JP2015223700A - Soft vinyl chloride resin-made industrial material sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft vinyl chloride resin-made industrial material sheet fur a canvas, a tarpaulin and a mesh sheet or the like, excellent in flexure flexibility, having highly suppressed plasticizer bleeding and containing no phthalate ester compound.SOLUTION: In a flexible laminate containing a fiber fabric as a base material and having a soft vinyl chloride resin layer on at least one face thereof, the soft vinyl chloride resin layer mainly contains vinyl chloride resin and contains at least one or more kind selected from isophthalic acid dialkyl ester, terephthalic acid dialkyl ester and cyclohexanedicarboxylic acid (including ortho, meth and para positional isomers) and a (meth)acrylate compound with a mass ration in a range of 10:1 to 3:1 and a crosslinked network conformation is formed by the (meth)acrylate compound in the soft vinyl chloride resin layer.

Description

  The present invention uses a textile fabric as a base material, a canvas obtained by coating a textile fabric base material with a soft vinyl chloride resin layer (for a seat house, a truck hood, a field sheet, etc.), a tarpaulin (for a tent structure, for building curing) , For electric signboards, for flexible containers) and mesh sheets (for building curing, protective nets, etc.), etc., especially without using phthalate ester compounds as plasticizers The present invention relates to an industrial material sheet that is excellent in plasticization efficiency, has a high degree of suppression of plasticizer bleed, and has excellent bending flexibility.

  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. Further, the bleed of the plasticizer has a problem that the surface of the molded product is made sticky, so that 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, as a plasticizer based on a non-phthalate ester compound, an anti-blocking agricultural polyvinyl chloride resin film (Patent Document 4) and a terephthalate ester plasticizer obtained by using a terephthalate ester plasticizer. The use of polyvinyl chloride wallpaper (Patent Document 5), which is excellent in cold resistance due to its use, diphthalic acid ester plasticizer that is di (2-ethylhexyl) isophthalate and / or diisononyl isophthalate, makes it safer for the human body An excellent vinyl chloride resin composition for covering electric wires and cables (Patent Document 6) has been proposed. However, in the plasticizers based on these non-phthalate ester compounds, the coordination space of the ester structure part with respect to the dipole of the linear vinyl chloride resin is bulky in terms of molecular structure, resulting in inferior plasticization efficiency and further increase in molecular weight Although the plasticization efficiency with (molecular weight 350 to 400) is further reduced, it is necessary to use a non-phthalate ester compound of a low molecular weight region having a molecular weight of about 250 to 300, but On the other hand, bleed (surface migration) is likely to occur due to the low molecular weight of the plasticizer, which leads to loss of volatilization of the plasticizer, and dust dirt adheres to the bleed plasticizer. Have problems such as making it dirty. However, in the above-described vinyl chloride resin compositions of Patent Documents 4 to 6, a specific method for suppressing or preventing bleeding (migration) of a terephthalic acid ester plasticizer or an isophthalic acid ester plasticizer has been studied. Absent. Accordingly, there is a demand for a soft vinyl chloride resin composition that has excellent plasticization efficiency, suppresses plasticizer bleeding, and has excellent flex flexibility, and in particular, a soft vinyl chloride resin composition using a non-phthalate ester compound. However, such a soft vinyl chloride resin composition has not yet existed.

JP 2001-207002 A JP 2002-363366 A JP 2011-231226 A Japanese Patent Laid-Open No. 2002-234983 JP 2012-184529 A JP 2012-89287 A

  The present invention uses a textile fabric as a base material, a canvas obtained by coating a textile fabric base material with a soft vinyl chloride resin layer (for a seat house, a truck hood, a field sheet, etc.), a tarpaulin (for a tent structure, for building curing) Industrial material sheets made of soft vinyl chloride resin, such as for use in electric signs, for electric signboards, for flexible containers, and mesh sheets (for building curing, protective nets, etc.), especially without using phthalate ester compounds as plasticizers An object of the present invention is to provide an industrial material sheet that is excellent in plasticizing efficiency, highly suppressed in plasticizer bleed, and excellent in flexibility in bending.

  As a result of research and examination on the industrial material sheet made of soft vinyl chloride resin in view of the above-mentioned present situation, the present inventor made an industrial material sheet made of soft vinyl chloride resin according to the present invention using at least a fiber fabric as a base material. In a flexible laminate in which a soft vinyl chloride resin layer is provided on one surface, the soft vinyl chloride resin layer mainly contains a vinyl chloride-based resin, and further includes a dialkyl ester of isophthalic acid, a dialkyl ester of terephthalic acid, 1,3- One or more plasticizers selected from cyclohexanedicarboxylic acid dialkyl ester, 1,4-cyclohexanedicarboxylic acid dialkyl ester, and 1,2-cyclohexanedicarboxylic acid dialkyl ester, and a (meth) acrylate compound in a mass ratio of 10: 1. Consists of a composition containing in the range of ~ 3: 1, (meth) acrylate compound However, by polymerizing in the soft vinyl chloride resin layer to form a crosslinked network three-dimensional structure, the resulting industrial material sheet has a high degree of plasticization and a high suppression of plasticizer bleed and excellent flexibility in bending. As a result, the present invention has been completed.

That is, the industrial material sheet made of a soft vinyl chloride resin of 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 layer mainly contains a vinyl chloride resin, and further, an isophthalic acid dialkyl ester ([Chemical group 1]), a terephthalic acid dialkyl ester ([Chemical group 2]), a 1,3-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 1] 3], 1,4-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 4]), and 1,2-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 5]). The (meth) acrylate compound comprising a plasticizer and a (meth) acrylate compound in a mass ratio of 10: 1 to 3: 1. , Is preferably at least one selected per molecule (meth) acryloyl group from a compound having 1 to 6. In the industrial material sheet obtained in this way, plasticizer bleed is highly suppressed while being excellent in plasticization efficiency, and yet exhibits excellent bending flexibility.

  In the industrial material sheet made of soft vinyl chloride resin of the present invention, the (meth) acrylate compound is selected from an alkyl chain, a hydroxyalkyl chain, an alkylene oxide, an alkylene glycol, pentaerythritol, and a trimethylolalkane as part of the molecular structure. In addition, an acrylate compound or a methacrylate compound containing one or more structural components is preferable. In the industrial material sheet obtained by this, plasticizer bleed is highly suppressed.

  In the industrial material sheet made of the soft vinyl chloride resin of the present invention, the (meth) acrylate compound is polymerized in the soft vinyl chloride resin layer to form a crosslinked network three-dimensional structure, thereby preventing bleeding (inhibition of the plasticizer). ) It is preferable to affect the effect. In the industrial material sheet obtained by this, plasticizer bleed is highly suppressed.

  In the industrial material sheet made of soft vinyl chloride resin of the present invention, an antifouling layer comprising an inorganic colloidal material having a primary particle diameter of 3 to 150 nm supported on a binder component is provided on the soft vinyl chloride resin layer. Is preferred. In the industrial material sheet obtained by this, plasticizer bleed is highly suppressed, and excellent bending flexibility and antifouling properties can be expressed.

  In the industrial material sheet made of soft vinyl chloride resin of the present invention, the binder component preferably contains a hydrolysis condensate of a silane coupling agent. In the industrial material sheet obtained by this, plasticizer bleed is highly suppressed, and excellent bending flexibility and antifouling properties can be expressed.

  In the industrial material sheet made of soft vinyl chloride resin according to the present invention, the inorganic colloidal substance is composed of titanium oxide sol, zinc oxide sol, tin oxide sol, silica (silicon oxide) sol, alumina (aluminum oxide) sol, zirconia (zirconium oxide) sol. And at least one selected from ceria (cerium oxide) sol and composite oxide (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol. In the industrial material sheet obtained by this, plasticizer bleed is highly suppressed, and excellent bending flexibility and antifouling properties can be expressed.

  The industrial material sheet made of the soft vinyl chloride resin of the present invention is particularly excellent in plasticizing efficiency without using a phthalate ester compound as a plasticizer, is highly suppressed in plasticizer bleeding, and has excellent flexibility in bending. So, canvas (for seat house, truck hood, field seat, etc.), tarpaulin (for tent structures, for building curing, for electric signboards, for flexible containers) and mesh sheet (for building curing, for protective nets, etc.) ) Etc. can be used for a long time as an industrial material sheet.

  The requirement of the industrial material sheet made of soft vinyl chloride resin of 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 soft vinyl chloride The resin layer mainly contains a vinyl chloride resin, and further, isophthalic acid dialkyl ester, terephthalic acid dialkyl ester, 1,3-cyclohexanedicarboxylic acid dialkyl ester, 1,4-cyclohexanedicarboxylic acid dialkyl ester, and 1,2-cyclohexanedicarboxylic acid It is comprised by the mixing | blending containing 1 or more types of plasticizers chosen from acid dialkyl ester, and (meth) acrylate compound in the range of mass ratio 10: 1-3: 1, and the said (meth) acrylate compound is 1 molecule. One or more selected from compounds having 1 to 6 (meth) acryloyl groups As essential Rukoto.

The fiber fabric as a base material used for the industrial material sheet made of the soft vinyl chloride resin of the present invention has a mass of 50 to 50 woven from synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers, or mixed fibers composed of two or more of these. 500 g / ^{m 2} approximately, which is preferably a mass 65~280g / ^{m 2} fabric. 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 plain fabric, twill woven fabric, satin woven fabric, imitation woven fabric made of filament yarn or spun yarn made of 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.

  Among the base fabrics used in the present invention, suitable fabrics for canvas are spun yarns (short fiber spun yarn) in the range of 10th (591 dtex) to 60th (97 dtex), especially 10th (591 dtex), 14th (422 dtex). 16th (370 dtex), 20th (295 dtex), 24th (246 dtex), 30th (197 dtex) spun yarns and a plain weave base fabric with a porosity of less than 5%. Specifically, a spun plain woven fabric having a weaving density of 50 to 70 warps and 40 to 60 wefts per inch using 20th single yarn or 20th twin yarn is suitable. These spun yarns include a core-sheath type, for example, an aramid fiber spun yarn as a core component, a polyester fiber short fiber tangled around its outer periphery as a sheath component, and further, for example, an aramid fiber multifilament yarn as a core component, Similarly, combinations of two types of fibers described in paragraph [0016] are exemplified, such as a sheath component obtained by tying short polyester fibers around the outer periphery. By making such a specification, it is possible to dramatically increase the tear strength of the canvas obtained and the ability to prevent holes from being formed by protrusions. A base fabric suitable for tarpaulin is a plain woven fabric having a porosity of 5% to 35%, preferably a porosity of 5% to 25% using a multifilament yarn of 278 to 1666 dtex, preferably 555 to 1111 dtex. Also, a base fabric suitable for the mesh sheet is a plain woven fabric having a porosity of 20 to 60%, preferably a porosity of 25 to 40% using a multifilament yarn of 222 to 1666 dtex, preferably 555 to 1111 dtex. A woven fabric. These tarpaulin and mesh base fabrics include ripstop base fabrics. For example, a part of warp and / or weft yarn of a base fabric made of polyester multifilament yarn is regularly or randomly aramid fiber multifilament yarn. And a combination arrangement from two types of fibers described in paragraph [0016]. By making such a specification, it becomes possible to dramatically increase the tear strength of the tarpaulin and mesh sheet obtained and the prevention of destruction by the projections.

In the soft vinyl chloride resin industrial material sheet of the present invention, the soft vinyl chloride resin layer mainly contains vinyl chloride resin, and further, as a plasticizer, isophthalic acid dialkyl ester (group of [Chemical Formula 1]), terephthalic acid dialkyl ester ([Chemical group 2]), 1,3-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 3]), 1,4-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 4]), and 1,2- One or more liquid compounds selected from cyclohexanedicarboxylic acid dialkyl esters (group of [Chemical Formula 5]) are included. 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.

  The plasticizer of 1,3-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 3]) 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 4]) is, for example, 1,4-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. The plasticizer of 1,2-cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical 5]) 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. 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 1,3-cyclohexanedicarboxylic acid structure, 1,4-cyclohexanedicarboxylic acid structure, and 1,2-cyclohexanedicarboxylic acid structure increase the steric hindrance due to the alkyl ester arrangement structure, and vinyl chloride. The plasticizing efficiency tends to decrease due to the coarsening of the coordination order of the ester polar part to the dipole of the resin.

  Other plasticizer components that can be used in combination with the plasticizers of [Group 1] to [Group 5] described in paragraphs [0019] and [0020] include tributyl acetyl citrate as necessary. , Di-2-ethylhexyl adipate, tri-2-ethylhexyl trimellitic acid, tricresyl phosphate, a reactive acrylic compound having two or more (meth) acryloyl groups at the molecular end or side chain, and an allyl group Two or more allyl phthalate compounds and the like can be used together in an amount of about 5 to 15% by mass relative to the plasticizers of ([Chemical Group 1] to (Chemical Group 5)).

  In the present invention, the soft vinyl chloride resin layer mainly contains a vinyl chloride resin, and includes the plasticizers of (group of [Chemical 1]) to (group of [Chemical 5]) described in paragraphs [0019] and [0020]. Including one or more types, including a plasticizer effectively plasticizes the vinyl chloride resin to form a soft vinyl chloride resin, and further includes a (meth) acrylate compound having 1 to 6 (meth) acryloyl groups per molecule By introducing a dense cross-linked structure into the soft vinyl chloride resin layer, the plasticizer bleed is highly suppressed, and the adhesion to the fiber fabric substrate is increased while the heat resistance of the soft vinyl chloride resin layer is improved. To do. The content ratio of the plasticizer of ([Chemical Group 1] to (Group of [Chemical Formula 5]) and the (meth) acrylate compound is preferably in the range of a mass ratio of 10: 1 to 3: 1. . The compounding amount of the plasticizer selected from (Group of [Chemical 1]) to (Group of [Chemical 5]) is 35 to 100 parts by mass, preferably 50 to 80 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. It is. Therefore, with respect to 100 parts by mass of the vinyl chloride resin, the (meth) acrylate compound used when 100 parts by mass of the plasticizer selected from (the group of [Chemical 1) to (the group of [Chemical 5]) is blended. The use amount range is 10 to 33.3 parts by mass, and similarly, it is used when 35 parts by mass of a plasticizer selected from (Group of [Chemical 1]) to (Group of [Chemical 5]) is used ( The use amount range of the (meth) acrylate compound is 3.5 to 11.65 parts by mass. The vinyl chloride resin is a homopolymer of a vinyl chloride monomer (emulsion polymerization type, suspension polymerization type having a polymerization degree of 700 to 3800) and other monomers copolymerizable with the vinyl chloride monomer. In the case of such a copolymer, the ratio of the vinyl chloride-containing component exceeding 60% by mass is desirable. 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 is processed with components other than vinyl chloride resins such as polyol compounds, chlorinated polyethylene, butyl rubber, acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer, and styrene-butadiene copolymer. For the purpose of a property improver, a flexibility improver, a low temperature property improver, a heat resistance improver, an impact modifier, etc., about 5 to 25% by mass can be used in combination with the vinyl chloride resin. In addition, the soft vinyl chloride resin layer includes a plasticizer selected from (group of [Chemical 1]) to (group of [Chemical 5]) and a known component for a soft vinyl chloride resin as a component other than the triisocyanate compound. Additives can be added in various amounts. As stabilizers for soft vinyl chloride resins, calcium zinc composite, barium zinc composite, organotin laurate, organotin mercaptite, and epoxy stabilizers can be used alone or in combination. It can be used in combination. If necessary, light stabilizers, ultraviolet absorbers, antioxidants, antibacterial agents, antifungal agents, colorants (pigments), fluorescent whitening agents, antistatic agents, waxes and the like can be included.

  In the present invention, the soft vinyl chloride resin layer contains a (meth) acrylate compound in combination with a plasticizer selected from (Group of [Chemical 1]) to (Group of [Chemical 5]). A dense cross-linked structure is formed in the soft vinyl chloride resin layer by the polyaddition reaction of the acrylate compound, thereby obtaining the effect of inhibiting the migration of the plasticizer. The (meth) acrylate compound contains at least one structural component selected from an alkyl chain, a hydroxyalkyl chain, an alkylene oxide, an alkylene glycol, pentaerythritol, and a trimethylolalkane as part of the molecular structure. And it is especially preferable that it is an acrylate compound or a methacrylate compound having 1 to 6 (meth) acryloyl groups per molecule. Specifically, as an acrylate compound having one (meth) acryloyl group and a methacrylate compound, carbon number of 5 such as isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, etc. 20 alkyl (meth) acrylates, hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates and other alkyl groups having 1 to 5 carbon atoms having hydroxyl groups, and Dimethylolcyclohexyl mono (meth) acrylate, hydroxycaprolactone (meth) acrylate, urethane (meth) acrylate, etc., ethylene oxide modified phenoxylated phosphoric acid (meth) acrylate, ethylene oxide Sid modified butoxylated phosphoric acid (meth) acrylate, ethylene oxide modified octyloxylated phosphoric acid (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate Polyalkylene glycol (meth) such as 2-ethylhexyl carbitol (meth) acrylate, N-vinyl-2-pyrrolidone, ethoxydiethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polypropylene oxide modified nonylphenyl (meth) acrylate Acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenylglycol Examples include (meth) acrylates having a cyclic skeleton such as dil (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentadieneoxyethyl (meth) acrylate. It is done.

  Specifically, as an acrylate compound having two (meth) acryloyl groups and a methacrylate compound, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polytetramethylene glycol di (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, alkylene oxide modified bisphenol A type di (meth) acrylate, caprolactone modified hydride Kishipibarin acid neopentyl glycol di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate and the like. Specifically, trimethylol such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctanetri (meth) acrylate as acrylate compounds having three (meth) acryloyl groups and methacrylate compounds Trimethylol C2 such as C2 to C10 alkane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxypolypropoxytri (meth) acrylate C10 alkane polyalkoxy tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, isocyanuric acid tris (ethyl Alkylene oxide modified trimethylolpropane tri (meth) such as xyl (meth) acrylate), pentaerythritol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate An acrylate etc. are mentioned. Specific examples of the acrylate compound having 4 or more (meth) acryloyl groups and the methacrylate compound include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate. It is done. Pentaerythritol polyethoxytetra (meth) acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. can be mentioned.

  These (meth) acrylate compounds are heated, irradiated with ultraviolet rays (for example, benzophenone is used in combination as a light amplifying agent), electron beam, catalyst (for example, heat curing using a vanadium system in combination), peroxide (for example, benzoyl peroxide), etc. The (meth) acryloyl group is cleaved by (meth) acryloyl group by addition polymerization to form a dense crosslinked network three-dimensional structure, and at the same time, it bonds to the functional group on the surface of the textile fabric, and soft vinyl chloride. A crosslinked network three-dimensional structure is formed in the entire resin layer, thereby firmly bonding the interface between the soft vinyl chloride resin layer and the fiber fabric, and at the same time, the crosslinked network three-dimensional structure coexists as a plasticizer in the soft vinyl chloride resin layer ([ A filter effect that makes it difficult for a molecule of a plasticizer selected from the group of [Chemical Formula 1] to (Group of [Chemical Formula 5]) to pass through the crosslinked network three-dimensional structure By bleeding prevention of these plasticizers (suppressed) to express the effect. Therefore, the finer the three-dimensional network of the crosslinked network three-dimensional structure, the higher the bleed prevention (suppression) effect of these plasticizers. In order to obtain a densified three-dimensional network, an acrylate compound having a relatively small molecular weight of a (meth) acrylate compound and having two or more (meth) acryloyl groups, and a methacrylate compound are described in paragraphs [0023] and [0024]. The selective use of one or more of the above is preferred.

  As a method for forming a soft vinyl chloride resin layer on a textile fabric, for example, an emulsion polymerization type vinyl chloride resin (100 parts by mass) is selected from (group of [Chemical 1]) to (group of [Chemical 5]). A known coating method using a paste-like composition mainly composed of a plasticizer (35 to 100 parts by mass) and a (meth) acrylate compound (0.35 to 33.3 parts by mass), such as dipping ( And double-sided processing on fiber fabrics), coating (single-sided processing or double-sided processing on fiber fabrics, knife coating, gravure coating, clearance coating, etc.). When the soft vinyl chloride resin industrial material sheet of the present invention is a canvas, the plain weave base fabric for canvas described in paragraph [0017] is dipped or coated, or a combination of dipping and coating is used to remove the gap between the textile fabrics ( The gap between the fiber yarns and the fiber yarns, and the gap between the filament single yarns constituting the fiber yarns and the filament single yarns) are impregnated with the paste-like composition, and both sides of the plain weave base fabric for canvas are pasty. The target canvas is obtained by forming a soft vinyl chloride resin layer by coating with a composition and heat-treating it to gel. Further, when the industrial material sheet made of soft vinyl chloride resin of the present invention is a mesh sheet, the filament single yarn constituting the fiber yarn is formed by dipping or coating means on the plain plain fabric described in paragraph [0017] A soft vinyl chloride resin layer is formed by impregnating the paste-like composition into the gap between the filament single yarn and coating the entire surface of the hollow plain woven fabric with the paste-like composition and gelling it by heat treatment. To obtain the desired mesh sheet. Further, when the industrial material sheet made of soft vinyl chloride resin of the present invention is tarpaulin, for example, suspension polymerization type vinyl chloride resin (100) is applied to one or both sides of the plain plain fabric described in paragraph [0017]. (Parts of [Chemical 1]) to (group of [Chemical 5]) and a (meth) acrylate compound (0.35 to 33.35 parts by mass). (3 parts by mass) of a compound composition as a main component, a film (sheet) molded by the calender method, or a film (sheet) extruded by the T-die method is heat laminated by a through-bridge method, or The target tarpaulin is obtained by laminating the adhesive. Although there is no limitation in the formation amount of these soft vinyl chloride resin layers, it is about 100-1000 mass% with respect to the mass of a fiber woven fabric in total of front and back, especially 150-500 mass%.

The surface of the soft vinyl chloride resin layer in the soft vinyl chloride resin industrial material sheet of the present invention is provided with an antifouling layer containing an inorganic colloidal material having a primary particle diameter of 3 to 150 nm supported on a binder component. In particular, it is preferable that the binder component contains a hydrolysis condensate of a silane coupling agent. Inorganic colloidal materials include titanium oxide sol, zinc oxide sol, tin oxide sol, silica (silicon oxide) sol, alumina (aluminum oxide) sol, zirconia (zirconium oxide) sol, ceria (cerium oxide) sol, and composite oxide ( One or more selected from zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sol can be used, and in particular, photocatalytically active titanium oxide sol, photocatalytically active zinc oxide sol, photocatalytically active tin oxide sol, etc. It is excellent in antifouling effect and preferable. The binder component is organic, and includes acrylic resin, fluorine copolymer resin, acrylic-silicon copolymer resin, acrylic-fluorine copolymer resin, acrylic-urethane copolymer resin, acrylic resin and fluorine copolymer resin, For example. The binder component is a compound having two or more different reactive groups in the molecule represented by the general formula: XR-Si (Y) ₃ as a silane coupling agent. For example, X = amino group, vinyl group, epoxy Group, chloro group, mercapto group and the like (R = alkyl chain), Y = methoxy group, ethoxy group and the like. These hydrolysates and cohydrolyzed compounds with alkoxysilane compounds can also be used. Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ- Examples include aminopropyltriethoxysilane, 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.

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.
<Heat-resistant>
<Evaluation based on heat-resistant creep characteristics of joined body>
The edges of the two sheets are overlapped in a straight line with a width of 4 cm and 4 cm width × 30
Using a high-frequency welder welding machine (YF-7000, manufactured by Yamamoto Vinita Co., Ltd .: output 7 kW) equipped with a cm-long weld bar (flat blade), sheets are fused and joined together at an anode current of 1.0A. A sheet was obtained. From this, the fusion bonded portion is overlapped and includes a width of 4 cm
Nine test pieces of 3 cm width × 30 cm length were collected, and subjected to a load of 60 ° C. × 25 kgf (condition 1) and 65 ° C. × 25 kgf using a creep tester (Toyo Seiki Seisakusho: 100 LDR type).
The heat resistant creep resistance was evaluated for 24 hours under three conditions of load (condition 2) and 70 ° C. × 25 kgf load (condition 3).
Evaluation criteria
1: After 24 hours, the joint is good without any change or abnormality.
2: The joint was broken and the test piece was divided in less than 24 hours.
<Recording time of destruction>
3: The joint part was destroyed within 1 hour, and the test piece was divided.
<Recording time of destruction>
Judgment of broken state: Thread drop breakage at joint (no thread breakage), body breakage, etc. (with thread breakage)
<Bending durability>
According to JIS L1096, paragraph 8.19 “Abrasion Strength B Method (Scott Method)”, the wear state (evaluated by the amount of wear residue) of the soft vinyl chloride resin layer at 1 kgf load 500 times, and the presence or absence of cracks (20 times greater) Visual observation with a magnifier) was evaluated.
1: Little wear debris and no cracks are observed 2: Some wear debris is observed but no cracks are observed 3: Cracks are observed <Inhibition effect of plasticizer bleed: wettability evaluation>
A sample of 10 cm x 10 cm size is sandwiched between two glass plates (10 cm x 10 cm size x 5 mm thickness), and this is left in a state where it is placed flat in a gear oven set at 65 ° C for 72 hours. The plasticizer bleed deterrence (preventiveness) was judged by visual inspection of the surface of the plate (fogging) and wetness (bleed), and by touch judgment.
1 (good): Level at which the glass plate surface is slightly fogged 2 (slightly defective): The glass plate surface is clouded and slips when touched 3 (bad): Remarkable wetting is observed on the glass plate surface, and 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: (A bleed prevention effect is recognized): Level of 50 mg or less 2: (A bleed prevention effect is recognized): A level of 50 to 150 mg 3: (A bleed prevention effect is not recognized): A level exceeding 150 mg

[Example 1]
A plain woven spun cloth made of polyester (PET) short fiber spun yarn was used as the base cloth 1.
<Textile fabric: Base fabric 1>
[Yarn density: 44 warp / twist (590 dtex) 44 / inch × 40 weft / twist (590 dtex) 40 / inch: porosity 4.2%: mass 228 g / m ² : corona discharge treatment on both sides]
A soft vinyl chloride resin paste sol composition of the following [Formulation 1] was prepared to an appropriate viscosity, and the base cloth 1 was immersed in a liquid bath filled with the paste sol composition of [Formulation 1]. The paste sol composition of [Formulation 1] is completely impregnated, the base fabric 1 is pulled up and simultaneously compressed with a rubber roll for 3 minutes in a hot air oven at 180 ° C. The thickness of the soft vinyl chloride resin layer formed on both sides of the base fabric 1 by proceeding the polyaddition reaction of the acrylate compound (1), impregnating with the paste sol composition of [Formulation 1] and coating A canvas having a diameter of 0.47 mm and a mass of 560 g / m ² was obtained.
[Formulation 1] Soft vinyl chloride resin paste sol composition Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1700) 100 parts by mass Di (2-ethylhexyl) isophthalate (C8: MW390) 60 parts by mass * R in [Chemical Formula 1] is Both are branched alkyl groups having 9 carbon atoms. Acrylate compound (1) (active ingredient 100%) 10 parts by mass * Tripropylene glycol diacrylate (having two acryloyl groups)
_{CH 2 = CHCO- (OCH 3 H} 6) 3 -OCOCH = CH 2
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Rutile titanium oxide (white pigment) 5 parts by weight * Di (2-ethylhexyl) isophthalate ) And the acrylate compound (1) is 60:10 (6: 1).

[Example 2]
In Example 1, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 1] was used, and R of di (2-ethylhexyl) terephthalate (C8: MW390: [Chemical Formula 2] was 2). Each of them is substituted with 60 parts by mass of a branched chain alkyl group having 9 carbon atoms), and further 10 parts by mass of acrylate compound (1) [trimethylolpropane triacrylate [acrylate compound having three acryloyl groups (2): ( CH ₂ ═CHCOOCH ₂ ) ₃ —CCH ₂ CH ₃ ] A canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 1 except that 10 parts by mass was substituted.

[Example 3]
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) (C8: MW393: [Chemical Formula 3] in which both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and 10 parts by mass of the acrylate compound (1) are converted to pentaerythritol tetraacrylate. [Acrylate compound having four acryloyl groups (3): (CH ₂ ═CHCOOCH ₂ ) ₄ —C] The thickness is 0.47 mm and the mass is 560 g / m ² as in Example 1 except that 10 parts by mass is substituted. I got the canvas.

[Example 4]
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) (C8: MW393: [Chemical Formula 4] in which both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and further 10 parts by mass of the acrylate compound (1) Methylolpropane triacrylate [acrylate compound having three acryloyl groups (4): [CH ₂ = CHCO— (OC ₂ H ₄ ) —OCH ₂ ] ₃ —CCH ₂ CH ₃ ] As in Example 1, a canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained.

[Example 5]
A stitched plain woven fabric made of polyester (PET) multifilament yarn was used as the base fabric 2.
<Textile fabric: Base fabric 2>
[Yarn density: 750 d / 3 yarns (833 dtex / 3 yarns) using warp yarns and coarse weaving yarns (mass of 225 g / mass) woven with 11 warps / inch and 11 wefts / inch m ² : porosity 11%: corona discharge treatment on both sides)
10 parts by mass of the acrylate compound (1) used in [Formulation 1] in Example 1 was replaced with ethylene oxide-modified bisphenol A diacrylate (acrylate compound having two acryloyl groups (5): C (CH ₃ ) ₂ (CH ₂ = CH—CO— (OC ₂ H ₄ ) ₂ —O— (C ₆ H ₄ ) ₂ ) [Formulation 2] substituted with 10 parts by mass was used as a paste sol composition.
A soft vinyl chloride resin paste sol composition of [Formulation 2] was prepared to an appropriate viscosity, and the base fabric 2 was immersed in a liquid bath filled with the paste sol composition of [Formulation 2]. Fully impregnating the paste sol composition of [Formulation 2], pulling up the base fabric 2, and simultaneously pressing with a rubber roll for 3 minutes in a hot air oven at 180 ° C., and gelation of the paste sol composition of [Formulation 2]; The thickness of the soft vinyl chloride resin layer formed on both surfaces of the base fabric 2 by proceeding with the polyaddition reaction of the acrylate compound (5), impregnating and coating with the paste sol composition of [Formulation 2] A mesh sheet having a thickness of .36 mm, a mass of 470 g / m ² and a porosity of 10% was obtained.

[Example 6]
In Example 5, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 2] was used, and R of di (2-ethylhexyl) terephthalate (C8: MW390: [Chemical Formula 2] was 2). Each of them is substituted with 60 parts by mass of a branched alkyl group having 9 carbon atoms, and further 10 parts by mass of the acrylate compound (5), ethylene oxide (n = 3) -modified isocyanuric acid triacrylate [having three acryloyl groups. Acrylate compound (6)] A mesh sheet having a thickness of 0.36 mm, a mass of 470 g / m ² and a porosity of 10% was obtained in the same manner as in Example 5 except that 10 parts by mass was substituted.

[Example 7]
In Example 5, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 2] was mixed with di-2-ethylhexyl 1,2-cyclohexanedicarboxylate (also known as 1,2-cyclohexanedicarboxylic acid). Dioctyl) (C8: MW393: [Chemical Formula 5] in which both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and 10 parts by mass of the acrylate compound (6) are converted to the acrylate compound (1 ) A mesh sheet having a thickness of 0.36 mm, a mass of 470 g / m ² and a porosity of 10% was obtained in the same manner as in Example 5 except that 10 parts by mass was substituted.

[Example 8]
In Example 5, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 2] was mixed with di-2-ethylhexyl 1,4-cyclohexanedicarboxylate (also known as 1,4-cyclohexanedicarboxylic acid). Dioctyl) (C8: MW393: [Chemical Formula 4] in which both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and further 10 parts by mass of the acrylate compound (6) are converted to the acrylate compound (2 ) A mesh sheet having a thickness of 0.36 mm, a mass of 470 g / m ² and a porosity of 10% was obtained in the same manner as in Example 5 except that 10 parts by mass was substituted.

[Example 9]
A stitched plain fabric made of polyester (PET) multifilament yarn was used as the base fabric 3.
<Textile fabric: Base fabric 3>
[Round density: 1000d (1111 dtex) warp yarn, coarse plain woven by weaving warp yarn 19 / inch and weft yarn 20 / inch (mass 190g / m ² : porosity 7%: corona on both sides) Discharge treatment)
A film with a thickness of 0.16 mm, calendered from 165 ° C to 180 ° C under a heat condition of 165 ° C to 180 ° C from a soft vinyl chloride resin compound of [Formulation 3] on both sides of the base fabric 3, and a film under a heat roll condition of 170 ° C by a laminator Was laminated in a softened state to obtain a tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² .
[Formulation 3] 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 * R in [Chemical Formula 1] is both two branched alkyl group acrylate compound of 9 carbon atoms (3) (active ingredient 100%) 10 parts by mass ※ to four chromatic pentaerythritol tetraacrylate [acryloyl _{group: (CH 2 = CHCOOCH 2)} 4 -C ]
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Rutile titanium oxide (white pigment) 5 parts by weight * Di (2-ethylhexyl) isophthalate ) And the acrylate compound (3) is 60:10 (6: 1).

[Example 10]
In Example 9, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 3] was replaced with R of di (2-ethylhexyl) terephthalate (C8: MW390: Chemical formula 2). The same as in Example 9, except that each was substituted with 60 parts by mass of a branched alkyl group having 9 carbon atoms, and further 10 parts by mass of the acrylate compound (3) was substituted with 10 parts by mass of the acrylate compound (4). A tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained.

[Example 11]
In Example 9, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 3] was mixed with di-2-ethylhexyl 1,3-cyclohexanedicarboxylate (also known as 1,3-cyclohexanedicarboxylic acid). Dioctyl) (C8: MW393: [Chemical Formula 3] in which both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and further 10 parts by mass of the acrylate compound (3) are converted to the acrylate compound (5 ) 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 9 except that 10 parts by mass was substituted.

[Example 12]
In Example 9, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390) used in [Formulation 3] was mixed with di-2-ethylhexyl 1,2-cyclohexanedicarboxylate (also known as 1,2-cyclohexanedicarboxylic acid). Dioctyl) (C8: MW393: [Chemical Formula 5] where both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and further 10 parts by mass of the acrylate compound (3) are substituted with the acrylate compound (6 ) 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 9 except that 10 parts by mass was substituted.

[Examples 13 to 24]
An antifouling layer according to the following [Composition 4] was formed on the surfaces of the canvases of Examples 1 to 4, the mesh sheets of Examples 5 to 8, and the tarpaulins of Examples 9 to 12, and the antifouling layers of Examples 13 to 16, respectively. A canvas provided with a soil layer on one surface, a mesh sheet provided with both surfaces of the antifouling layers of Examples 17 to 20, and a tarpaulin provided with the antifouling layer of Examples 21 to 24 on one surface were obtained.
<Anti-fouling layer>
The base materials of Examples 1 to 12 were applied to a coating machine under 100 mesh gravure roll coating conditions, subjected to surface treatment with an antifouling composition of the following [Composition 4] on a soft vinyl chloride resin layer, and heated at 120 ° C. Dry in oven for 3 minutes. This antifouling layer is more effective after curing at room temperature for about 3 days.
[Formulation 4] 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 Benzotriazole compound (ultraviolet absorber) 1 part by mass Polyethylene Glycol type nonionic active agent (antistatic agent) 1 part by weight Diluent (water) 100 parts by weight

  The sheets of Examples 1 to 12 are all excellent in plasticizing efficiency without using a phthalate ester compound as a plasticizer, are highly suppressed in plasticizer bleed, and are excellent in bending flexibility. Canvas (for sheet houses, truck hoods, field seats, etc.), tarpaulins (for tent structures, for building curing, for electric signboards, for flexible containers) and mesh sheets (for building curing, for protective nets, etc.) It can be used for industrial material sheets for a long time. In particular, the sheets of Examples 13 to 24 (canvas, mesh, tarpaulin) provided with an antifouling layer on the sheets of Examples 1 to 12 are excellent in antifouling properties, and even if dust stains adhere to the sheet, it is at the level of several weeks. Dust can be easily removed by wiping or wiping with a wiping cloth, etc., no dust re-adhesion trouble due to generation of static electricity during wiping is observed, and a soft vinyl chloride resin layer is provided with an antifouling layer As a result, the bleed prevention (suppression) effect of the plasticizer was further improved, and the outdoor pot life was doubled.

[Comparative Example 1]
In Example 1, the acrylate compound (1) used in [Formulation 1]: A canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 1 except that tripropylene glycol diacrylate was omitted. It was.

[Comparative Example 2]
In Example 1, the acrylate compound (1) used in [Formulation 1] was reduced to 3 parts by mass, and di (2-ethylhexyl) isophthalate (C8: MW390: [Chemical Formula 1]) and the acrylate compound (1) The mass ratio was changed to 60 parts by mass: 3 parts by mass (20: 1), and a canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 1.

[Comparative Example 3]
In Example 1, the amount of acrylate compound (1) used in [Formulation 1] was increased to 30 parts by mass, and di (2-ethylhexyl) isophthalate (C8: MW390: [Chemical Formula 1]) and acrylate compound (1) The mass ratio was changed to 60 parts by mass: 30 parts by mass (2: 1), and a canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 1.

[Comparative Example 4]
In Example 1, 60 parts by mass of di (2-ethylhexyl) isophthalate (C8: MW390: [Chemical Formula 1]) used in [Formulation 1] was mixed with di-2-ethylhexyl-phthalate (also known as dioctyl phthalate: DOP) A canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 1 except that 60 parts by mass was substituted.

[Comparative Example 5]
60 parts by mass of di (2-ethylhexyl) terephthalate (C8: MW390: [Chemical Formula 2]) used in the formulation of Example 2 was replaced with 60 parts by mass of diheptyl phthalate (also known as diheptyl phthalate: DHP). Except for this, a canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 2.

[Comparative Example 6]
60 parts by mass of di-2-ethylhexyl 1,3-cyclohexanedicarboxylate (also known as dioctyl 1,3-cyclohexanedicarboxylate) (C8: MW393: [Chemical Formula 3]) used in the formulation of Example 3 was added to diisononyl phthalate. (Alias: diisononyl phthalate: DINP) A canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 3 except that 60 parts by mass was substituted.

[Comparative Example 7]
60 parts by mass of di-2-ethylhexyl 1,4-cyclohexanedicarboxylate (also known as dioctyl 1,4-cyclohexanedicarboxylate) (C8: MW393: [Chemical Formula 4]) used in the formulation of Example 4 was added to adipic acid. A canvas having a thickness of 0.47 mm and a mass of 560 g / m ² was obtained in the same manner as in Example 4 except that 60 parts by mass of di-2-ethylhexyl (also known as dioctyl adipate: DOA) was substituted.

  The canvas of Comparative Example 1 does not contain an acrylate compound in the soft vinyl chloride resin layer, so that the obtained canvas is inferior in plasticizer bleed prevention (deterrence), and further lacks heat resistance. The joints are easily broken under high temperature environment such as summer. The canvas of the comparative example 2 with respect to the comparative example 1 contains an acrylate compound in the soft vinyl chloride resin layer, but the combined amount of the acrylate compound with respect to the plasticizer amount is 10: 1 which is the lower limit of the present application. By setting the ratio to 20: 1, which is lower than the canvas of Comparative Example 1, the obtained canvas is inferior in plasticizer bleed prevention (deterrence) and further lacks heat resistance. It became easy to break under high temperature environment such as summer. Compared to Comparative Example 1, the canvas of Comparative Example 3 is 2: 1 in which the combined amount of the acrylate compound with respect to the plasticizer amount exceeds the mass ratio amount of 3: 1 of the upper limit of the present application. Practical durability, including poorly compatible and excessively rigid three-dimensional structure of cross-linked network, resulting in poor flexibility of the resulting canvas, accompanied by wear deterioration and surface cracks of the soft vinyl chloride resin layer in a short period of time It became lacking in sex. Since the canvases of Comparative Examples 4 to 6 used a phthalate ester plasticizer in the soft vinyl chloride resin layer, the initial compatibility with the acrylate compound in the soft vinyl chloride resin composition was poor, and the soft vinyl chloride resin composition If the materials are not sufficiently stirred and aged, the gelation process is performed with the components in a non-uniform dispersion state. This causes local instability in the cross-linking of the soft vinyl chloride resin layer, resulting in phthalic acid. It became a factor that hinders the suppression of bleeding of ester plasticizers. In the canvas of Comparative Example 7, the use of di-2-ethylhexyl adipate (also known as dioctyl adipate) as a plasticizer in the soft vinyl chloride resin layer promotes bleeding of the plasticizer, and the plasticizer is applied to the canvas surface. It oozed out and became sticky, and it became a volatilization loss, and at the same time, dust stains adhered to the canvas surface and stuck, making it easy to get dirty and deteriorating the appearance.

  According to the present invention, since the plasticizing efficiency is excellent without using a phthalate ester compound as a plasticizer, the plasticizer bleed is highly suppressed, and the bending flexibility is excellent. Industrial material sheets such as tarpaulins (for tent structures, for building curing, for electric signboards, for flexible containers) and mesh sheets (for building curing, protective nets, etc.) Can be used for a long time.

Claims (6)

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 further comprises isophthalic acid Dialkyl ester ([Chemical group 1]), terephthalic acid dialkyl ester ([Chemical group 2]), 1,3-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 3]), 1,4-cyclohexanedicarboxylic acid dialkyl ester One or more plasticizers selected from an ester ([Chemical group 4]) and a 1,2-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 5]), and a (meth) acrylate compound in a mass ratio of 10 : It is comprised by the mixing | blending containing in the range of 1-3: 1, and the said (meth) acrylate compound has 1-6 (meth) acryloyl groups per molecule. Soft vinyl chloride resin industrial material sheet, characterized in that at least one member selected from compounds.
  An acrylate in which the (meth) acrylate compound contains at least one structural component selected from an alkyl chain, a hydroxyalkyl chain, an alkylene oxide, an alkylene glycol, pentaerythritol, and a trimethylolalkane as part of the molecular structure. The industrial material sheet made of soft vinyl chloride resin according to claim 1, which is a compound or a methacrylate compound.   The said (meth) acrylate compound superposes | polymerizes in the said soft vinyl chloride resin layer, and acts on the bleeding prevention (suppression) effect of the said plasticizer by forming a bridge | crosslinking network three-dimensional structure. Industrial material sheet made of soft vinyl chloride resin.   The soft antifouling layer according to any one of claims 1 to 3, wherein an antifouling layer comprising an inorganic colloidal substance having a primary particle diameter of 3 to 150 nm supported on a binder component is provided on the soft vinyl chloride resin layer. Industrial material sheet made of vinyl chloride resin.   The industrial material sheet made of a soft vinyl chloride resin according to claim 4, wherein the binder component contains a hydrolysis condensate of a silane coupling agent.   The inorganic colloidal material includes titanium oxide sol, zinc oxide sol, tin oxide sol, silica (silicon oxide) sol, alumina (aluminum oxide) sol, zirconia (zirconium oxide) sol, ceria (cerium oxide) sol, and composite oxide ( The industrial material sheet made of soft vinyl chloride resin according to claim 4, which is one or more selected from zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sol.