JP6383926B2 - Industrial tarpaulin - Google Patents

Description

The present invention uses a textile fabric as a base material, and is obtained by coating a soft vinyl chloride resin layer on a textile base material. Architectural curing, flexible container, wind pipe, oil fence, flexible water tank, water storage tank, water shielding of industrial waste disposal site Industrial tarpaulins used for laying, flexible signboards, sheet shutters, partitions, awnings / awnings, floor seats, optical ceiling membranes, railway vehicle hoods, cable covers, boat covers, grain / feed covers, waterproof apron, waterproof bags, And industrial tarpaulins used for medium to large tent membrane structures such as tent warehouses, pavilions, sports / leisure domes, planetariums, gas holders and the like. In the following paragraphs, the descriptions of industrial tarpaulins and tent film structure film materials mean industrial tarpaulins (tent film structure film materials).

  In soft vinyl chloride resin moldings containing a large amount of phthalic acid diester plasticizers such as dioctyl phthalate (DOP), diisononyl phthalate (DINP), and diheptyl phthalate (DHP), the plasticizer migrates to the surface as a time-dependent phenomenon. Soft vinyl chloride resin that gradually loses the plasticizer in the molding due to (bleed) and volatilizes it, which hardens the texture of the molding and eventually causes cracks in the molding. There is a problem that causes its own brittleness and deterioration. In addition, the plasticizer bleed has caused a problem that the surface of the molded product becomes sticky, and dust and dust are deposited on the sticky surface so that it becomes easy to get dirty in a short period of time, and the deposited dirt is difficult to remove.

  Recently, phthalate plasticizers are considered to be a mutagenic substance, and in the fields of toys, food wraps, medical devices, etc., replacement with non-phthalate plasticizers is beginning to be considered. . For example, Patent Document 1 exemplifies a vinyl chloride resin plasticizer containing 1,2-cyclohexanedicarboxylic acid diester as a vinyl chloride resin plasticizer using a non-phthalate ester compound. [0057] In the case of a vinyl chloride resin containing 1,2-cyclohexanedicarboxylic acid diester, if a large amount of 1,2-cyclohexanedicarboxylic acid diester is blended, the bleed on the surface of the molded product becomes severe. The same point is described in paragraph [0015] of Japanese Patent Application Laid-Open No. 2010-260967. Similarly, there is a disclosure of a case (Patent Document 2) in which 1,2-cyclohexanedicarboxylic acid diester is blended as an agricultural vinyl chloride resin film blended with a non-phthalate ester plasticizer. Also disclosed is the incorporation of 1,2-cyclohexanedicarboxylic acid diisononyl ester as a vinyl chloride resin film having excellent roll peelability, blocking resistance, transparency, printability and high frequency welder suitability (Patent Document 3). However, in the above-mentioned vinyl chloride resin molded products of Patent Documents 1 to 3, a specific method for suppressing or preventing bleeding of these 1,2-cyclohexanedicarboxylic acid diesters has been studied. Not. On the other hand, by blending cyclohexanedicarboxylic acid alkyl ester in a specific amount range with a mixture of a styrene thermoplastic resin and a polyester thermoplastic resin or polyurethane thermoplastic resin in a specific ratio range, various base resin and It is disclosed that a thermoplastic elastomer having a high adhesiveness, good moldability, low stickiness, good bleed resistance (observed at 23 ° C. for 48 hours) and good rubber feel can be obtained (Patent Document 4). ing. However, in the case of observation at 23 ° C. for 48 hours, the reliability of bleed resistance is insufficient for outdoor applications such as industrial tarpaulins and film materials for tent structures, and reliability of at least 2400 hours at room temperature is required.

  On the other hand, as a plasticizer based on a non-phthalate ester compound, a blocking-resistant agricultural polyvinyl chloride resin film using a terephthalate ester plasticizer (Patent Document 5) and a terephthalate ester plasticizer were used. Polyvinyl chloride wallpaper with excellent cold resistance (Patent Document 6), for covering electric wires and cables with excellent safety for human bodies containing isophthalate plasticizers such as di (2-ethylhexyl) isophthalate and / or diisononyl isophthalate A vinyl chloride resin composition (Patent Document 7) has been proposed. However, plasticizers based on these non-phthalate ester compounds are inferior in plasticization efficiency due to the bulky structure of the coordination space of the ester structure part relative to the dipole of the linear vinyl chloride resin, and the molecular weight increases ( Further reduction in plasticization efficiency with a molecular weight of 350 to 400) necessitates the use of non-phthalate ester compounds in the low molecular weight region with a molecular weight of about 250 to 300, but the low molecular weight of the plasticizer Is likely to cause plasticizer bleed (surface migration), and the plasticizer volatilization loss tends to harden the texture of the molded product, or dust adheres to the bleed material, which tends to make the molded product look dirty. There is. However, in the vinyl chloride resin compositions and the like of Patent Documents 5 to 7, there is no disclosure or suggestion of means for inhibiting or preventing bleed (migration) of terephthalic acid ester plasticizers or isophthalic acid ester plasticizers. Accordingly, a soft vinyl chloride resin composition in which plasticizer bleed is suppressed to a very small amount over a long period of time, and the contamination such as change in texture and dust dirt is reduced, and in particular, soft vinyl chloride by a non-phthalate ester compound. There is no industrial tarpaulin or tent structure film material using a resin composition, and such an industrial tarpaulin or tent structure film material has been desired.

JP 2001-207002 A JP 2002-363366 A JP 2011-231226 A JP 2010-163557 A Japanese Patent Laid-Open No. 2002-234983 JP 2012-184529 A JP 2012-089287 A

  INDUSTRIAL APPLICABILITY The present invention uses a textile fabric as a base material, architectural curing obtained by coating a soft vinyl chloride resin layer on the textile base material, flexible containers, wind pipes, oil fences, flexible water tanks, water storage tanks, and impermeable laying of industrial waste disposal sites. Industrial tarpaulins used for flexible signboards, sheet shutters, partitions, awnings and rain shields, floor sheets, optical ceiling membranes, railway vehicle hoods, cable covers, boat covers, grain / feed covers, waterproof apron, waterproof bags, etc. Tarpaulins used for medium to large tent membrane structures such as tent warehouses, pavilions, sports / amusement domes, planetariums, gas holders, etc., especially plasticizer bleed is suppressed to a very small amount over a long period of time, and texture changes and dust Providing industrial material sheets with minimal contamination such as dirt A.

  The present inventors have studied and studied an industrial tarpaulin and a tent structure film material made of a soft vinyl chloride resin in view of the above-mentioned situation, and as a result, an industrial tarpaulin and a tent structure film material according to the present invention are A flexible laminate comprising a textile fabric as a base material and a soft vinyl chloride resin layer provided on at least one surface thereof, wherein the soft vinyl chloride resin layer mainly comprises a vinyl chloride resin and a plasticizer; The soft polyvinyl chloride resin layer contains the acrylic copolymer rubber component in a specific amount range, and by using a specific plasticizer, the obtained tarpaulin and the membrane material for tent structure, especially the plasticizer bleed are long. The present invention was completed by finding that it was suppressed to a very small amount over a period of time, and that contamination such as texture change and dust contamination was slight.

That is, the industrial tarpaulin and the membrane material for a tent structure of the present invention are a flexible laminate in which a soft vinyl chloride resin layer is provided on at least one surface of a textile fabric as a base material, The vinyl resin layer mainly contains a vinyl chloride resin and a plasticizer, the soft vinyl chloride resin layer contains 1 to 10% by mass of an acrylic copolymer rubber component, and the plasticizer is isophthalic acid. Dialkyl ester ([Chemical group 1]), terephthalic acid dialkyl ester ([Chemical group 2]), 1,2-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 3]), 1,3-cyclohexanedicarboxylic acid dialkyl ester It is at least one selected from an ester ([Chemical Group 4]) and a 1,4-cyclohexanedicarboxylic acid dialkyl ester ([Chemical Group 5]). Masui. In the membrane material for tarpaulins and tent structures obtained in this way, plasticizer bleed is suppressed to a very small amount over a long period of time, and contamination such as texture change and dust dirt is minimized.

  In the industrial tarpaulin and tent structure film material of the present invention, the acrylic copolymer rubber component is 1) a random copolymer obtained by polymerization of a plurality of alkyl (meth) acrylate monomers, and 2) (meth) acrylic. A block copolymer containing at least one polymer block (A) and an isobutylene polymer block (B), or at least a methacrylic polymer block (A) and an acrylic polymer block (C), respectively. 1) Block copolymer containing 3) Graft copolymer by polymerization of one or more alkyl (meth) acrylate monomers and vinyl monomers, 4) According to one or more alkyl (meth) acrylate monomers Graft copolymer by polymerization of polymer and silicone rubber 5) One or more alkyl (meth) acrylates It is preferable aromatic vinyl copolymer, is at least one selected from - and rate-based monomer, butadiene monomer, by polymerizing the aromatic vinyl monomer acrylate - butadiene. By containing such an acrylic copolymer rubber component, it is excellent in compatibility and retention with non-phthalate ester compounds, thereby making the plasticizer (non-phthalate ester compound) bleed longer. In addition, it suppresses to a very small amount and minimizes contamination such as texture change and dust dirt.

  In the industrial tarpaulin and tent structure membrane material of the present invention, a fluororesin layer is formed on the soft vinyl chloride resin layer, and the fluororesin constituting the fluororesin layer is vinyl fluoride (VF) or vinylidene fluoride. (VdF), trifluoroethylene (TrEE), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), a polymer obtained by homopolymerizing one kind of monomer selected from hexafluoropropylene (HFP), or these It is preferable that it is 1 or more types chosen from the copolymer formed by copolymerizing 2 or more types of these monomers, or the copolymer formed by copolymerizing these 1 or more types of monomers with a vinyl monomer. The tarpaulin and tent structure membrane material obtained in this way has a fluororesin layer as a barrier layer to prevent bleed of plasticizers over a long period of time, and at the same time minimizes changes in texture and dust contamination. And exhibit excellent antifouling properties and excellent soil removability.

  The industrial tarpaulin and tent structure membrane material of the present invention is a binder component in which an inorganic colloidal material having a primary particle diameter of 3 to 150 nm contains a hydrolysis condensate of a silane coupling agent on the soft vinyl chloride resin layer. An antifouling layer is provided, and the inorganic colloidal substance is a photocatalytic titanium oxide sol, a photocatalytic zinc oxide sol, a photocatalytic tin oxide sol, a titanium oxide sol, a zinc oxide sol, a tin oxide sol, a silica sol, One or more metal oxides selected from aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and complex oxide (zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sol are preferable. The tarpaulin and tent structure membrane material obtained in this way has an antifouling layer as a barrier layer, and the bleed of the plasticizer is suppressed to a very small amount over a long period of time. At the same time, it exhibits excellent antifouling properties and excellent soil removability, and further exhibits excellent antistatic properties.

  The membrane material for industrial tarpaulins and tent structures of the present invention is especially useful for building curing and flexible containers because plasticizer bleed is suppressed to a very small amount over a long period of time, and the contamination such as texture change and dust contamination is minimized. , Wind pipes, oil fences, flexible aquariums, water storage tanks, water barrier laying of industrial waste disposal sites, flexible signboards, seat shutters, partitions, awnings and rain shields, floor seats, optical ceiling membranes, railroad vehicle hoods, cable covers, boats Long as a tarpaulin used for medium to large tent membrane structures such as industrial tarpaulins used for covers, grain / feed covers, waterproof apron, waterproof bags, tent warehouses, pavilions, sports amusement domes, planetariums, gas holders, etc. It can be used stably for a period.

  The industrial tarpaulin and tent structure membrane material according to the present invention is a flexible laminate in which a soft vinyl chloride resin layer is provided on at least one surface of a textile fabric as a base material. The vinyl resin layer mainly contains a vinyl chloride resin and a non-phthalic acid plasticizer, and further contains a soft vinyl chloride resin layer (mainly a vinyl chloride resin and a plasticizer. (Including known compounding agents for vinyl chloride resin such as a fuel, a filler, and a pigment) 1 to 10% by mass of an acrylic copolymer rubber component, and a non-phthalic acid plasticizer is a dialkyl ester of isophthalic acid , Terephthalic acid dialkyl esters, 1,2-cyclohexanedicarboxylic acid dialkyl esters, 1,3-cyclohexanedicarboxylic acid dialkyl esters, and 1,4-cyclohexane To mandatory that at least one member selected from carboxylic acid dialkyl ester.

The fiber woven fabric as a base material used for the industrial tarpaulin and the membrane material for tent structure of the present invention is a mass woven from synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these. 50-500 g / m ² , preferably a woven fabric with a mass of 65-280 g / m ² . Synthetic fibers include nylon fibers, vinylon fibers, polypropylene fibers, polyester fibers, ultrahigh molecular weight polyethylene fibers, aramid fibers, and heterocyclic polymer fibers. Examples of natural fibers include cotton, hemp and kenaf, and examples of semisynthetic fibers include rayon and acetate. Examples of the inorganic fiber include glass fiber, silica fiber, alumina fiber, and carbon fiber. In particular, in the present invention, known woven fabrics such as a plain fabric, a raschel woven fabric, a twill woven fabric, a satin woven fabric, and an imitation woven fabric using a filament yarn or a spun yarn made of a synthetic fiber can be used. These base fabrics may be subjected to water repellent treatment, water absorption prevention treatment, adhesion treatment, flame retardant treatment, and the like as necessary. The fiber fabric used in the present invention is preferably a plain fabric made of polyester fiber, vinylon fiber, nylon fiber, glass fiber or the like.

A base fabric suitable for tarpaulin in the present invention is a multifilament yarn of 278 to 3333 dtex, preferably 555 to 2222 dtex (a flat yarn having a non-twisted cross-section, a right-handed or left-handed twisted yarn or a twisted yarn, and a substantially elliptical cross-section. A plain woven fabric and a Russell woven fabric having a void porosity of 5% to 35%, particularly a porosity of 5% to 25% using yarns are preferable. There are no particular restrictions on the warp and weft driving density of these fabrics, but there are fabrics obtained by driving 10 to 80 yarns per inch using the yarn as warps and wefts, and a fabric having a basis weight of 50 to 500 g / m ² . Is suitable. The base fabric that can be used in the present invention includes a ripstop fabric. As the ripstop fabric, for example, a mixed fabric in which a part of warp and / or weft of a base fabric made of polyester multifilament yarn is regularly or randomly substituted with an aramid fiber multifilament yarn, similarly, paragraph [0014] And a mixed woven fabric in which two or more kinds of fibers described in 1) are combined. By making such specifications, the tear strength of tarpaulins obtained and the ability to prevent breakthrough due to protrusions are effectively improved.

The soft vinyl chloride resin layer in the industrial tarpaulin and tent structure membrane material of the present invention mainly contains a vinyl chloride resin and a plasticizer, and the soft vinyl chloride resin layer further contains an acrylic copolymer rubber component. 1 to 10% by mass and the plasticizer to be used is diphthalic acid dialkyl ester ([Chemical group 1]), terephthalic acid dialkyl ester ([Chemical group 2]), dialkyl 1,2-cyclohexanedicarboxylate Selected from ester ([Chemical 3] group), 1,3-cyclohexanedicarboxylic acid dialkyl ester ([Chemical 4] group), and 1,4-cyclohexanedicarboxylic acid dialkyl ester ([Chemical 5] group) Contains one or more liquid compounds. In the group of dialkyl esters represented by [Chemical Formula 1] to [Chemical Formula 5], each R is the same or different and is an aliphatic monovalent group having 4 to 13 carbon atoms (C), such as a linear alkyl group. Represents a branched alkyl group, an alicyclic group, or the like.

  As the plasticizer for the dialkyl ester of isophthalic acid ([Chemical Group 1]), for example, di (2-ethylhexyl) isophthalic acid (C8: MW390) synthesized by an esterification reaction of isophthalic acid and 2-ethylhexanol is particularly preferable. Other dibutyl isophthalate (C4: MW278), diisobutyl isophthalate (C4: MW278), dihexyl isophthalate (C6: MW334), diheptyl isophthalate (C7: MW362), dinonyl isophthalate (C9: MW418), diisononyl isophthalate (C9: MW418), diisodecyl isophthalate (C10: MW447), didecyl isophthalate (C10: MW447), butylbenzyl isophthalate (C4, C7: MW312), and the like. For example, di-2-ethylhexyl terephthalate (dioctyl terephthalate) (C8: MW390) synthesized by esterification reaction of terephthalic acid and 2-ethylhexanol is used as a plasticizer of terephthalic acid dialkyl ester ([Chemical Group 2]). Particularly preferred, other dibutyl terephthalate (C4: MW278), diisobutyl terephthalate (C4: MW278), dihexyl terephthalate (C6: MW334), diheptyl terephthalate (C7: MW362), dinonyl terephthalate (C9: MW418) Examples are diisononyl terephthalate (C9: MW418), diisodecyl terephthalate (C10: MW447), didecyl terephthalate (C10: MW447), and butylbenzyl terephthalate (C4, C7: MW312). It is. In the group of dialkyl esters shown in [Chemical Formula 1] and [Chemical Formula 2], R is the same or different from each other, and an aliphatic monovalent group having 4 to 10 carbon atoms, such as a linear alkyl group, branched It is preferably a chain alkyl group. When the number of carbon atoms is 11 or more, the steric hindrance due to the arrangement structure of the alkyl ester increases due to the isophthalic acid structure and the terephthalic acid structure, and the coordination order of the ester polar part to the dipole of the vinyl chloride resin becomes coarse. There is a tendency for plasticization efficiency to decrease.

  A plasticizer of 1,2-cyclohexanedicarboxylic acid dialkyl ester ([Chemical Group 2]) is, for example, 1,2-cyclohexanedicarboxylic acid di-2-ethylhexyl obtained by hydrogenating the benzene ring of DOP (dioctyl phthalate). (Also known as dioctyl 1,2-cyclohexanedicarboxylate) (C8: MW393), other dibutyl 1,2-cyclohexanedicarboxylate (C4: MW281), diisobutyl 1,2-cyclohexanedicarboxylate (C4: MW281), 1 , 2-cyclohexanedicarboxylic acid dihexyl (C6: MW337), 1,2-cyclohexanedicarboxylic acid diheptyl (C7: MW362), 1,2-cyclohexanedicarboxylic acid dinonyl (C9: MW421), 1,2-cyclohexanedicarboxylic acid diisono (C9: MW421), 1,2-cyclohexanedicarboxylate diisodecyl (C10: MW450), 1,2-cyclohexanedicarboxylate didecyl (C10: MW450), 1,2-cyclohexanedicarboxylate butylbenzyl (C4, C7: MW315) And the like. The plasticizer of 1,3-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 4]) is, for example, 1,3-cyclohexanedicarboxylic acid di-2 obtained by hydrogenating the benzene ring of (Chemical group 1). -Ethylhexyl (also known as dioctyl 1,3-cyclohexanedicarboxylate) (C8: MW393) is particularly preferred, and dibutyl 1,3-cyclohexanedicarboxylate (C4: MW281), diisobutyl 1,3-cyclohexanedicarboxylate (C4: MW281) 1,3-cyclohexanedicarboxylic acid dihexyl (C6: MW337), 1,3-cyclohexanedicarboxylic acid diheptyl (C7: MW365), 1,3-cyclohexanedicarboxylic acid dinonyl (C9: MW421), 1,3-cyclohexanedicarboxylic acid Diisononyl (C9: W421), 1,3-cyclohexanedicarboxylate diisodecyl (C10: MW450), 1,3-cyclohexanedicarboxylate didecyl (C10: MW450), 1,3-cyclohexanedicarboxylate butylbenzyl (C4, C7: MW315), etc. Is done. The plasticizer of 1,4-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 5]) is, for example, 1,2-cyclohexanedicarboxylic acid di-2 obtained by hydrogenating the benzene ring of (Chemical group 2). -Ethylhexyl (also known as dioctyl 1,4-cyclohexanedicarboxylate) (C8: MW393) is particularly preferred, and dibutyl 1,4-cyclohexanedicarboxylate (C4: MW281), diisobutyl 1,4-cyclohexanedicarboxylate (C4: MW281) 1,4-cyclohexanedicarboxylic acid dihexyl (C6: MW337), 1,4-cyclohexanedicarboxylic acid diheptyl (C7: MW362), 1,4-cyclohexanedicarboxylic acid dinonyl (C9: MW421), 1,4-cyclohexanedicarboxylic acid Diisononyl (C9: W421), 1,4-cyclohexanedicarboxylate diisodecyl (C10: MW450), 1,4-cyclohexanedicarboxylate didecyl (C10: MW450), 1,4-cyclohexanedicarboxylate butylbenzyl (C4, C7: MW315), etc. Is done. In the group of dialkyl esters represented by these [Chemical Formula 3] to [Chemical Formula 5], R is the same or different from each other, and an aliphatic monovalent group having 4 to 10 carbon atoms, such as a linear alkyl group, branched It is preferably a chain alkyl group. When the number of carbon atoms is 11 or more, the steric hindrance due to the arrangement of the alkyl ester in the cyclohexanedicarboxylic acid structure becomes large, and the coordination order of the ester polar part to the dipole of the vinyl chloride resin becomes coarse, resulting in a decrease in plasticization efficiency. Tend to.

  Other plasticizer components that can be used in combination with the plasticizers described in paragraphs [0017] and [0018] ([Chemical group 1] to (Chemical group 5)) include acetylcitric acid as necessary. Tributyl, di-2-ethylhexyl adipate, tri-2-ethylhexyl trimellitic acid, tricresyl phosphate, reactive acrylic compound having two or more (meth) acryloyl groups at the molecular end or side chain, and allyl group Allyl phthalate-based compounds having 2 or more can be used together in an amount of about 5 to 15% by mass with respect to each of the plasticizers of ([Chemical group 1] to (Chemical group 5)].

  In the present invention, the soft vinyl chloride resin layer contains a vinyl chloride resin as a main component, and includes the plasticizers of (group of [Chemical 1]) to (group of [Chemical 5]) described in paragraphs [0017] and [0018]. Containing one or more types, and by including a plasticizer, the vinyl chloride resin is effectively plasticized into a soft vinyl chloride resin, and further a soft vinyl chloride resin layer (vinyl chloride resin, mainly containing a plasticizer, if necessary) In addition, known vinyl chloride resin compounding agents such as stabilizers, flame retardants, fillers, pigments, etc.) contain 1 to 10% by mass of an acrylic copolymer rubber component so that the flexible vinyl chloride resin layer can be flexibly flexible. At the same time, the compatibility with non-phthalate ester plasticizers of [Chemical group 1] to [Chemical group 5] is excellent, whereby non-phthalic acid is contained in the acrylic copolymer rubber component. Ester compounds are stable In makes it possible to prevent a small amount over the bleeding of plasticizer long time. The content ratio of the plasticizer of ([Chemical group 1] to (Group of [Chemical group 5]) and the acrylic copolymer rubber component is preferably in the range of 65: 1 to 65:10. The preferred blending amount of the non-phthalate ester plasticizer selected from the group of [Chemical 1] to [Chemical 5] is 35 to 100 parts by mass, preferably 50 to 100 parts by mass of the vinyl chloride resin. 80 parts by mass. Therefore, when 100 parts by mass of the above non-phthalate ester plasticizer is added to 100 parts by mass of the vinyl chloride resin (the acrylic copolymer rubber component is included in the mass of the soft vinyl chloride resin layer), The amount of the copolymer rubber component used is in the range of 2.05 (1% by mass) to 22.3 (10% by mass), and 35 parts by mass of the above non-phthalate ester plasticizer is blended in the same manner. The use amount range of the acrylic copolymer rubber component used in the case is 1.35 (1% by mass) to 15 (10% by mass) parts by mass. The usage range of the acrylic copolymer rubber component varies depending on the blending amount of the stabilizer, flame retardant, filler, pigment and the like blended in the soft vinyl chloride resin layer.

  Vinyl chloride resin is a copolymer of vinyl chloride monomer homopolymer (emulsion polymerization type, suspension polymerization type with a polymerization degree of 700-3800) and other monomers that can be copolymerized with vinyl chloride monomer. In the case of such a copolymer, a copolymer having a vinyl chloride-containing component exceeding 60% by mass is treated as a vinyl chloride resin in the requirements of the present invention. Examples of copolymer components include α-olefins having 2 to 30 carbon atoms, acrylic acid and esters thereof, methacrylic acid and esters thereof, maleic acid and esters thereof, vinyl acetate, vinyl propionate, and alkyl vinyl ether. Compound etc. are mentioned. The soft vinyl chloride resin layer may contain various arbitrary amounts of known additives for soft vinyl chloride resin. As stabilizers for soft vinyl chloride resin, calcium zinc composite, barium zinc composite, organic tin Stabilizers such as laurate, organotin mercaptite, and epoxy can be used alone or in combination. If necessary, it may contain a light-resistant stabilizer, an ultraviolet absorber, an antioxidant, an antibacterial agent, an antifungal agent, a colorant (pigment), a fluorescent whitening agent, an antistatic agent, a wax and the like.

  In the present invention, as an acrylic copolymer rubber component contained in the soft vinyl chloride resin layer, 1) a random copolymer obtained by polymerization of a plurality of alkyl (meth) acrylate monomers, 2) (meth) acrylic polymer block (A ) And at least one isobutylene polymer block (B), or a block copolymer containing at least one methacrylic polymer block (A) and acrylic polymer block (C). A polymer, 3) a graft copolymer by polymerization of one or more alkyl (meth) acrylate monomers and a vinyl monomer, 4) a polymer by polymerization of one or more alkyl (meth) acrylate monomers, Graft copolymer by polymerization with silicone rubber, 5) One or more alkyl (meth) acrylates One or more selected from an acrylate-butadiene-aromatic vinyl copolymer obtained by polymerization of a monomer with a butadiene monomer and an aromatic vinyl monomer, and having a glass transition temperature of 2 or more at 10 ° C. or lower Is preferred. Here, the notation of “(meth) acrylate...” Is a notation representing both or either of acrylate and methacrylate, and the notation of “(meth) acrylic... The following descriptions are all handled in the same manner.

  As an acrylic copolymer rubber component, 1) As a random copolymer by polymerization of a plurality of alkyl (meth) acrylate monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) Acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, 4-hydroxybutyl (meth) acrylate, lauryl (meth) acrylate, Two or more kinds selected from alkyl (meth) acrylate monomers such as stearyl (meth) acrylate, preferably a random copolymer obtained by polymerization of two kinds of monomers, having a glass transition temperature of 2 or more at 10 ° C. or lower. preferable

  As the acrylic copolymer rubber component, 2) a block copolymer containing at least one (meth) acrylic polymer block (A) and an isobutylene polymer block (B), or a methacrylic polymer block A block copolymer containing at least one of (A) and an acrylic polymer block (C) and having a glass transition temperature of 2 or more at 10 ° C. or lower is preferable. These are AB type, or AC type diblock copolymer, ABA type, or ACA type triblock copolymer, BAB type, or C- type. AC type triblock copolymer, (AB) n type, or (AC) n type multiblock copolymer. The composition ratio of the (meth) acrylic polymer block (A) and the isobutylene polymer block (B) constituting the block copolymer is 5 to 90% by weight for the component (A) and 95 to 95% for the component (B). 10% by weight, particularly preferably 20 to 50% by weight of component (A) and 80 to 50% by weight of component (B). The composition ratio of the methacrylic polymer block (A) and the acrylic polymer block (C) constituting the block copolymer is 5 to 90% by weight for the (A) component and 95 to 95% for the (C) component. 10% by weight, particularly preferably 20 to 50% by weight of component (A) and 80 to 50% by weight of component (C). The (meth) acrylic polymer block (A) is the same as the acrylic copolymer rubber component described in paragraph [0023], and the acrylic polymer block (C) is an acrylic copolymer described in paragraph [0023]. Among the combined rubber components, the polymer is limited to acrylic monomers that are not meta-based.

  As the acrylic copolymer rubber component, 3) in the graft copolymer obtained by polymerization of one or more kinds of alkyl (meth) acrylate monomers and vinyl monomers, the alkyl (meth) acrylate rubbers are described in paragraph [0023]. The same acrylic copolymer rubber component as described, and may be a polyorganosiloxane / (meth) acrylate composite rubber. Examples of vinyl monomers include aromatic alkenyl compounds such as styrene, α-methylstyrene, vinyl toluene, and acrylonitrile; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylics such as methyl acrylate, ethyl acrylate, and n-butyl acrylate. Acid esters; various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methacrylic acid-modified silicones and fluorine-containing vinyl compounds can be used alone or in combination of two or more. Such an acrylic rubber-based graft copolymer preferably has a glass transition temperature of 2 or more at 10 ° C. or lower. As a specific acrylic copolymer rubber, trade name “Kane Ace” FM series manufactured by Kaneka Corporation is exemplified.

  As the acrylic copolymer rubber component, 4) a graft copolymer obtained by polymerization of one or more alkyl (meth) acrylate monomers and a silicone rubber, the alkyl (meth) acrylate rubber is: The silicone rubber is the same as the acrylic copolymer rubber component described in paragraph [0023], and the silicone rubber is a: main skeleton component) organosiloxane, b: cross-linking introduction agent) polyfunctional silane compound, c: graft crossover agent) vinyl The ratio of the alkyl (meth) acrylate rubber to the silicone rubber is a silicone rubber made of a copolymer of a silane compound having a polymerizable group, and the ratio of the alkyl (meth) acrylate rubber to the silicone rubber is 95: 5 to 50: A range of 50. Examples of the organosiloxane of a) include 6- to 12-membered cyclic siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. Examples of silane compounds include tetramethoxysilane, tetraethoxysilane, triethoxymethylsilane, triethoxyethylsilane, and the like, and c) silane compounds having a vinyl polymerizable group include allyl methacrylate, diallyl phthalate, and cyanuric acid. Triallyl, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, silane compounds having a mercapto group in the molecule, cyclic vinyl siloxane having a vinyl polymerizable group in the molecule, tetravinyl Tetramethyl cyclotetrasiloxane, etc. tetra methacryloyloxypropyl tetramethyl cyclotetrasiloxane and the like. The copolymerization ratios of these a), b) and c) are preferably in the range of a) 70 to 99.9%, b) 0 to 15%, c) 0 to 15%, and the glass transition temperature to 10 ° C. or less. What has 2 or more is preferable. As the acrylic rubber-based graft copolymer, trade name “METABBRENE” S series manufactured by Mitsubishi Rayon Co., Ltd. is exemplified.

  As an acrylic copolymer rubber component, 5) an acrylate-butadiene-aromatic vinyl copolymer obtained by polymerization of one or more alkyl (meth) acrylate monomers, a butadiene monomer, and an aromatic vinyl monomer; The (meth) acrylate monomer is the same as the acrylic copolymer described in paragraph [0023], the butadiene monomer is preferably 1,3-butadiene, the aromatic vinyl monomer is styrene, α-substituted styrene, and nuclear substitution. Styrene and its derivatives, such as α-methylstyrene, chlorostyrene and vinylstyrene, are exemplified, and the range of butadiene units is 55 to 85% by weight and aromatic vinyl compound units are preferably 15 to 45% by weight. Each unit is random. Either an array or a block array may be used. Such an acrylate-butadiene-aromatic vinyl copolymer preferably has a glass transition temperature of 2 or more at 10 ° C. or lower. Specifically, trade names “Kane Ace” B series and M series manufactured by Kaneka Corporation are exemplified.

  As a method of forming a soft vinyl chloride resin layer on a textile fabric, for example, a non-phthalic acid selected from (group of [Chemical 1]) to (group of [Chemical 5]) on a vinyl chloride resin (100 parts by mass) Using a compound composition containing an ester plasticizer (35 to 100 parts by mass) and an acrylic copolymer rubber component in an amount of 1 to 10% by mass based on the soft vinyl chloride resin layer, this is calendered. A film (sheet) molded to a thickness of 0.05 mm to 1.0 mm or a film (sheet) extruded to a thickness of 0.05 mm to 1.0 mm by the T-die method is used for a fiber woven fabric having a void ratio of 5 to 35%. Laminate on both sides, and tarpaulin is obtained by a thermal laminating method based on the fusing bridge effect. In addition, when using fiber fabrics with a void porosity of less than 5%, the fiber fabrics are pre-impregnated with an adhesive, or gravure coated, or knife coated, and dry laminated using an adhesive. Get a tarpaulin. These adhesives include known emulsion type adhesives (for example, urethane type used in combination with isocyanate type curing agents), known solvent type adhesives (eg, urethane type used in combination with isocyanate type curing agents), and paste-like soft chlorides. A vinyl resin composition (paste sol or organosol) can be used.

  By forming a fluororesin layer on the soft vinyl chloride resin layer, the tarpaulin and tent structure film material obtained can be prevented from bleeding for a long period of time because the fluororesin layer becomes a barrier layer. In addition to exhibiting the effect, it exhibits excellent antifouling properties and excellent soil removability. The fluororesin constituting this fluororesin layer is composed of vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene (TrEE), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene ( Polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), polytrifluoroethylene (PTrEE), polytetrafluoroethylene (PTFE), polychloro, which is obtained by homopolymerizing one monomer selected from HFP) Examples thereof include trifluoroethylene (PCTFE) and polyhexafluoropropylene (PHFP). Also, a VdF-TFE copolymer resin, a VdF-CTFE copolymer resin, a VdF-HFP copolymer resin, a TFE-CTFE copolymer resin, a TFE, which are obtained by copolymerizing two or more monomers exemplified above. -HFP copolymer resin, CTFE-HFP copolymer resin, VdF-TFE-CTFE copolymer resin, VdF-TFE-HFP copolymer resin, TFE-CTFE-HFP copolymer resin, VdF-CTFE-HFP Examples thereof include copolymer resins and VdF-TFE-CTFE-HFP copolymer resins. The fluororesin layer is formed by calendering the above-mentioned resin raw material (compound) or by molding a single layer or multiple layers by T-die extrusion, and using a fluororesin dispersion (fine resin particle dispersion). In this case, the fluororesin layer is formed by fusing and integrating fine resin particles through a baking process subsequent to a coating process such as a dipping squeezing in a liquid bath or knife coating or clearance coating.

Also, a fluoroolefin copolymer resin obtained by copolymerizing one or more fluororesin monomers exemplified above with a vinyl monomer, and a soluble resin having solubility in an organic solvent is known in the art such as gravure coating and knife coating. A fluororesin layer can be formed by coating. Vinyl monomers that can be used are 1) β-methyl-β-alkyl-substituted α-olefins represented by CH ₂ ═CR (CH ₃ ) (* R is an alkyl group having 1 to 8 carbon atoms), 2) CH ₂ = CHOR, CH ₂ = CHCH ₂ OR (* R is an alkyl vinyl ether or alkyl allyl ether represented by an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group), 3) CH ₂ = COOR, CH ₂ = OCOR, CHCOOR = COOR, CHCOOR = OCOR (* R is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. A vinyl group-containing ester represented by (alkyl-substituted phenyl group). These fluoroolefin copolymer resins have a reactive group such as a hydroxyl group and a carboxyl group in the copolymer vinyl component, and known curing agents (crosslinking agents) such as isocyanate compounds, aziridine compounds, oxazoline compounds, carbodiimide compounds, and melamine compounds. ) With respect to the fluoroolefin copolymer resin (solid content) in an amount of 1 to 20% by mass, preferably 3 to 15% by mass, in terms of solid content. Rain and weather resistance can be improved. Of these, isocyanate compounds are particularly preferred because of their excellent reactivity with hydroxyl groups, and aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds are particularly preferred from the viewpoint of weather resistance.

In addition, an inorganic colloid material having a primary particle diameter of 3 to 150 nm is formed on the soft vinyl chloride resin layer (may be on the fluororesin layer described in paragraphs [0029] and [0030]) as a silane coupling agent. By providing an antifouling layer supported on a binder component containing a hydrolyzed condensate, the resulting tarpaulin and tent structure membrane material has a barrier layer as the antifouling layer, and the plasticizer bleeds for a long time. It is possible to exhibit excellent antifouling properties and excellent soil removability, as well as to exhibit excellent antistatic properties at the same time as the effects that are prevented over time. The inorganic colloid materials used are photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and composite One or more metal oxides selected from oxide (zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sols can be used, particularly photocatalytically active titanium oxide sols, photocatalytically active zinc oxide sols, and photocatalysts. An active tin oxide sol is preferred because of its excellent antifouling effect. As the binder component, a silane coupling agent can be used, and these are compounds having two or more different reactive groups in the molecule represented by the general formula: XR-Si (Y) ₃ , for example, X = amino group, Examples thereof include vinyl group, epoxy group, chloro group, mercapto group (R = alkyl chain), Y = methoxy group, ethoxy group and the like. These hydrolysates and cohydrolyzed compounds with alkoxysilane compounds can also be used. Specifically, the silane coupling agent is vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycol. Sidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino Examples include propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. Although there is no limitation in the content rate of the inorganic colloid substance which occupies for an antifouling layer, 25-50 mass% is especially preferable. These antifouling layers are formed by applying and drying a solution of a resin soluble in a solvent or water, or an emulsion by a coating method such as spray coating or gravure coating. As necessary, the binder component is an acrylic resin, a fluorine copolymer resin, an acrylic-silicon copolymer resin, an acrylic-fluorine copolymer resin, an acrylic-urethane copolymer resin, an acrylic resin and a fluorine copolymer resin. Blends can also be used in combination.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. Below, the evaluation method of the sheet | seat of an Example and a comparative example is demonstrated.
<Inhibition effect of plasticizer bleed: wettability evaluation>
A sample of 10 cm × 10 cm size is sandwiched between two glass plates (10 cm × 10 cm size × 5 mm thickness), and this is left standing for 2400 hours in a state of being placed flat at 23 ° C., and the glass plate surface immediately after taking out (fogging) ) The plasticizer bleed deterrence (prevention) was judged by visual inspection and finger touching for presence or absence of bleed (bleed).
1 (Good): Level at which no fogging is observed on the glass plate surface 2 (Slightly bad): Level at which the glass plate surface is fogged and slips when touched 3 (Bad): Remarkable wetting is observed on the glass plate surface, and on the sample surface Level where wetting is observed <Inhibition effect of plasticizer bleed: Volatile loss assessment>
A 10 cm × 10 cm sample with a clear mass was allowed to stand in a gear oven set at 85 ° C. for 72 hours, and the volatilization amount of the plasticizer was determined from the mass of the sample after removal. The deterrence (prevention) of the plasticizer bleed was judged based on “large” and “small”.
1: (Bleed prevention effect is recognized): Less than 10 mg 2: (Slight bleed prevention effect is recognized): Less than 10-30 mg 3: (Bleed prevention effect is not recognized): More than 30 mg <Plasticizer bleed prevention effect: Antifouling evaluation>
About the sample of the outdoor exposure 60 days (May-June) installed in the south inclination angle 30 degree | times, the color difference (DELTA) E value (contrast with a blank) of a sample was measured and antifouling property was determined by the following reference | standard. (Exposed in Soka City, Saitama Prefecture)
1: Good as antifouling property for 60 days: ΔE = less than 5 2: Slightly inferior as antifouling property for 60 days: ΔE = less than 5 to 8 3: Inferior as antifouling property for 60 days: ΔE = 8 or more

[Example 1]
A flat woven fabric <base fabric 1> made of polyester (PET) multifilament yarn was used.
<Textile fabric: Base fabric 1>
[Rough density flat woven fabric woven with a warp yarn of 1000 d (1111 dtex) with a warp yarn of 19 / inch and a weft yarn of 20 / inch (mass 190 g / m ² : porosity 7%: fluorine type) Water repellent treatment with polymer resin emulsion)
A film having a thickness of 0.16 mm, which is calendered from 170 ° C. to 180 ° C. under a heat condition of 170 ° C. to 180 ° C. from a soft vinyl chloride resin compound of [Formulation 1] on both sides of the base fabric 1, is heated under a heat roll condition of 175 ° C. by a laminator. Was softened and a tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained by bridging the gap.
[Formulation 1] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Di (2-ethylhexyl) isophthalate (C8: MW390) 60 parts by mass Acrylic copolymer rubber component ( 1) 10 parts by mass * Trade name “Kane Ace” FM40: manufactured by Kaneka Corporation: graft copolymer of alkyl (meth) acrylate monomer and vinyl monomer Epoxidized soybean oil (plasticizer) 5 parts by mass Antimony trioxide (Flame retardant) 5 parts by weight Aluminum hydroxide (Flame retardant) 5 parts by weight Barium / zinc composite stabilizer 2 parts by weight Rutile titanium oxide (white pigment) 5 parts by weight * Acrylic copolymer rubber for soft vinyl chloride resin layer The content ratio of component (1) is 5.2% by mass.

[Example 2]
60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 1] in Example 1 was replaced with 60 parts by mass of di (2-ethylhexyl) terephthalate (C8: MW390), and Tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² as in Example 1 except that [Formulation 2] was used in which 10 parts by mass of the acrylate compound (1) was replaced with 10 parts by mass of the acrylate compound (2). Got.
[Formulation 2] Soft vinyl chloride resin compound composition Suspension polymerization Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Di (2-ethylhexyl) terephthalate (C8: MW390) 60 parts by mass Acrylic copolymer rubber component ( 2) 10 parts by mass * Product name “METABBRENE” S-2001: manufactured by Mitsubishi Rayon Co., Ltd .: Graft copolymer by polymerization of a polymer with an alkyl (meth) acrylate monomer and a silicone rubber Epoxidized soybean oil (plastic) Agent) 5 parts by weight Antimony trioxide (flame retardant) 5 parts by weight Aluminum hydroxide (flame retardant) 5 parts by weight Barium / zinc composite stabilizer 2 parts by weight Rutile titanium oxide (white pigment) 5 parts by weight * Soft vinyl chloride resin The content ratio of the acrylic copolymer rubber component (2) to the layer is 5.2% by mass.

[Example 3]
60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 1] in Example 1 was added to di-2-ethylhexyl 1,2-cyclohexanedicarboxylate (also known as 1,2-cyclohexanedicarboxylic acid). Dioctyl) 60 parts by weight, and the same as in Example 1 except that 10 parts by weight of the acrylate compound (1) and 10 parts by weight of the acrylate compound (3) were used. A tarpaulin of .75 mm and a mass of 940 g / m ² was obtained.
[Formulation 3] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid di-2-ethylhexyl (also known as dioctyl 1,2-cyclohexanedicarboxylate) 60 Part by mass Acrylic copolymer rubber component (3) 10 parts by mass * Product name “Kane Ace” B-513: Kaneka Corporation: Acrylate-butadiene-aromatic vinyl copolymer Epoxidized soybean oil (plasticizer) 5 parts by mass Antimony trioxide (flame retardant) 5 parts by weight Aluminum hydroxide (flame retardant) 5 parts by weight Barium / zinc composite stabilizer 2 parts by weight Rutile titanium oxide (white pigment) 5 parts by weight * Acrylic co-polymer for soft vinyl chloride resin layer The content ratio of the polymer rubber component (3) is 5.2% by mass.

[Example 4]
In Example 1, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 1] was mixed with di-2-ethylhexyl 1,3-cyclohexanedicarboxylate (also known as 1,3-cyclohexanedicarboxylic acid). Dioctyl) 60 parts by mass, and further using [Formulation 4] in which 10 parts by mass of the acrylate compound (1) was replaced with 10 parts by mass of the acrylate compound (4), the thickness was 0. A tarpaulin of .75 mm and a mass of 940 g / m ² was obtained.
[Formulation 4] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylate di-2-ethylhexyl (also known as 1,3-cyclohexanedicarboxylate dioctyl) 60 Part by mass Acrylic copolymer rubber component (4) 10 parts by mass * Product name “METABBRENE” W-300A: manufactured by Mitsubishi Rayon Co., Ltd .: block copolymer by methacrylic polymer block and acrylic polymer block epoxy Soybean oil (plasticizer) 5 parts by weight Antimony trioxide (flame retardant) 5 parts by weight Aluminum hydroxide (flame retardant) 5 parts by weight Barium / zinc composite stabilizer 2 parts by weight Rutile titanium oxide (white pigment) 5 parts by weight * The content ratio of the acrylic copolymer rubber component (4) to the soft vinyl chloride resin layer is 5.2% by mass. is there.

[Example 5]
60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 1] in Example 1 was mixed with di-2-ethylhexyl 1,4-cyclohexanedicarboxylate (also known as 1,4-cyclohexanedicarboxylic acid). Dioctyl) The same as in Example 1 except that [Formulation 5] was used in which 60 parts by mass was substituted and 10 parts by mass of the acrylate compound (1) was replaced by 10 parts by mass of the acrylate compound (5). A tarpaulin of .75 mm and a mass of 940 g / m ² was obtained.
[Formulation 5] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylate di-2-ethylhexyl (also known as 1,4-cyclohexanedicarboxylate dioctyl) 60 Part by mass Acrylic copolymer rubber component (5) 10 parts by mass * Product name "Kane Ace" M-570: Kaneka Corporation: Acrylate-butadiene-aromatic vinyl copolymer Epoxidized soybean oil (plasticizer) 5 parts by mass Antimony trioxide (flame retardant) 5 parts by weight Aluminum hydroxide (flame retardant) 5 parts by weight Barium / zinc composite stabilizer 2 parts by weight Rutile titanium oxide (white pigment) 5 parts by weight * Acrylic co-polymer for soft vinyl chloride resin layer The content ratio of the polymer rubber component (5) is 5.2% by mass.

[Examples 6 to 10]
An adhesive layer according to the following [Formulation 6] is formed on the surface of each tarpaulin obtained in Examples 1 to 5, and a polyvinylidene fluoride (PVdF) transparent film having a thickness of 50 μm is heated at 180 ° C. with the adhesive layer interposed. Lamination was performed to obtain a tarpaulin having a thickness of 0.85 mm and a mass of 1080 g / m ² provided with a fluororesin layer. A sixth embodiment based on the first embodiment, a seventh embodiment based on the second embodiment, and a tenth embodiment based on the fifth embodiment in the same manner.
<Adhesive layer>
The base materials of Examples 1 to 5 were put on a coating machine under 80 mesh gravure roll coating conditions, and coated with the adhesive composition of [Formulation 6] on the soft vinyl chloride resin layer, and then heated in a 120 ° C hot air oven. Dry for 3 minutes.
[Formulation 6] Adhesive composition Acrylic resin grafted with polyethyleneimine as a reactive group (solid content concentration 30% by mass, amine equivalent: 1400 g / eq) 100 parts by mass bisphenol A type epoxy resin (epoxy equivalent: 200 g / eq) 7 parts by weight benzotriazole compound (ultraviolet absorber) 0.5 parts by weight methyl ethyl ketone 100 parts by weight

[Examples 11 to 15]
An antifouling layer according to the following [Composition 7] was formed on the surface of each tarpaulin obtained in Examples 1 to 5, and a tarpaulin having a thickness of 0.76 mm and a mass of 960 g / m ² was obtained. An eleventh embodiment based on the first embodiment, an twelfth embodiment based on the second embodiment, and a fifteenth embodiment based on the fifth embodiment in the same manner.
<Anti-fouling layer>
The base materials of Examples 1 to 5 were applied to a coating machine under 80 mesh gravure roll coating conditions, coated on the soft vinyl chloride resin layer with the antifouling composition of [Formulation 7], and a hot air oven at 120 ° C. For 3 minutes.
[Formulation 7] Antifouling composition silica sol (particle size 20-30 nm: solid content 48% by mass) 100 parts by mass Vinyltriethoxysilane (silane coupling agent) 50 parts by mass Zinc oxide particles (particle size 15 nm) (ultraviolet absorber) 0.5 parts by weight Polyethylene glycol type nonionic active agent (antistatic agent) 1 part by weight Diluent (water) 100 parts by weight

  The tarpaulins of Examples 1 to 5 are all excellent in plasticizing efficiency without using a phthalate ester compound as a plasticizer, and the plasticizer bleed is highly suppressed, and contamination such as dust dirt is minimized. Since it is excellent in bending flexibility, it can be used for a long period of time for industrial material sheets such as for tent structures, for building curing, for electric signboards, and for flexible containers. In particular, hydrolytic condensation of an inorganic colloid substance and a silane coupling agent on the surface of each of the tarpaulins of Examples 6 to 10 and the surfaces of the tarpaulins of Examples 1 to 5 provided with a fluororesin layer on the surface of the tarpaulins of Examples 1 to 5, respectively. In each of the tarpaulins of Examples 11 to 15 provided with an antifouling layer composed of a product, the plasticizer bleed is further suppressed more than the tarpaulins of Examples 1 to 5, and more than the tarpaulins of Examples 1 to 5. Furthermore, the contamination such as dust stains became minor, and even if the dust stains adhered, if the level was several weeks, the adhered contaminants could be easily removed by wiping with a wiping cloth or the like. Further, since the tarpaulin of the present invention is processed into a long length, it is shipped in roll form and stored in roll form until use. In such a state, the tarpaulin of Examples 6 to 15 is particularly soft chloride on the back side. If the vinyl resin layer is in intimate contact with the fluororesin layer or antifouling layer on the surface, and the plasticizer bleeds from the soft vinyl chloride resin layer on the backside, the bleed plasticizer moves to the fluororesin layer or antifouling layer. Even if a fluororesin layer or an antifouling layer is formed by transferring, there is a problem accompanied by dust dirt immediately after use. However, in the tarpaulins of Examples 6 to 15, the soft vinyl chloride resin layer on the back surface itself The occurrence of such a contamination trouble was not recognized due to the excellent plasticizer migration inhibiting effect.

[Comparative Example 1]
In Example 1, a graft copolymer of the alkyl (meth) acrylate monomer as the acrylic copolymer rubber component (1) used in [Blend 1] and a vinyl monomer (trade name “Kaneace” FM40: A tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained in the same manner as in Example 1 except that 10 parts by mass of (made by Kaneka Corporation) was omitted. The obtained tarpaulin did not contain an acrylic copolymer rubber component in the soft vinyl chloride resin layer, so that the plasticizer was inferior in bleed deterrence and easily contaminated by dust adhesion.

[Comparative Example 2]
In Example 3, 60 parts by mass of di-2-ethylhexyl 1,2-cyclohexanedicarboxylate (also known as dioctyl 1,2-cyclohexanedicarboxylate) used in [Formulation 3] was mixed with di-2-ethylhexyl-phthalate (also known as: A tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained in the same manner as in Example 3 except that 60 parts by mass of dioctyl phthalate (DOP) was substituted. In the obtained tarpaulin, it was confirmed that the bleed inhibiting property of the plasticizer is insufficient as compared with the tarpaulins of Examples 1 to 5.

[Comparative Example 3]
In Example 3, 60 parts by mass of di-2-ethylhexyl 1,2-cyclohexanedicarboxylate (also known as dioctyl 1,2-cyclohexanedicarboxylate) used in [Formulation 3] was mixed with diheptyl phthalate (also known as diheptyl phthalate: DHP) A tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained in the same manner as in Example 3 except that 60 parts by mass was substituted. In the obtained tarpaulin, it was confirmed that the bleed inhibiting property of the plasticizer is insufficient as compared with the tarpaulins of Examples 1 to 5.

[Comparative Example 4]
In Example 3, 60 parts by mass of di-2-ethylhexyl 1,2-cyclohexanedicarboxylate (also known as dioctyl 1,2-cyclohexanedicarboxylate) used in [Formulation 3] was mixed with di-2-ethylhexyl adipate (also known as: Dioctyl adipate: DOA) A tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained in the same manner as in Example 3 except that 60 parts by mass was substituted. In the obtained tarpaulin, it was confirmed that the bleed inhibiting property of the plasticizer is insufficient as compared with the tarpaulins of Examples 1 to 5.

[Comparative Example 5]
In Example 1, a graft copolymer of the alkyl (meth) acrylate monomer as the acrylic copolymer rubber component (1) used in [Blend 1] and a vinyl monomer (trade name “Kaneace” FM40: 10 parts by mass of Kaneka Co., Ltd., ethylene-methyl methacrylate copolymer resin by copolymerization of ethylene and methyl methacrylate (MMA) (trade name “Aklift” WK307: MMA 25% by mass: MFR7: manufactured by Sumitomo Chemical Co., Ltd.) A tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained in the same manner as in Example 1 except that the amount was replaced with 10 parts by mass. The obtained tarpaulin was inferior in the compatibility between the soft vinyl chloride resin layer and the ethylene-methyl methacrylate copolymer resin, and formed plastic with poor dispersion, so that the plasticizer compared with the tarpaulins of Examples 1 to 5 The bleed deterrence was clearly insufficient.

  According to the present invention, the plasticizer bleed is suppressed to a very small amount over a long period of time, and the contamination such as change in texture and dust dirt is minimized, and the bending flexibility is excellent, so that the building curing, flexible container, wind pipe, oil Fence, flexible water tank, water storage tank, impermeable laying of industrial waste disposal site, flexible signboard, sheet shutter, partition, awning / rain protection, floor sheet, optical ceiling membrane, railway vehicle connection hood, cable cover, boat cover, grain / feed A long-term stable use as a tarpaulin for medium to large tent membrane structures such as industrial tarpaulins used for covers, waterproof apron, waterproof bags, tent warehouses, pavilions, sports amusement domes, planetariums, gas holders, etc. can do.

Claims (4)

A flexible laminate having a textile fabric as a base material and a soft vinyl chloride resin layer provided on at least one surface thereof, wherein the soft vinyl chloride resin layer mainly contains a vinyl chloride resin and a plasticizer. Further, the soft vinyl chloride resin layer contains 1 to 10% by mass of an acrylic copolymer rubber component, and the plasticizer is an isophthalic acid dialkyl ester (group of [Chemical Formula 1]), a terephthalic acid dialkyl ester ( [Chemical group 2], 1,2-cyclohexanedicarboxylic acid dialkyl ester (Chemical group 3), 1,3-cyclohexanedicarboxylic acid dialkyl ester (Chemical group 4), and 1,4-cyclohexane An industrial tarpaulin which is at least one selected from dicarboxylic acid dialkyl esters (group of [Chemical Formula 5]).
  The acrylic copolymer rubber component is 1) a random copolymer by polymerization of a plurality of alkyl (meth) acrylate monomers, 2) a (meth) acrylic polymer block (A) and an isobutylene polymer block (B ), Or a block copolymer containing at least one methacrylic polymer block (A) and an acrylic polymer block (C), and 3) one or more types of block copolymers A graft copolymer by polymerization of an alkyl (meth) acrylate monomer and a vinyl monomer, 4) a graft copolymer by polymerization of one or more alkyl (meth) acrylate monomers, and a silicone rubber, 5) One or more alkyl (meth) acrylate monomers, butadiene monomer, aromatic vinyl Acrylate by polymerization of Le monomers - butadiene - industrial tarpaulin according to claim 1 the aromatic vinyl copolymer, one or more members selected from the it.   A fluororesin layer is formed on the soft vinyl chloride resin layer, and the fluororesin constituting the fluororesin layer is vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene (TrEE), tetrafluoroethylene ( A polymer obtained by homopolymerizing one monomer selected from TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), or a copolymer obtained by copolymerizing two or more of these monomers, or The industrial tarpaulin according to claim 1 or 2, wherein the industrial tarpaulin is one or more selected from copolymers obtained by copolymerizing one or more of these monomers with a vinyl monomer. On the soft vinyl chloride resin layer, an antifouling layer is provided in which an inorganic colloidal material having a primary particle diameter of 3 to 150 nm is supported on a binder component containing a hydrolysis condensate of a silane coupling agent, Inorganic colloidal materials include photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and composite oxide The industrial tarpaulin according to claim 1 or 2, which is at least one metal oxide selected from sols (zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex).