH group at the molecular (both) terminals, and can 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, as a part of the rubber crosslinking, it can be an organic-inorganic hybrid rubber crosslinking containing silica.

[0024] 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 generating chemical bonds between the functional groups on the silica surface and the -COOH and -OH groups at the molecular (both) ends of the liquid synthetic rubber. This reaction is formed by dehydration condensation between the -COOH and -OH groups at the molecular (both) ends 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. The generation of this rubber crosslinking is carried out 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 the chemical bonding between the liquid synthetic rubber and silica. This strengthens the rubber crosslinking, and the marking areas A and B marked on specific parts of the industrial material sheet become more durable, making it possible to clearly determine whether to recycle or dispose of the product after a long period of time.

[0025] Silica has a BET specific surface area of ​​100 to 300 m 2Synthetic amorphous silica having a particle size of 1 to 40 μm or less is preferred. 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 the molecular (both) 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. The silane coupling agent is represented by the general formula: XR-Si(Y) 3 It is an alkoxysilane compound having two or more different reactive groups in the molecule represented by the formula: X = amino group (aminosilane), vinyl group (vinylsilane), epoxy group (epoxysilane), methacryl group (methacrylsilane), acrylic group (acrylicsilane), chloro group (chlorosilane), mercapto group (mercaptosilane), isocyanurate group (isocyanuratesilane), isocyanate group (isocyanatesilane), etc. (R = alkyl chain), Y = methoxy group, ethoxy group, etc. Surface modification of silica is carried out by converting the silanol groups of silica into -Si-R-Si(Y). 3 The modification is the (-O) of the siloxane bond of silica. 3 It may be Si-RX modified.

[0026] The method for producing an 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. 2) The soft vinyl chloride resin composition (paste sol) is applied to the fabric by dipping (immersion-impregnation-roll squeezing-heat treatment gelation of the paste sol) or 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 thickness of the industrial material sheet is about 0.35 to 1.0 mm. The soft vinyl chloride resin film is formed in the range of 0.1 to 0.3 mm by calendar rolling molding of the soft vinyl chloride resin composition (compound) or T-die extrusion molding, and the thickness of the industrial material sheet is about 0.35 to 1.0 mm. 3) The liquid synthetic rubber can be converted into a rubber crosslinked network by using 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 polyvinyl chloride resin composition, so that a homogeneous rubber crosslinked network is formed throughout the soft polyvinyl 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 polyvinyl 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 polyvinyl chloride resin coating layer, i.e., as a cold resistance imparting agent. The remaining liquid synthetic rubber is 10 parts by mass or less per 100 parts by mass of the 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, the formation position is one side end, and it is possible to obtain the effect of distinguishing the product from similar products of other companies by using mirror embossing (glossy), matte embossing (matte), pattern embossing (design), character engraving (relief engraving of manufacturer name, product name, etc.), etc., particularly by engraving the manufacturer name, product name, etc.

[0027] Furthermore, 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 containing 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. Furthermore, 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.

[0028] 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 an indication part and a background, and the combination of the mirror part and the matte part in one or more patterns selected from "mirror convex part (indication part) / matte concave part (background)", "mirror concave part (indication part) / matte convex part (background)", "matte convex part (indication part) / mirror concave part (background)", and "matte concave part (indication part) / mirror convex part (background)" improves the visual contrast effect, so that the imprinted area A becomes 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 in which light is diffusely reflected by fine unevenness. The indication part is a collection of one or more types of concave parts and / or convex parts selected from letters, numbers, symbols, and figures (marks), and specifically, the manufacturer 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 is preferably a rectangle or an ellipse. 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 sewing product and the waterproof sheet sewing product. The marking area A is formed periodically in the longitudinal direction during the production of the industrial material sheet, and its formation position 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 and connecting them by lap joints, 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 will become the lap part, and in particular to form the marking area A on the back surface. The marking area A is continuously formed 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 one mark 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.Embossing is performed by pressing an embossing roll set at 100-180°C against a pair of rubber rolls, and the engraved markings are fixed by cooling (air-cooled and water-cooled rolls) after embossing. It is preferable that the engraved area A is on the inside of the tent membrane sewing product or the waterproof sheet sewing product to protect it from damage such as soot, rain, and ultraviolet rays. For example, 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 easy to separate the material for later recycling (weed control sheet) or disposal.

[0029] In addition, the tent membrane sewn product and the waterproof sheet sewn product of the present invention are welded by overlapping the ends of the industrial material sheets by 3 to 10 cm and connecting them by lap. This welding is performed by pressing a heated mold, specifically, pressing for 3 to 5 seconds by 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 the waterproof sheet sewn product, and this imprinting area B is stamped by pressing 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 and 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. In the engraving area B, information on the tent membrane sewing manufacturer or the waterproof sheet sewing manufacturer is designed, which is 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 engraving 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 engraving area B is formed by the mold bar, and letters, numbers, symbols, figures (marks) are designed in reverse on the mold bar. The engraving area B clarifies the sewing manufacturer information of the tent membrane sewing product or the waterproof sheet sewing product. It is preferable that the engraving area B is provided on the inside of the tent membrane sewing product and the inside of the waterproof sheet sewing product at intervals of 1 to 3 m, and is protected from damage such as soot, wind, rain, and ultraviolet rays. For example, the engraving area B "HIRAOKA" indicates that the sewing manufacturer is Hiraoka Ori-sen Co., Ltd., and the clarity of the engraving area B is maintained for a long time, making it possible to inquire about the manufacturer.

[0030] 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-shielding properties as good as 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 land, fallow land, solar power generation equipment installation areas, railway track slopes, etc., and the waterproof properties cut off water supply to plants (especially weeds), while the light-shielding properties cut off 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 suppressing 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 fixed to the ground with anchor pins, etc., in the same way as conventional weed control sheets. For tent membrane structures, white and ivory are particularly easy to obtain, while for truck hoods and waterproof sheets, dark green and olive drab are particularly easy to obtain. This type of 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 weed control sheets, if the user blindly lays down the weed control sheets without knowing the information on the materials such as the tent membrane sewing material and waterproof sheet sewing material, this is the same as dumping waste materials. Therefore, by clarifying the basic information of the tent membrane sewing material and waterproof sheet sewing material (stamped area B), and the basic information of the industrial material sheet that constitutes the tent membrane sewing material and waterproof sheet sewing material (stamped area A), it is possible to reuse as weed control sheets and fulfill the corporate (company) responsibility for disposal after reuse. If either engraved area A or engraved area B is unknown, 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 tent membrane sewn material and waterproof sheet sewn material into weed control sheets, at least the information on engraved area A is required.

[0031] 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 measuring 25 mm wide x 120 mm long including the imprinted area A was taken from the industrial material sheet. After leaving it in a 25℃ environment for 24 hours, it was attached to a Scott-type testing machine and subjected to a load of 1 kgf. The load was applied in a constant temperature room at 25°C and the surface after the test was The surface condition was observed, and the dynamic cold resistance was judged as follows. 1: No significant wear or abrasion is observed on the markings in the engraved area A 2: Significant wear is observed on the markings in the engraved area A, but they are still legible. 3: The markings in the engraved area A are worn down and cannot be read. (2) Abrasion resistance of the engraved area A: JIS L1096 8.19.3 C method) Tapered method A 13 cm diameter disk containing the imprinted area A taken from the industrial material sheet was used as the test piece. The abrasion tester was attached to a Taber type abrasion tester (wear wheel CS-10), and a load of 2.45 N was applied to the marking area A. After applying abrasive loads of 1000 and 2000 revolutions, the engraved area A was observed under a magnifying glass. The identification of the marking part in the engraved area A was evaluated. 1: No significant wear or abrasion is observed on the markings in the engraved area A 2: Significant wear is observed on the markings in the engraved area A, but they are still legible. 3: The markings in the engraved area A are worn down and cannot be read. (3) Formation of imprint area A 3-1) When manufacturing the industrial material sheet, the right edge of the industrial material sheet excluding the end 10 cm is Marking area A is printed at 8 m / min speed with a 30-inch diameter embossing roll at 240 cm intervals. The embossing roll is engraved with the words "PET&PVC" in reverse Gothic font. (1 character: 2cm x 2cm, line width 5mm, mirror surface: character spacing 5mm) Concave mirror surface due to display (Height difference 0.5mm), background is designed with matte convex part, industrial material sheet The marking area A was set to 180° along the longitudinal direction of the edge of the sheet. The embossing is performed by pressing the embossed sheet with a pair of rubber rolls. After embossing, the sheet is cooled (by air and water-cooled rolls). The marking is fixed. The marking area A is a matte-finished concave portion including a mirror-finished convex portion (marking portion). (Background: Height 3.5 cm x Width 19 cm) The area other than the engraved area A on the embossing roll is The outside is a mirror surface. 3-2) As in 1) above, "PET&PVC" in inverted Gothic font (1 character: 2cm 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 matte background design is a mirror image. The concave surface (display area) and the matte convex surface (background: height 3.5 cm x width 19 cm) are The boss roll has a mirror surface except for the marking area A. 3-3) As in 1) above, "PET&PVC" in inverted Gothic font (1 character: 2cm x 2cm line width 5mm matte finish: 5mm character spacing) Concave matte finish (height difference 0.5mm) The engraved area A obtained by using an embossing roll with a mirror-surface convex design in the background is The mirror concave surface (background: height 3.5 cm x width 19 cm) including the ground convex part (display part) The boss roll has a matte finish except for the marking area A. 3-4) As in 1) above, "PET&PVC" in inverted Gothic font (1 character: 2cm x 2cm line width 5mm matte finish: 5mm character spacing) Convex matte finish (height difference 0.5mm) The engraved area A obtained by using an embossing roll with a mirror-like concave design in the background is The mirror surface includes a concave portion (display area) (background: height 3.5 cm x width 19 cm). The boss roll has a matte finish except for the marking area A. (4) Formation of imprint area B The ends of two industrial material sheets are overlapped in a straight line parallel to each other with a width of 4 cm. A lap sewing section is provided, and a high-precision weld bar (stamping blade) measuring 4 cm wide x 30 cm long is attached. High frequency welder (Yamamoto Vinita Co., Ltd. YTO-8A type: high frequency output 8KW) The lap stitching part was aligned with the weld bar under oscillation with an anode current of 1.0A. The soft polyvinyl chloride resin coating layer was melted by high frequency oscillation to obtain a sewn product. The weld bar is engraved with the word "HIRAOKA" in inverted Gothic font (1 Characters: 2cm x 2cm, line width 5mm, mirror surface: character spacing 5mm, convex mirror surface (height difference 0.5 mm), and the background is designed with a matte textured recess in the marking area B. In the figure, the surface other than the engraved area B is a mirror surface.

[0032] Example 1 <Fabric (1)> The fabric was woven in a plain weave 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 300T / m) as the warp yarn and 10-count single-ply polyester staple spun yarn (S-twist 400T / m) as the weft yarn. The void ratio was 0 in appearance in terms of fuzz, and the mass was 240g / m 2 The fabric used was size 5. The fabric was treated for water repellency (dipping, heat treatment) with an acrylate / vinyl chloride resin copolymer emulsion (solid content 5% by mass) having a perfluoroalkyl group with 6 or less carbon atoms to prevent rainwater penetration (water absorption) in case of an abnormality 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 consisted of 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 for 3 minutes in a hot air oven at 180°C to form a soft vinyl chloride resin coating layer of 290 g / m 2 is formed on the entire surface of the fabric (1), and the imprint area A described in paragraph

[0031] 3-1) is provided on the back surface, and the mass is 530 g / m 2 A dark green waterproof canvas (1) was obtained. The imprinted area B described in paragraph (4) of (0031) was provided on the back surface of the sewn part of the sewn product of this waterproof canvas (1). 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 mass 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 liquid rubber: Contains 15% by mass of styrene as a block copolymer component. Properties: Average molecular weight 3000 with -COOH groups at both ends of the molecule *HMDI: Hexamethylene diisocyanate HMDI trimer (isocyanurate) has three isocyanate groups

[0033] Example 2 The processing liquid of Example 1 was changed from that of Blend 1 to that of Blend 2, and the marking area A described in paragraph

[0031] 3-2) was provided on the back surface. The same as Example 1, except that the mass was 530 g / m 2 A dark green waterproof canvas (2) was obtained. The imprinted area B described in paragraph (4) of (0031) was provided on the back surface of the sewn part of the sewn product of this waterproof canvas (2). The processing fluid of <Mixture 2> is prepared by replacing 10 parts by mass of the butadiene-based liquid rubber of <Mixture 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 ends of the molecule, and has an average molecular weight of 2500.

[0034] Example 3 The processing liquid of Example 1 was changed from Blend 1 to Blend 3, and the marking area A described in paragraph

[0031] 3-3) was provided on the back surface. The same as Example 1, except that the mass was 530 g / m 2 A dark green waterproof canvas (3) was obtained. The imprinted area B described in paragraph (4) of (0031) was provided on the back surface of the sewn part of the sewn product of this waterproof canvas (3). The processing fluid for <Mixture 3> is prepared by replacing 10 parts by mass of the butadiene-based liquid rubber in <Mixture 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 ends of the molecule, and has an average molecular weight of 5,000.

[0035] Example 4 The processing liquid of Example 1 was changed from <Composition 1> to <Composition 4>, and the marking area A described in paragraph

[0031] 3-4) was provided on the back surface. The same as Example 1, except that the mass was 530 g / m 2 A dark green waterproof canvas (4) was obtained. The imprinted area B described in paragraph (4) of (0031) was provided on the back surface of the sewn part of the sewn product of this waterproof canvas (4). The processing fluid of Blend 4 is prepared by adding 2 parts by mass of surface-modified silica particles to the processing fluid of Blend 1. The surface-modified silica particles are dry silica (gel method: average particle diameter 2 μm, BET specific surface area 300 m 2 / g) was stirred at 24°C for 3 hours in a 5% by mass aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (a silane coupling agent), separated, and dried. 3 ) 3 Modification and bonding to the siloxane moiety (-O) 3 Si-R-NH 2 Modifications are mixed.

[0036] Example 5 <Fabric (2)> A plain weave fabric was used for the warp and weft groups, which consisted of 1000 denier (1111 dtex) polyethylene terephthalate (PET) fibers (192 filaments) and S-twisted 50 T / m. The warp group had a weave of 16 threads per inch, and the weft group had a weave of 16 threads per inch. The mass of this fabric was 150 g / m 2 The porosity (total of holes) was 14%. This fabric was treated for water repellency (dipping, heat treatment) with an acrylate / vinyl chloride resin copolymer emulsion (solid content 5% by mass) having a perfluoroalkyl group with 6 or less carbon atoms to prevent rainwater from penetrating (absorbing water) 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. 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 melt-laminated by thermocompression bonding with a laminator on both sides of the substrate as the front and back soft vinyl chloride resin coating layers. Furthermore, the imprint area A described in 3-1) of paragraph

[0031] was provided on the back side, and a thickness of 0.7 mm and a mass of 830 g / m2 were obtained. 2 A white tent tarpaulin (1) was obtained. The imprinted area B described in paragraph (4) of

[0031] was provided on the back surface of the sewn part of the sewn product of the tent tarpaulin (1). [Formulation 5]: Soft polyvinyl chloride resin composition (compound) Straight polyvinyl chloride resin (K value 71.5) 100 parts by mass Diisononyl phthalate (DINP plasticizer) 60 parts by weight Butadiene-based liquid rubber* 10 parts by mass 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 liquid rubber: Contains 15% by mass of styrene as a block copolymer component. Properties: Average molecular weight 3000 with -COOH groups at both ends of the molecule *HMDI: Hexamethylene diisocyanate HMDI trimer (isocyanurate) has three isocyanate groups

[0037] Example 6 In Example 5, compound 〈Mixture 5〉 was changed to compound 〈Mixture 6〉. The same as in Example 5 except that the engraved area A described in 3-2) of

[0031] was provided on the back side, the thickness was 0.7 mm, and the mass was 830 g / m 2 A white tent tarpaulin (2) was obtained. The imprinted area B described in paragraph (4) of

[0031] was provided on the back surface of the sewn part of the sewn product of the tent tarpaulin (2). Compound 6 is prepared by replacing 10 parts by mass of the butadiene liquid rubber in Compound 5 with 10 parts by mass of isoprene liquid rubber. The isoprene liquid rubber contains 10% by mass of acrylonitrile as a block copolymer component, has -COOH groups at both ends of the molecule, and has an average molecular weight of 2500.

[0038] Example 7 The compound of Example 5 was changed from the compound of <Recipe 5> to the compound of <Recipe 7>, and the engraving area A described in paragraph

[0031] 3-3) was provided on the back surface. The thickness was 0.7 mm, and the mass was 830 g / m. 2 A white tent tarpaulin (3) was obtained. The imprinted area B described in paragraph (4) of (0031) was provided on the back surface of the sewn part of the sewn product of the tent tarpaulin (3). Compound 7 is prepared by replacing 10 parts by mass of the butadiene-based liquid rubber in Compound 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 ends of the molecule, and has an average molecular weight of 5,000.

[0039] Example 8 The compound of Example 5 was changed from the compound of <Recipe 5> to the compound of <Recipe 8>, and the engraving area A described in paragraph

[0031] 3-4) was provided on the back surface, but the same as Example 5. The thickness was 0.7 mm and the mass was 830 g / m 2 A white tent tarpaulin (4) was obtained. The imprinted area B described in paragraph (4) of (0031) was provided on the back surface of the sewn part of the sewn product of the tent tarpaulin (4). The processing fluid of <Recipe 8> is made by adding 2 parts by mass of surface-modified silica particles to the compound of <Recipe 5>. The surface-modified silica particles are dry silica (gel method: average particle size 2 μm, BET specific surface area 300 m 2 / g) was stirred at 24°C for 3 hours in a 5% by mass aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (a silane coupling agent), separated, and dried. 3 ) 3 Modification and bonding to the siloxane moiety (-O) 3 Si-R-NH 2 Modifications are mixed.

[0040] 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 form a product 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.

[0041] [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 × length 10 m sewn together to a width of 402 cm × length 10 m) was laid 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.

[0042] [Table 1]

[0043] [Table 2]

[0044] Waterproof canvases (1) to (4) of Examples 1 to 4 and tarpaulins for tents of Examples 5 to 8 (1) to (4) all have an engraving area A consisting of a display area and a background, and the appearance of the display area and background in all cases creates 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 polyvinyl 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 polyvinyl chloride resin coating layer. In the soft polyvinyl chloride resin coating layer before the 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 polyvinyl chloride resin coating layer, improving the wear resistance and abrasion resistance of the soft polyvinyl 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 (via 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, facilitating the subsequent separation for recycling (weed control sheet) / disposal. 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 make a decision at the time of recycling / disposal. In Example 9, it was demonstrated that the used sewn product of the waterproof canvas (1) in Example 1 can be reused as a weed control sheet, and in Example 10, it was demonstrated that the used sewn product of the tarpaulin (1) for tent membrane in Example 5 can be reused as a weed control sheet. Therefore, it is also possible to reuse the waste materials of the waterproof canvases (2) to (4) in Examples 2 to 4 and the tarpaulins (2) to (4) for tent membrane in 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 further, carbon dioxide emissions will be reduced.

[0045] [Comparative Example 1] A waterproof canvas (5) was obtained in the same manner as in Example 1, except that in the design used in Example 1, the engraved area A "PET&PVC" in inverted Gothic font (one character: 2 cm x 2 cm, line width 5 mm, mirror surface: character spacing 5 mm) had a concave mirror surface (height difference 0.5 mm) and the background was a matte convex portion, and the background was a mirror convex portion.

[0046] [Comparative Example 2] A waterproof canvas (6) was obtained in the same manner as in Example 1, except that in the design used in Example 1, the marking area A had inverted Gothic font characters (one character: 2 cm × 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 background with a matte convex portion, the marking area was made concave matte (height difference 0.5 mm).

[0047] [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 engraved area A used in Example 5, inverted Gothic font characters (1 character: 2 cm × 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 background convexity, the background was made into a mirror convexity.

[0048] [Comparative Example 4] In the design used in Example 5, the marking area A had inverted Gothic font characters (1 character: 2 cm × 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, but the marking area was made concave matte (height difference 0.5 mm), and a tarpaulin for tent membranes (6) was obtained in the same manner as in Example 5.

[0049] [Table 3]

[0050] [Comparative Example 5] The same procedure as in Example 1 was repeated except that 10 parts by mass of butadiene-based liquid rubber (having -COOH groups at both ends of the molecule and an average molecular weight of 3000) was omitted from the processing liquid of <Composition 1> in Example 1, and a mass of 530 g / m 2 I got dark green waterproof canvas (7). The soft polyvinyl chloride resin coating layer of the waterproof canvas (7) did not have a rubber cross-linked network, and therefore the marking area A formed on 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 unreadable due to wear.

[0051] [Comparative Example 6] The same procedure as in Example 1 was repeated except that 10 parts by mass of the 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 a butadiene-based liquid rubber having an average molecular weight of 3000 and no functional groups at both molecular terminals, and a mass of 530 g / m 2I got a dark green waterproof canvas (8). The soft polyvinyl chloride resin coating layer of the waterproof canvas (8) did not have a rubber cross-linked network, and therefore the marking area A formed on 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 unreadable due to wear.

[0052] [Comparative Example 7] The same procedure as in Example 1 was repeated 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). 2 From the dark green waterproof canvas (9), The soft polyvinyl chloride resin coating layer of the waterproof canvas (9) did not have a rubber cross-linked network, and therefore the marking area A formed on 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.

[0053] [Table 4] [Industrial Applicability]

[0054] 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 the marking information, the consumption of petrochemical raw materials is reduced since new weed control sheets are not required, which also leads to a reduction in carbon dioxide emissions. [Explanation of symbols]

[0055] 1-1: Mirror convex part (display part) 1-2: Satin Depression (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-finished surface (display area) 4-2: Mirror convex part (background)

Claims

1. 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).

2. 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, wherein 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 the pressure of the die bar during high-frequency welding.

3. 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, wherein 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 the pressure of the mold bar during high-frequency welding.

4. 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.

5. 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.

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