JP6318348B2 - Industrial material sheet made of soft vinyl chloride resin - Google Patents

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 excellent in plasticization efficiency, highly suppressed in plasticizer bleed, and excellent in weather resistance.

  In the vinyl chloride resin paste sol composition, a prescription containing an isocyanate compound has been used for a long time to improve adhesion to a coated substrate. For example, isocyanate polymerization in which trimylene diisocyanate or diphenylmethane diisocyanate is trimerized. The composition of the product is representative (Patent Document 1). However, when these isocyanate polymers are blended into the vinyl chloride resin paste sol composition, the thickening behavior of the paste sol over time caused by the addition reaction of the isocyanate groups with the composition will affect the coatability of the paste sol composition. Due to the deterioration and further the addition reaction of the isocyanate group, the adhesion to the coated substrate may be insufficient against the purpose. In order to solve this problem, a long-chain alkylphenol is temporarily reacted with an isocyanate group to inactivate (block) the isocyanate group in the paste sol composition, thereby stabilizing the viscosity of the paste sol composition. A method for regenerating an isocyanate group by thermally dissociating the temporary reaction product during coating of the composition has been devised. For example, a block body of an aromatic diisocyanate polymer has been proposed (Patent Document 2). However, when an aromatic diisocyanate trimer and a polymer as in Patent Document 1 and Patent Document 2 are used in a coating composition for an article for outdoor use, the benzene ring is mutated into a quinone structure due to ultraviolet rays. Had the problem of yellowing (browning) coloration. Therefore, non-yellowing polyisocyanate compounds such as trimers and polymers of aliphatic diisocyanates such as hexamethylene diisocyanate, and trimers and polymers of alicyclic diisocyanates such as isophorone diisocyanate have been proposed. A plastisol composition (Patent Document 3) composed of a polyfunctional block urethane prepolymer in which a group is protected has been proposed. However, in the plastisol composition containing such a polyfunctional block urethane prepolymer, the plasticizer used is di-n-octyl-phthalate, di-2-ethylhexyl-phthalate (DOP), diisononyl phthalate (DINP), diheptyl phthalate. In the case of a phthalate compound such as (DHP), the initial compatibility with the non-yellowing polyisocyanate compound (polyfunctional block urethane prepolymer) in the soft vinyl chloride resin composition is poor due to steric hindrance, 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, which causes the mechanical properties of the coating film and molded product to become locally unstable. It was.

  In recent years, phthalate ester compounds are a substance of concern for mutagenic substances, and in the fields of toys, food wraps, medical equipment, etc., replacement with plasticizers using non-phthalate ester compounds has been studied. Anti-blocking agricultural polyvinyl chloride resin film (Patent Document 4) by using terephthalic acid ester plasticizer as the agent, and polyvinyl chloride having excellent cold resistance by using terephthalic acid ester plasticizer Vinyl chloride resin composition for electric wire / cable coating with excellent safety for human body by including wallpaper (Patent Document 5), isophthalic acid ester plasticizer which is di (2-ethylhexyl) isophthalate and / or diisononyl isophthalate A thing (patent document 6) etc. are proposed. However, in plasticizers based on these non-phthalate ester compounds, the coordination of the ester structure to the dipole of the linear vinyl chloride resin is inefficient in terms of molecular structure, resulting in poor plasticization efficiency and further increase in molecular weight. (Molecular weight 350-400) tends to reduce the plasticization efficiency, so it is necessary to use a non-phthalate ester compound in the low molecular weight region having a molecular weight of about 250-300. Lowering the molecular weight of the agent makes it easier to cause bleeding (surface migration), which causes plasticizer volatilization loss, or dust dirt adheres to the bleeding plasticizer, resulting in poor appearance in a short period of time, etc. Have problems. Accordingly, there has been a demand for a soft vinyl chloride resin composition that is excellent in plasticizing efficiency, suppresses plasticizer bleeding, and has excellent weather resistance, 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-A-57-105441 JP 62-41278 A JP 2001-354818 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 plasticization efficiency, highly suppressed in plasticizer bleed, and excellent in weather resistance.

  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 triisocyanate compound having no benzene ring in the molecular structure At a specific mass ratio, and this triisocyanation As a result of the product forming a cross-linked structure in the soft vinyl chloride resin layer, the resulting industrial material sheet was found to have excellent plasticization efficiency, but also highly suppressed plasticizer bleed and excellent weather resistance. The present invention has been completed.

That is, the soft vinyl chloride resin industrial material sheet of the present invention is a soft vinyl chloride resin industrial material sheet made of a flexible laminate in which a fiber woven fabric is used as a base material and a soft vinyl chloride resin layer is provided on at least one surface thereof. Wherein the soft vinyl chloride resin layer mainly contains a vinyl chloride resin, and further, a dialkyl ester of isophthalic acid (a group of [Chemical Formula 1]), a dialkyl ester of terephthalic acid (a group of [Chemical Formula 2]), 1, 3 -Cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 3]), 1,4-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 4]), and 1,2-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 5] group) 1) or more plasticizers selected from the above and triisocyanate compounds in a mass ratio of 10: 0.1 to 10: 1. , And is constituted by including a nanosilica particles are surface hydroxyl-modified silicon oxide, the triisocyanate compound, the group of isocyanurate modified triisocyanate formula 6 (R = formula 9 - [Formula 11]), the burette Selected from the group of modified triisocyanate [Chemical Formula 7] (R = [Chemical Formula 9] to [Chemical Formula 11]) and the group of trimethylol alkyl modified triisocyanate [Chemical Formula 8] (R = [Chemical Formula 9] to [Chemical Formula 11]) In the flexible laminate, the triisocyanate compound forms at least a surface of the fiber fabric and a crosslinked structure including a bond to the nanosilica particles in the soft vinyl chloride resin layer. It is preferable. In the industrial material sheet obtained in this way, plasticizer bleed is highly suppressed while having excellent plasticization efficiency, and excellent weather resistance is exhibited.

The soft vinyl chloride resin industrial material sheet of the present invention is the triisocyanate compound, the isocyanurate-modified triisocyanate [Chemical Formula 6] group, the bullet modified triisocyanate [Chemical Formula 7] group, and the trimethylol alkyl-modified group. Each group of triisocyanate [Chemical Formula 8] is composed of three types of hexamethylene diisocyanate (HMDI) [Chemical Formula 12], hydrogenated xylylene diisocyanate (H ₆ XDI) [Chemical Formula 13], and isophorone diisocyanate (IPDI) [Chemical Formula 14]. It is a trimer based on any one selected compound, and the triisocyanate compound is preferably at least one selected from these nine types. In the industrial material sheet obtained in this way, plasticizer bleed is highly suppressed and excellent weather resistance can be expressed.

  In the industrial material sheet made of soft vinyl chloride resin of the present invention, in the flexible laminate, the triisocyanate compound has a cross-linked structure including at least a bond to the surface of the fiber fabric formed on the soft vinyl chloride resin layer. Is preferred. In the industrial material sheet obtained in this way, plasticizer bleed is highly suppressed and excellent weather resistance can be expressed.

  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 weather resistance 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 weather resistance 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 weather resistance and antifouling properties can be expressed.

  The industrial material sheet made of the soft vinyl chloride resin of the present invention is excellent in plasticizing efficiency without using a phthalate ester compound as a plasticizer, is highly suppressed in plasticizer bleed, and is excellent in weather resistance. So, canvas (for seat houses, truck hoods, field sheets, 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 a long time as an industrial material sheet.

  The requirement of the industrial material sheet made of the soft vinyl chloride resin of the present invention is that, in a flexible laminate in which a soft vinyl chloride resin layer is provided on at least one surface of a textile fabric, the soft vinyl chloride resin layer is A vinyl chloride resin is mainly contained, and further, as a plasticizer, an isophthalic acid dialkyl ester compound, a terephthalic acid dialkyl ester compound, a 1,3-cyclohexanedicarboxylic acid dialkyl ester compound, a 1,4-cyclohexanedicarboxylic acid dialkyl ester compound, and 1 , 2-cyclohexanedicarboxylic acid dialkyl ester compound and at least one selected from the group consisting of a triisocyanate compound and a curing agent in a mass ratio of 10: 0.1 to 10: 1. The compound is isocyanurate-modified tri Isocyanate compounds, biuret modified triisocyanates, essential that that this is trimethylol alkyl-modified one or more members selected from triisocyanates.

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, The combination from two types of fibers similarly described in the paragraph [0015], such as a sheath component obtained by tying polyester short fibers around the outer periphery, can be mentioned. 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 [0015]. 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 represented by these [Chemical Formula 1] and [Chemical Formula 2], R is the same or different from each other, particularly an aliphatic monovalent group having 4 to 10 carbon atoms, such as a linear alkyl group, A branched alkyl group is preferred. R may have 11 to 13 carbon atoms, but the steric hindrance due to the arrangement structure of the alkyl ester is increased by 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 is increased. There is a tendency that the plasticizing efficiency is lowered by the densification.

  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 shown in these [Chemical Formula 3] to [Chemical Formula 5], R is the same or different from each other, particularly an aliphatic monovalent group having 4 to 10 carbon atoms, such as a linear alkyl group, A branched alkyl group is preferred. R may have 11 to 13 carbon atoms, but the 1,3-cyclohexanedicarboxylic acid structure, 1,4-cyclohexanedicarboxylic acid structure, and 1,2-cyclohexanedicarboxylic acid structure may cause steric hindrance due to the arrangement structure of the alkyl ester. The plasticization efficiency tends to decrease due to the increase in the coordination order of the ester polar part to the dipole of the vinyl chloride resin.

  Other plasticizer components that can be used in combination with the plasticizers of [Group 1] to [Group 5] described in paragraphs [0018] and [0019] 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 with respect to the plasticizers of ([Chemical group 1]) to ([Chemical group 4]).

  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 [0018] and [0019]. Including one or more types, plasticizers can be used to effectively plasticize vinyl chloride resins to make soft vinyl chloride resins, and by adding a triisocyanate compound, the soft vinyl chloride resin layer can be given adhesion and heat resistance. At the same time, the introduction of a cross-linked structure highly suppresses plasticizer bleed. And it is preferable that the content ratio of the plasticizer and the triisocyanate compound (the group of [Chemical group 1) to (the group of [Chemical formula 5]) is in the range of the mass ratio of 10: 0.1 to 10: 1. . The compounding amount of the plasticizer selected from (the group of [Chemical 1]) to (the 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. Part. Therefore, the amount of the triisocyanate compound used when 100 parts by mass of a plasticizer selected from (group of [Chemical 1]) to (group of [Chemical 5]) is blended with 100 parts by mass of the vinyl chloride resin. The range is 1 to 10 parts by mass, and similarly, the use of a triisocyanate compound used when 35 parts by mass of a plasticizer selected from (Group of [Chemical 1]) to (Group of [Chemical 5]) is blended. The amount range is 0.35 to 3.5 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 includes a group of isocyanurate-modified triisocyanate [Chemical 6] in combination with a plasticizer selected from (Group of [Chemical 1]) to (Group of [Chemical 5]). (R = [Chemical Formula 9] to [Chemical Formula 11]), a group of bullet modified triisocyanate [Chemical Formula 7] (R = [Chemical Formula 9] to [Chemical Formula 11]), a group of trimethylol alkyl modified triisocyanate [Chemical Formula 8] One or more triisocyanate compounds selected from (R = [Chemical Formula 9] to [Chemical Formula 11]) are contained, and these triisocyanate compounds have a crosslinked structure including a bond to the surface of the fiber fabric with a soft vinyl chloride resin. It is what is formed in the layer. These groups of [Chemical Formula 6] to [Chemical Formula 8] do not have a benzene ring in the chemical structure, so that they do not mutate into a colored quinone structure under the influence of ultraviolet rays. The light fastness when using an industrial material sheet made of vinyl chloride resin outdoors can be stably maintained for a long time in the initial state. These [Chemical Formula 6], [Chemical Formula 7] and [Chemical Formula 8] triisocyanate compound groups are respectively hexamethylene diisocyanate (HMDI) [Chemical Formula 12], hydrogenated xylylene diisocyanate (H ₆ XDI) [Chemical Formula 13] , Isophorone diisocyanate (IPDI) [Chemical Formula 14] is a trimer based on any one compound selected from three types. Specific examples of the triisocyanate compound that can be used in the present invention are 1). Isocyanurate-modified triisocyanate which is a trimer of hexamethylene diisocyanate (HMDI) [Chemical Formula 12] ([Chemical Formula 6]-[Chemical Formula 9]), 2). Hydrogenated xylylene diisocyanate (H ₆ XDI) Isocyanurate-modified triisocyanate ([Chemical 6]-[Chemical 10] system) which is a trimer of [Chemical 13], 3). Isophorone diisocyanate (IPDI) Isocyanurate-modified triisocyanate which is a trimer of [ Chem . 14] ([Chem. 6]-[Chem. 11] system), 4). Burette-modified triisocyanate which is a trimer of hexamethylene diisocyanate (HMDI) [Chemical Formula 12] ([Chemical Formula 7]-[Chemical Formula 9]), 5). Hydrogenated xylylene diisocyanate (H ₆ XDI) Bullet-modified triisocyanate which is a trimer of [ Chem . 13] ([Chem. 7]-[Chem. 10] system), 6). Isophorone diisocyanate (IPDI) Bullet-modified triisocyanate which is a trimer of [ Chem . 14] ([Chem. 7]-[Chem. 11] system), 7). Trimethylol alkyl-modified triisocyanate which is a trimer of hexamethylene diisocyanate (HMDI) [Chemical Formula 12] ([Chemical Formula 8]-[Chemical Formula 9]), 8). Hydrogenated xylylene diisocyanate (H ₆ XDI) Trimethylol alkyl-modified triisocyanate ([Chemical Formula 8]-[Chemical Formula 10]), which is a trimer of [Chemical Formula 13], 9). Nine types of trimethylol alkyl-modified triisocyanate ([Chemical Formula 8]-[Chemical Formula 11]), which is a trimer of isophorone diisocyanate (IPDI) [Chemical Formula 14], can be mentioned. One selected from these nine types The above can be used. The nine types of triisocyanate compounds are preferably in the form of a blocked isocyanate compound in which a blocking agent is temporarily added in order to suppress the reactivity of the isocyanate groups of these triisocyanate compounds. Examples of blocking agents include alcohols, phenols, active methylenes, mercaptans, acid amides, acid imides, imidazoles, ureas, oximes, amines, imides, pyridines and pyrazoles. It is done. These blocked isocyanates individually regenerate the nine types of triisocyanate compounds by dissociating the blocking agent by heating at a specific temperature.

These triisocyanate compounds form a cross-linked structure by bonding of isocyanate groups by addition of isocyanate groups by heating or a catalyst, and at the same time, form bonds to the surface of the fiber fabric, and the entire soft vinyl chloride resin layer is formed. A crosslinked structure is formed, thereby firmly bonding the interface between the soft vinyl chloride resin layer and the fiber fabric. Accordingly, it is preferable that the textile fabric is treated with a silane coupling agent, treated with nanosilica, or treated with corona discharge. In particular, the soft vinyl chloride resin layer preferably contains a polyol compound, and the triisocyanate compound undergoes an addition reaction with the polyol compound to form a urethane bond, thereby generating a crosslinked urethane component in the soft vinyl chloride resin layer. The wear resistance, heat resistance, impact resistance, etc. of the softer vinyl chloride resin layer can be improved. The polyol compound is used in the same amount (mass ratio 1: 1) as the triisocyanate compound, and these are specifically ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, decamethylene glycol, diethylene glycol and other low molecular polyols having a number average molecular weight of 62 to less than 500, and polyester polyols, polyamide ester polyols, polycarbonate polyols, polyether polyols, polyether ester polyols, polyolefin polyols, etc. Number polymeric polyol having an average molecular weight from 500 to 30,000 can be used for. The nanosilica particles are surface hydroxyl group-modified silicon oxide (SiO ₂ ) having a large number of hydroxyl groups on the particle surface, a particle diameter of 10 to 50 nm, and a BET specific surface area of 150 to 300 m ² / g. The triisocyanate compound further reacts with the hydroxyl group on the surface of the nanosilica particles, thereby further improving the adhesion to the fiber fabric subjected to the nanosilica adhesion treatment.

  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) was selected from (group of [Chemical 1]) to (group of [Chemical 5]). Paste of plasticizer (35-100 parts by mass), triisocyanate compound (0.35-10 parts by mass), polyol compound (0.35-10 parts by mass), surface hydroxyl group-modified nanosilica particles (5-20 parts by mass) Using the composition, known coating methods such as dipping (double-sided processing on fiber woven fabric), coating (single-sided processing or double-sided processing on fiber woven fabric, knife coating, gravure coating, clearance coating, etc.) and the like can be mentioned. . 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 [0016] 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 [0016], and 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. 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 [0016]. (Parts of [Chemical 1]) to (group of [Chemical 5]), a triisocyanate compound (0.35 to 10 parts by mass), and a polyol compound. (0.35-10 parts by mass), surface hydroxyl group-modified nanosilica particles (5-20 parts by mass) compound composition using a calender method (sheet), or T-die method The target tarpaulin is obtained by subjecting the (sheet) to thermal lamination or adhesive laminating by the through-hole bridge method. 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 the front and back, and 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 specimens 3 cm wide x 30 cm long were collected and subjected to a creep tester (manufactured by Toyo Seiki Seisakusho:
100 LDR type) with a heat resistance creep resistance of 24 under three conditions of 60 ° C. × 25 kgf load (condition 1), 65 ° C. × 25 kgf load (condition 2), and 70 ° C. × 25 kgf load (condition 3).
Time evaluation.
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)
<Light fastness>
The discoloration of the sheet piece was evaluated with a color difference ΔE (JIS Z8729) every 120 hours, 240 hours, and 480 hours of irradiation time using JIS K7350-3 “Plastic—exposure test method using laboratory light source: ultraviolet fluorescent lamp”. (Based on sheet pieces before promotion)
ΔE = 0-2.9: 1 = Slight discoloration (maintain initial appearance)
ΔE = 3 to 5.9: 2 = Slightly discolored (no problem in practical use)
ΔE = 6 to 11.9: 3 = light brown color (impacts practical use)
ΔE = 12˜: 4 = changes to dark brown (impairs practical use)
<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. Then, the addition reaction of the triisocyanate compound was advanced, impregnated with the paste sol composition of [Formulation 1], and coated to form a soft vinyl chloride resin layer on both sides of the base fabric 1 0.47 mm in thickness A canvas having 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 branched alkyl groups having 9 carbon atoms Ethylene glycol (polyol) 3.5 parts by mass Epoxidized soybean oil (plasticizer) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) ) 2 parts by mass Surface hydroxyl group-modified silica particles (75 nm) 5 parts by mass Rutile-type titanium oxide (white pigment) 5 parts by mass Triisocyanate compound 3 parts by mass * Isocyanine which is a trimer of hexamethylene diisocyanate (HMDI) Rate-modified triisocyanate ([Chem. 6]-[Chem. 9] system)
* The mass ratio of di (2-ethylhexyl) isophthalate to the triisocyanate compound is 60: 3 (20: 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 alkyl group having 9 carbon atoms, and further 3 parts by mass of a triisocyanate compound: isocyanurate-modified triisocyanate ([Chem. 6]-[Chem. 9] system) (HMDI) The thickness of 0.47 mm was the same as in Example 1 except that 3 parts by mass of isocyanurate-modified triisocyanate ([Chem. 6]-[Chem. 10] system), which is a trimer of [Chem. A canvas having a mass of 560 g / m ² was obtained.

[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] where both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and triisocyanate compound: isocyanurate-modified triisocyanate (Chemical Formula 6) -[Chemical 9] system) 3 parts by mass is replaced with 3 parts by mass of isocyanurate-modified triisocyanate ([Chemical 6]-[Chemical 11] system) which is a trimer of hexamethylene diisocyanate (HMDI) [Chemical 12]. Except that, 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.

[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 triisocyanate compound: isocyanurate-modified triisocyanate (Chemical Formula 6) -[Chemical 9] system) 3 parts by mass was replaced with 3 parts by mass of burette-modified triisocyanate ([Chemical 7]-[Chemical 9] system) which is a trimer of isophorone diisocyanate (IPDI) [Chemical 13]. 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)
Triisocyanate compound used in [Formulation 1] in Example 1: 3 parts by mass of isocyanurate-modified triisocyanate ([Chemical Formula 6]-[Chemical Formula 9] system) trimer of isophorone diisocyanate (IPDI) [Chemical Formula 13] [Blend 2] substituted with 3 parts by mass of a burette-modified triisocyanate ([Chemical Formula 7]-[Chemical Formula 10]) 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]; A thickness of 0.36 mm in which a soft vinyl chloride resin layer was formed on both surfaces of the base fabric 2 by proceeding with the addition reaction of the triisocyanate compound, impregnating and coating with the paste sol composition of [Formulation 2], A mesh sheet having 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 3 parts by mass of a triisocyanate compound: burette-modified triisocyanate ([Chemical Formula 7]-[Chemical Formula 10]) is added to isophorone diisocyanate (IPDI). ) The thickness of 0.36 mm and the mass of 470 g were the same as in Example 5 except that it was replaced with 3 parts by weight of a buret-modified triisocyanate ([Chem. 7]-[Chem. 11] system) which is a trimer of / ^{m 2,} to obtain a porosity of 10% of the mesh sheet.

[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] where both R are branched alkyl groups having 9 carbon atoms) are substituted by 60 parts by mass, and triisocyanate compound: burette-modified triisocyanate (Chemical Formula 7) [Chemical Formula 10] 3 parts by mass of trimethylol alkyl-modified triisocyanate ([Chemical Formula 8]-[Chemical Formula 9]) 3 which is a trimer of hydrogenated xylylene diisocyanate (H ₆ XDI) [Chemical Formula 14] A mesh sheet having a thickness of 0.36 mm, a mass of 470 g / m ² , and a porosity of 10% is obtained in the same manner as in Example 5 except that the mass parts are replaced. It was.

[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 triisocyanate compound: burette-modified triisocyanate (Chemical Formula 7) [Chemical Formula 10] 3 parts by mass of trimethylol alkyl-modified triisocyanate ([Chemical Formula 8]-[Chemical Formula 10]) 3 which is a trimer of hydrogenated xylylene diisocyanate (H ₆ XDI) [Chemical Formula 14] 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 the mass part was replaced. Obtained.

[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 branched alkyl groups having 9 carbon atoms Ethylene glycol (polyol) 3.5 parts by mass Epoxidized soybean oil (plasticizer) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) ) 2 parts by mass Surface hydroxyl group-modified silica particles (75 nm) 5 parts by mass Rutile titanium oxide (white pigment) 5 parts by mass Triisocyanate compound 3 parts by mass * 3 amounts of hydrogenated xylylene diisocyanate (H ₆ XDI) Trimethylol alkyl-modified triisocyanate ([Chemical Formula 8]-[Chemical Formula 11])
* The mass ratio of di (2-ethylhexyl) isophthalate to the triisocyanate compound is 60: 3 (20: 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). Each of them is substituted with 60 parts by mass of a branched alkyl group having 9 carbon atoms, and triisocyanate compound: trimethylol alkyl-modified triisocyanate ([Chemical Formula 8]-[Chemical Formula 11] system) is converted to hexamethylene diisocyanate (HMDI). ) The thickness is 0.75 mm as in Example 9, except that 3 parts by mass of isocyanurate-modified triisocyanate ([Chem. 6]-[Chem. 9] system) which is a trimer of [Chem. 12] is substituted. A tarpaulin having 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] is substituted with 60 parts by mass of both branched alkyl groups having 9 carbon atoms) and triisocyanate compound: trimethylol alkyl-modified triisocyanate (Chemical Formula 8) ]-[Chemical 11] system) was replaced with 3 parts by mass of burette-modified triisocyanate ([Chemical formula 7]-[Chemical 9] system) which is a trimer of isophorone diisocyanate (IPDI) [Chemical formula 13]. As in Example 9, a tarpaulin having a thickness of 0.75 mm and a mass of 940 g / m ² was obtained.

[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 triisocyanate compound: trimethylol alkyl-modified triisocyanate (Chemical Formula 8) ]-[Chemical Formula 11]) is a trimethylol alkyl-modified triisocyanate ([Chemical Formula 8]-[Chemical Formula 9] system) 3 mass which is a trimer of hydrogenated xylylene diisocyanate (H ₆ XDI) [Chemical Formula 14] 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 the parts were replaced with parts.

[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 24 are excellent in plasticizing efficiency without using a phthalate ester compound as a plasticizer, highly suppressed in plasticizer bleeding, and excellent in weather resistance. (Seat house use, truck hood use, field product seats, etc.), tarpaulins (for tent structures, building curing, for electric signboards, flexible containers), and mesh sheets (for building curing, protective nets, etc.) It can be used for a long time for material sheets. In particular, the sheets of Examples 13 to 24 (canvas, meshes, tarpaulins) provided with an antifouling layer on the sheets of Examples 1 to 12 are excellent in antifouling properties, and even if dust dirt adheres, it may be at the level of several weeks. For example, dust can be easily removed by wiping or wiping with a wiping cloth, etc., and there is no problem of dust reattachment due to generation of static electricity during wiping, and an antifouling layer is provided on the soft polyvinyl chloride resin layer. As a result, the plasticizer bleed prevention (suppression) effect was further improved, and the outdoor pot life was doubled.

[Comparative Example 1]
In Example 1, the triisocyanate compound used in [Formulation 1]: Isocyanurate-modified triisocyanate ([Chemical Formula 6]-[Chemical Formula 9]) 3 parts by mass were omitted, and the thickness was 0. A canvas of .47 mm and a mass of 560 g / m ² was obtained.

[Comparative Example 2]
In Example 1, the triisocyanate compound used in [Formulation 1]: 3 parts by mass of isocyanurate-modified triisocyanate ([Chem. 6]-[Chem. 9]), 3 amounts of tolylene diisocyanate (TDI) [Chem. 15] 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 3 parts by mass of the isocyanurate-modified aromatic triisocyanate [Chemical Formula 16] was substituted.

[Comparative Example 3]
In Example 1, the triisocyanate compound used in [Formulation 1]: 3 parts by mass of isocyanurate-modified triisocyanate ([Chem. 6]-[Chem. 9]), 3 amounts of tolylene diisocyanate (TDI) [Chem. 15] 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 3 parts by mass of the burette-modified aromatic triisocyanate [Chemical Formula 17], which is the body, was substituted.

[Comparative Example 4]
In Example 1, the triisocyanate compound used in [Formulation 1]: 3 parts by mass of isocyanurate-modified triisocyanate ([Chem. 6]-[Chem. 9]), 3 amounts of tolylene diisocyanate (TDI) [Chem. 15] 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 3 parts by mass of trimethylolpropane-modified aromatic triisocyanate [Chemical Formula 18] was substituted.

[Comparative Example 5]
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 6]
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 7]
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 8]
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 form a cross-linked structure by not containing a triisocyanate compound in the soft vinyl chloride resin layer, so that the resulting bonded canvas has insufficient heat resistance at the joint, and the joint is destroyed in a high temperature use environment. It became easy. Also, because the plasticizer bleed is not suppressed by not forming a cross-linked structure, the plasticizer oozes out on the surface of the canvas and becomes sticky, which causes volatilization loss, and at the same time dust dirt adheres to the canvas surface and sticks. It was easy to damage the appearance. The canvases of Comparative Examples 2 to 4 use a triisocyanate compound having a benzene ring in the structure of the soft vinyl chloride resin layer, thereby generating a chromophore having a quinone structure under the influence of ultraviolet rays such as sunlight. The canvas became brown over time and the appearance deteriorated. The canvases of Comparative Examples 5 to 7 have poor initial compatibility with the triisocyanate compound in the soft vinyl chloride resin composition due to the use of the phthalate plasticizer in the soft vinyl chloride resin layer, and the soft vinyl chloride resin If the composition is not sufficiently agitated and aged, the gelation process is carried out 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 phthalates. It became the cause of inhibiting the suppression of the bleeding of the acid ester plasticizer. The canvas of Comparative Example 8 uses di-2-ethylhexyl adipate (also known as dioctyl adipate) as the plasticizer in the soft vinyl chloride resin layer, which promotes the bleed of the plasticizer and the plasticizer on the canvas surface. It oozes out and becomes sticky, which causes volatilization loss, and at the same time, dust dirt adheres to the surface of the canvas and sticks to it.

  According to the present invention, canvas (for a seat house) is excellent because it is excellent in plasticizing efficiency without using a phthalate ester compound as a plasticizer, is highly suppressed in plasticizer bleeding, and has excellent weather resistance. , For truck hoods, field sheets, etc., long as 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 period.

Claims (5)

A soft vinyl chloride resin industrial material sheet made of a flexible laminate having a fiber 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 is a vinyl chloride type Resin is mainly included, and diphthalic acid dialkyl ester ([Chemical group 1]), terephthalic acid dialkyl ester ([Chemical group 2]), 1,3-cyclohexanedicarboxylic acid dialkyl ester ([Chemical group 3] group) 1, one or more plasticizers selected from 1,4-cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical Formula 4]) and 1,2-cyclohexanedicarboxylic acid dialkyl ester (Group of [Chemical Formula 5]), and tri mass an isocyanate compound ratio of 10: 0.1 to 10: include one of a range, and a nanosilica particles are surface hydroxyl-modified silicon oxide Is constituted by a-law, the triisocyanate compound, the group of isocyanurate modified triisocyanate formula 6 (R = formula 9 - [Formula 11]), the group of biuret modified triisocyanate [Formula 7] (R = [Formula 9] - [formula 11]), there is trimethylol group of alkyl-modified triisocyanate formula 8 (R = [Formula 9] - [formula 11]) one or more selected from, the flexible A soft vinyl chloride resin industrial material , wherein the triisocyanate compound has a cross-linked structure including at least a surface of the fiber fabric and a bond to the nanosilica particles in the soft vinyl chloride resin layer Sheet.
In the triisocyanate compound, the group of the isocyanurate-modified triisocyanate [Chem. 6], the group of the bullet-modified triisocyanate [Chem. 7], and the group of the trimethylol alkyl-modified triisocyanate [Chem. 8] are each hexamethylene. Diisocyanate (HMDI) [Chemical Formula 12], hydrogenated xylylene diisocyanate (H ₆ XDI) [Chemical Formula 13], isophorone diisocyanate (IPDI) [Chemical Formula 14] The industrial material sheet made of soft vinyl chloride resin according to claim 1, which is a trimer and the triisocyanate compound is at least one selected from these nine types.
3. The soft vinyl chloride resin industry according to claim 1 or 2 , wherein 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. Material sheet. The industrial material sheet made of soft vinyl chloride resin according to claim 3 , 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 3 , which is at least one selected from zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sol.