JP2016074162A - Japanese paper-tone composite sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a Japanese paper-tone composite sheet that has flameproofness and flexibility, exhibits a Japanese paper-tone appearance and a Japanese paper-tone appearance when light is transmitted, and can exhibit flameproofness stably over a long period of time especially in an embodiment where it comprises as a component a soft vinyl chloride resin with use of a non-phthalic acid plasticizer.SOLUTION: In a flame-retardant flexible laminate which is produced by using a flame-retarded Japanese paper or a flame-retarded nonwoven fabric as a substrate and forming a soft vinyl chloride resin layer on at least one surface of the substrate and has irregular shading depending upon optical transparency, the soft vinyl chloride resin layer comprises as main components 100 pts.mass of vinyl chloride resin and 15 to 60 pts.mass of a cyclohexanedicarboxylic acid dialkyl ester and further comprises 5 to 40 pts.mass of phosphate.SELECTED DRAWING: None

Description

  The present invention relates to an optical ceiling film having irregular shading in light transmission obtained by providing a soft vinyl chloride resin layer on a base material of Japanese paper or non-woven fabric, a lighting shade, a blind, a partition, and an indoor wall material. Flame proof and flexible laminated sheet used for paper sliding doors, furniture, bathroom / greenhouse curtains, illuminated signboards, lantern display objects, projection screens, bags / pouches, stationery / miscellaneous, Japanese paper-like appearance and light transmission The present invention relates to a composite sheet that sometimes exhibits a Japanese paper-like appearance, and particularly to a composite sheet that includes a soft vinyl chloride resin using a non-phthalic acid plasticizer as a component.

  The interior material with the appearance of Japanese paper is the same using reinforced Japanese paper laminated with a transparent resin film on Japanese paper, decorative paper with Japanese paper enclosed in a transparent resin plate, and non-woven fabric made of synthetic fibers that mimics Japanese paper. There are various types of reinforced Japanese paper and decorative panels, such as hotels, inns, resort / amusement facilities, commercial facilities such as shopping malls, public facilities such as stations, airports, ceremonial halls, multipurpose halls, school buildings, government buildings, It is used everywhere in office buildings, condominiums, detached houses, etc., for partitions, blinds, lighting shades, shoji screens, joinery, and row lamp type display objects.

  As specific examples of materials for blinds having a Japanese paper-like design appearance, Examples 1 to 5 and 7 of Patent Document 1 are composed of a vinyl chloride resin layer / Japanese paper-like appearance layer (nonwoven fabric) / vinyl chloride resin layer. A material for blinds that has a Japanese paper-like appearance with excellent Japanese paper-like visibility, has a Japanese-paper-like design against light reflection, is soft, has excellent shape retention, and flame resistance is disclosed. ing. In Examples 1 to 5 and 7 described above, the requirements for flameproofing are satisfied only by making the Japanese paper-like appearance layer into a glass nonwoven fabric. In the configuration of the polyester nonwoven fabric as shown in Example 6, JIS-L1091 A-1 It does not satisfy the flameproofness of Category 3 of the method and A-2 method test. (Paragraph [0051] Table 1) However, the glass nonwoven fabric was poor in Japanese paper appearance because it was oriented linearly when the nonwoven fabric was rolled because the chopped strands of the constituent elements were high in rigidity and difficult to bend. Although it is difficult to satisfy flameproofness with a polyester nonwoven fabric, it is easy to obtain a Japanese paper-like appearance. Further, the present applicant, as Patent Document 2, as a non-combustible building material suitable for a partition material and an optical ceiling material, as a laminate of a sheet-like woven fabric made of glass long fibers and a flame-retardant nonwoven fabric sheet, We proposed a flexible Japanese paper-like incombustible sheet in which a flame retardant resin layer was provided between the flame retardant nonwoven sheet and the flame retardant nonwoven sheet and the flame retardant resin layer were partially bonded. Certainly, this sheet can achieve both flameproofness and Japanese paper-like appearance, but it reveals the problem that the partially bonded flame-retardant nonwoven sheet is easy to peel off depending on the usage environment and cleaning maintenance method. there were.

  At present, phthalic acid diester plasticizers such as dioctyl phthalate (DOP), diisononyl phthalate (DINP), and diheptyl phthalate (DHP) are widely used as plasticizers in vinyl chloride resin products. In the fields of food wraps, medical devices, agricultural films, etc., replacement with non-phthalate plasticizers has been promoted to ensure safety. For example, as an example of a non-phthalate ester plasticizer, 1,2-cyclohexanedicarboxylic acid diesters are known. Patent Document 3 discloses roll peelability, blocking resistance, transparency, printability, and high-frequency welder suitability. As a vinyl chloride resin film excellent in the above, a film using 1,2-cyclohexanedicarboxylic acid diisononyl ester as a plasticizer is disclosed, and the possibility of use in combination with another plasticizer is also described. However, Japanese paper-like building materials still contain 1,2-cyclohexanedicarboxylic acid diesters, including the provision of flameproof performance and the stable expression of flameproofness in Category 3 of JIS-L1091A-1 method and A-2 method test. The spread of the products used has not yet progressed.

JP2013-19254A JP 2011-131504 A JP 2011-231226 A

  The present invention relates to a composite sheet having irregular shading in light transmission obtained by providing a flame-retardant Japanese paper or flame-retardant nonwoven fabric as a base material and providing a soft vinyl chloride resin layer on the base material. Flameproof when used in shades, blinds, partitions, indoor wall materials, shoji / jointing furniture, bathroom / greenhouse curtains, electric signs, display lamps, projection screens, bags / porch, stationery / miscellaneous goods In an embodiment that is flexible and has a Japanese paper-like appearance and a Japanese paper-like appearance when transmitting light, and that contains a soft vinyl chloride resin using cyclohexanedicarboxylic acid dialkyl ester as a non-phthalic acid plasticizer as a constituent element. An object of the present invention is to provide a Japanese paper-like composite sheet that can stably exhibit flame resistance for a long period of time.

  As a result of research and examination of the Japanese paper-like composite sheet in view of the above-mentioned present situation, the present inventor uses a flame-retardant Japanese paper or a flame-retardant nonwoven as a base material, and a soft vinyl chloride resin on at least one surface of the base material. In flame-retardant flexible laminates with layers, flameproofness and flexibility can be stably maintained for a long period of time by including cyclohexanedicarboxylic acid dialkyl esters and phosphates in the soft vinyl chloride resin layer. And it discovered that the composite sheet which expresses a Japanese paper-like external appearance and a Japanese paper-like external appearance at the time of light transmission was obtained, and came to complete this invention.

That is, the Japanese paper-like composite sheet of the present invention is irregular in light transmittance, in which a flame retardant Japanese paper or a flame retardant nonwoven fabric is used as a base material, and a soft vinyl chloride resin layer is provided on at least one surface of the base material. A flame retardant flexible laminate having a shadow, wherein the soft vinyl chloride resin layer comprises 100 parts by mass of a vinyl chloride resin and 15-60 parts by mass of a cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical Formula 1]). It is preferable to contain 5 to 40 parts by mass of a phosphate contained in the main body. In the composite sheet obtained by this, the flameproofness and flexibility of Category 3 of the JIS-L1091A-1 method and the A-2 method test are stably maintained for a long time, and the Japanese paper-like appearance and the Japanese paper-like appearance at the time of light transmission. Appearance can be expressed.

  In the Japanese paper-like composite sheet of the present invention, the flame-retardant flexible laminate is composed of the base material having a porosity of 5 to 35% and soft vinyl chloride having a thickness of 0.05 to 0.5 mm formed on the surface thereof. It is preferable to be comprised by the resin film or sheet | seat. By using flame retardant Japanese paper or flame retardant nonwoven fabric with a porosity of 5 to 35% as a base material, a contrast effect between the void portion and the solid portion can be obtained, and the texture of the fiber pattern of the Japanese paper is more emphasized. Since the Japanese paper tone is clear, it is particularly suitable for applications such as optical ceiling membranes, partitions, indoor wall materials, shojis and fittings, and the entire surface of the base material is a flexible polyvinyl chloride resin film or sheet having a thickness of 0.05 to 0.5 mm. By coating with, it is excellent in durability and dimensional stability, and furthermore, it is possible to stably impart flame resistance of Category 3 of JIS-L1091A-1 method and A-2 method test to the entire composite sheet. .

  The Japanese paper-like composite sheet of the present invention comprises the base material having the flame-retardant flexible laminate having a porosity of 0 to less than 5%, a soft vinyl chloride resin paste sol coating on the surface thereof, and a heating gel thereof It is preferable to be composed of a soft vinyl chloride resin layer having a thickness of 0.01 to 0.2 mm formed by the conversion. By using flame retardant Japanese paper or flame retardant nonwoven fabric with a porosity of less than 0-5% as the base material, the flame resistance of Category 3 of JIS-L1091A-1 method and A-2 method test is stabilized on the entire composite sheet The entire composite sheet is excellent in durability, flexibility, dimensional stability, etc. by forming the entire base material with a soft vinyl chloride resin layer having a thickness of 0.01 to 0.2 mm. As a result, a flameproof material with an enhanced Japanese paper feel can be obtained, so that it can be suitably used particularly for lighting shades, shojis / joints, row lamp display objects, and the like.

  The Japanese paper-like composite sheet of the present invention is any one selected from boric acid esterification, phosphoric acid esterification, and silicic acid esterification on the cellulose hydroxyl group of natural fibers forming the Japanese paper in the flame retardant Japanese paper. It is preferable that the chemical modification treatment is performed. This makes it possible to stably impart the flameproofness of Category 3 of the JIS-L1091A-1 method and the A-2 method test to the entire composite sheet obtained.

  In the Japanese paper-like composite sheet of the present invention, the flame retardant nonwoven fabric includes 1) a dispersion containing a flame retardant in a synthetic fiber forming the nonwoven fabric, and 2) a raw material polymer of the synthetic fiber forming the nonwoven fabric with a phosphorus compound. It is preferably any one selected from those using a polymerized copolymer, and 3) those obtained by attaching a flame retardant between the surface of the synthetic fiber and the fiber by post-processing after the production of the nonwoven fabric. This makes it possible to stably impart the flameproofness of Category 3 of the JIS-L1091A-1 method and the A-2 method test to the entire composite sheet obtained.

  The Japanese paper-like composite sheet of the present invention, in the flame retardant Japanese paper, 1) using dyed fibers as part of natural fibers, 2) using a plurality of types of natural fibers, 3) natural fibers having different fiber diameters It is preferable to form a Japanese paper-like appearance by using one or more of fiber bundles. This makes it possible to further enhance the Japanese paper-like appearance and Japanese paper-light-transmitting appearance of the composite sheet obtained, especially optical ceiling membranes and partitions, indoor wall materials, shojis / joints, lighting shades, row lamp type display objects, etc. It can be used in a suitable manner.

  In the flame retardant nonwoven fabric of the present invention, the Japanese paper-like composite sheet is 1) using colored fibers as part of the synthetic fibers, 2) using a plurality of types of synthetic fibers, and 3) having different fiber bundle diameters. It is preferable to form a Japanese paper-like appearance by using one or more of synthetic fiber bundles. This makes it possible to further enhance the Japanese paper-like appearance and Japanese paper-light-transmitting appearance of the composite sheet obtained, especially optical ceiling membranes and partitions, indoor wall materials, shojis / joints, lighting shades, row lamp type display objects, etc. It can be used in a suitable manner.

  The Japanese paper-like composite sheet of the present invention is an antifouling agent comprising an inorganic colloidal material having a primary particle size of 3 nm to 150 nm supported on a binder component containing a hydrolysis condensate of a silane coupling agent on the soft vinyl chloride resin layer. The inorganic colloidal substance is a photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol It is preferable that the cerium oxide sol and the composite oxide (zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sol be one or more metal oxides. This not only provides anti-fouling properties such as increased wiping and removal of dust dirt and oil stains attached to the surface of the composite sheet obtained, or a self-cleaning effect due to a photocatalytic substance, but also manifests an antistatic effect. It also makes it possible to provide an anti-adhesion effect for allergenic dust such as pollen and mite carcasses.

  In the Japanese paper composite sheet of the present invention, a fluororesin layer is formed on the soft vinyl chloride resin layer, and the fluororesin forming the fluororesin layer is composed of vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoro A polymer obtained by homopolymerizing one monomer selected from ethylene (TrEE), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), or two or more monomers thereof It is preferable that it is 1 or more types chosen from the copolymer formed by copolymerizing these, or the copolymer formed by copolymerizing these 1 or more types of monomers with a vinyl monomer. As a result, it is possible to develop antifouling properties such as increasing the wiping and removing properties such as dust dirt and oil stains adhering to the surface of the composite sheet obtained, and it can be used for a long time.

  The Japanese paper-like composite sheet of the present invention contains a cyclovinyldicarboxylic acid dialkyl ester and a phosphate in a soft vinyl chloride resin layer, thereby stably maintaining flameproofness and flexibility for a long period of time, and has a Japanese paper-like appearance. And composite sheets that exhibit a Japanese paper-like appearance when transmitting light, especially light ceiling membranes, lighting shades, blinds, partitions, indoor wall materials, shojis / furnitures, bathrooms / greenhouse curtains, electric signs, row lamp type display objects Suitable for use in projection screens, bags, pouches, stationery and sundries.

  The requirement of the Japanese paper-like composite sheet of the present invention is that a flame-retardant flexible laminate comprising a flame-retardant Japanese paper or a flame-retardant nonwoven as a base material and a soft vinyl chloride resin layer provided on at least one surface of the base material. It is essential that the soft vinyl chloride resin layer mainly contains a vinyl chloride resin and a dialkyl ester of cyclohexanedicarboxylic acid, and further contains phosphates. In addition, these Japanese papers may be any of known color patterns / patterns made by known Japanese paper making techniques such as paper, paper, forced paper, paper, cloud dragon paper, waste paper, hemp paper, etc. . Non-woven fabrics are used by combining dyed or original fibers with some of the fibers used (cut fibers), and by using together fiber bundles (including core-sheath fibers having thermal adhesiveness) with different fiber diameters and lengths. What constitutes the handle is particularly preferred.

  Flame retardant Japanese paper as a base material used for the Japanese paper-like composite sheet of the present invention is any one selected from boric acid esterification, phosphoric acid esterification, and silicic acid esterification on the cellulose hydroxyl group of natural fibers forming the Japanese paper. Or those subjected to one kind of chemical modification treatment. The natural fibers that form Japanese paper are natural raw grass fibers extracted and extracted from basts, stems and leaves of plants such as bamboo shoots, cocoons, husks, kenaf, hemp, jute, cocoons, cocoons, bamboo, bananas, bagasse and trees. , And can be used alone with regenerated cellulose fibers such as rayon and cupra, or mixed use to further enhance the Japanese paper pattern, these fibers are optionally bleached with chlorinated compounds or monopersulfuric acid, after bleaching It is preferable to use any combination of those dyed in an arbitrary color tone, those obtained by immersing them in an alkaline aqueous solution such as caustic soda and ammonia, and mercerized. These natural raw fiber fibers have a length in the range of 10 to 150 mm and contain at least 50% by mass of fibers having a length of 25 to 75 mm with respect to the whole Japanese paper. In addition, it is preferable because sufficient Japanese paper strength can be obtained, and it is preferable that the natural raw grass fiber has a diameter of 20 to 500 μm, and a fiber having a diameter of 50 to 300 μm as a main component. Moreover, it is preferable because sufficient Japanese paper strength can be obtained. In flame-retardant Japanese paper, either 1) using dyed fibers as part of natural fibers, 2) using multiple types of natural fibers, or 3) using natural fiber bundles with different fiber diameters By forming the Japanese paper-like appearance by using one or more kinds, the Japanese paper-like appearance and the Japanese paper light-controlling appearance can be more emphasized.

Japanese paper is made by a known Japanese paper-making method. In particular, by using Japanese paper with a porosity of 5 to 35% and a mass of 15 to 150 g / m ² as a base material, a contrast effect between the void portion and the substantial portion can be obtained. Because the texture of the Japanese paper fiber pattern is emphasized and the Japanese paper tone becomes clear even in the distance, it is particularly suitable for applications such as optical ceiling membranes, partitions, indoor wall materials, shojis, and fittings. It is excellent in durability and dimensional stability by being covered with a soft vinyl chloride resin film or sheet having a thickness of 05 to 0.5 mm, and the composite sheet as a whole is flameproof in Category 3 of the JIS-L1091A-1 method and A-2 method test. Can be stably provided. The Japanese paper used is subjected to a flame retardant treatment with any one (or more) selected from boric acid esterification, phosphoric acid esterification, and silicic acid esterification in the range of 1 to 15 g / m ² in increase. Thus, flame-retardant Japanese paper is obtained, and bleaching treatment, dyeing treatment, and mercerization treatment may be performed as necessary. 1) Boric acid esterification treatment includes boric acid such as orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ), and sodium tetraborate hydrate (Na ₂ B ₄ O ₇ · 10H ₂ O), The boric acid esterification reaction is completed by impregnating Japanese paper with an aqueous solution of one or more selected from borate salts such as sodium pentaborate (NaB ₅ O ₈ ) and drying by heat treatment at a temperature of 100 to 150 ° C. To obtain a flame-retardant Japanese paper having a borated esterified cellulose element. 2) Phosphate esterification treatment is carried out using phosphoric acids such as orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid, polyphosphoric acid (HPO ₃ ) n, phosphorous acid, phosphinic acid, and metals derived from these phosphoric acids. By impregnating Japanese paper with an aqueous solution of at least one selected from phosphates such as salts and ammonium salts and drying by heat treatment at a temperature of 100 to 150 ° C., the phosphoric acid esterification reaction is completed and phosphoric acid esterification is achieved. Obtain a flame retardant Japanese paper with cellulose elements. 3) Silicate esterification treatment is performed by impregnating Japanese paper with an aqueous solution of at least one selected from silicic acid and silicates such as sodium silicate (water glass), lithium silicate, and potassium silicate. Heat treatment drying at a temperature of 150 ° C. completes the silicic acid esterification reaction to obtain a flame-retardant Japanese paper of a silicic acid esterified cellulose element.

The flame retardant nonwoven fabric as a base material used for the Japanese paper-like composite sheet of the present invention is 1) a material containing a flame retardant dispersed in a synthetic fiber forming the nonwoven fabric, and 2) phosphorus in the raw material polymer of the synthetic fiber forming the nonwoven fabric. One using a copolymer obtained by copolymerizing a compound, 3) any one selected from a surface of a synthetic fiber and a flame retardant adhered or exhausted by post-processing after the production of the nonwoven fabric, A mass of 15 to 150 g / m ² is used. The synthetic fiber forming the nonwoven fabric is specifically polyester fiber, nylon fiber, vinylon fiber, polypropylene fiber, polyethylene fiber, core / sheath fiber of polypropylene (core) / polyethylene (sheath), polyester (core) / polyethylene (sheath), Examples include single-use or mixed use of high-melting point polyester (core) / low-melting point polyethylene (sheath) core-sheath fiber, aramid fiber, and heterocyclic polymer fiber, and these are preferably in the form of a multifilament yarn. Non-woven fabric was obtained by spinning a filament cut fiber (fineness of 1.5 to 121 dtex, fiber length of 10 to 150 mm) obtained by melt spinning a thermoplastic resin by a spunbond method, a dry method, a wet method, or the like. A material obtained by pressing a fleece bonded between fibers by a chemical bond method, a needle punch method, a spunlace method, a thermal bond method, or the like can be used. In particular, multifilament yarns such as glass fiber, silica fiber, alumina fiber, and carbon fiber may be blended into the nonwoven fabric for the purpose of emphasizing design and reinforcing flame retardancy by a dry method up to 50% by mass relative to the mass of the nonwoven fabric. . These nonwoven fabrics may be subjected to water repellent treatment, water absorption prevention treatment, adhesion treatment, and the like as necessary. Any one of 1) using colored fibers as a part of synthetic fibers, 2) using a plurality of types of synthetic fibers, and 3) using synthetic fiber bundles having different fiber bundle diameters. By using one or more kinds, the Japanese paper tone appearance and the Japanese paper light control transmission appearance can be more emphasized.

  In flame retardant nonwoven fabrics, 1) As flame retardants to be added and used during melt spinning of synthetic fibers forming nonwoven fabrics, phosphoric acid amide condensates, aliphatic phosphate esters, aromatic phosphate esters, alkoxyphosphazenes, halogenated Phosphorus compounds such as alkyl polyphosphate phosphonates can be mentioned, and the addition amount of the phosphorus compound is preferably 500 to 10,000 ppm as the phosphorus atom content in the fiber. 2) As a specific example of using a copolymer polymer obtained by copolymerizing a phosphorus compound as a raw material polymer of a synthetic fiber forming a nonwoven fabric, an acid component containing a phosphorus atom and / or Alternatively, a flame retardant polyester copolymer resin obtained by copolymerizing a glycol component as a third component and having a phosphorus atom content of 500 to 10,000 ppm can be used. The phosphorus atom-containing compound to be copolymerized is preferably an aromatic phosphate compound having two hydroxyl groups, carboxylic acid groups and the like per molecule. 3) As a flame retardant to be attached or exhausted between the surface of the synthetic fiber and the fiber by post-processing after the production of the nonwoven fabric, metal phosphate, metal organic phosphate, aromatic condensed phosphate ester, phosphonate, Phosphoric acid-containing compounds such as phosphonic acids, phosphinic acids (salts), phosphazenes, and ammonium polyphosphates are preferred.

The soft vinyl chloride resin layer in the Japanese paper-like composite sheet of the present invention mainly contains 100 parts by mass of a vinyl chloride resin and 15-60 parts by mass of a cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical Formula 1]), It is preferable to contain 5-40 mass parts of phosphates. Cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical Formula 1]) is selected from 1,2-cyclohexanedicarboxylic acid dialkylester group, 1,3-cyclohexanedicarboxylic acid dialkylester group, and 1,4-cyclohexanedicarboxylic acid dialkylester group One or more selected compounds. In the group of dialkyl esters represented by [Chemical Formula 1], in the formula, 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 or a branched chain. It represents an alkyl group, an alicyclic group, and the like.

  Examples of the plasticizer of the dialkyl ester of cyclohexanedicarboxylic acid (the group of [Chemical Formula 1]) include di-2-ethylhexyl cyclohexanedicarboxylate (also known as dioctyl cyclohexanedicarboxylate) (C8: MW393) and diisononyl cyclohexanedicarboxylate (C9: MW421). Particularly preferred are dibutyl cyclohexanedicarboxylate (C4: MW281), diisobutylcyclohexanedicarboxylate (C4: MW281), dihexyl cyclohexanedicarboxylate (C6: MW337), diheptylcyclohexanedicarboxylate (C7: MW362), dinonyl cyclohexanedicarboxylate (C9). : MW421), cycloisodicarboxylate diisodecyl (C10: MW450), cyclohexanedicarboxylate didecyl (C10: W450), butylbenzyl cyclohexanedicarboxylate (C4, C7: MW315) and the like, all of which have a dicarboxylic acid dialkyl ester bonded to the cyclohexane ring in the ortho position (ie, 1.2-position), meta position (ie, 1.3-position) and para-position (that is, 1.4-position) are all included.

  These plasticizers of cyclohexanedicarboxylic acid dialkyl esters (group of [Chemical Group 1]) are used in combination with 5 to 40 parts by mass of phosphate, thereby being transparent (perspective) to the soft vinyl chloride resin layer. Flame retardancy can be imparted while maintaining the state. Specific examples of the phosphate include tricresyl phosphate (also known as TCP: tricresyl phosphate), triphenyl phosphate (also known as TPP: triphenyl phosphate), trixylenyl phosphate (also known as TXP: trixylenyl phosphate), and cresyl diphenyl phosphate. (Also known as CDP: cresyl diphenyl phosphate), octyl diphenyl phosphate (ODP), cresyl 2,6-xylenyl phosphate, resorcinol bisdiphenyl phosphate and other aromatics, trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl Aliphatics such as phosphate (TBP), trioctyl phosphate (TOP), trichloroethyl phosphate, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate Feto, tris (dichloropropyl) phosphate, tris (tribromoneopentyl) phosphate, halogen-containing, such as tris (2,3-dibromopropyl) phosphate and the like. If necessary, polyester oligomer, tributyl acetyl citrate, di-2-ethylhexyl adipate, tri-2-ethylhexyl trimellitic acid, reactive acrylic compound having two or more (meth) acryloyl groups at the molecular end or side chain A liquid compound such as an allyl phthalate compound having two or more allyl groups may be used as an auxiliary plasticizer component.

  The vinyl chloride resin used 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 that can be copolymerized with the vinyl chloride monomer. In the case of such a copolymer, a copolymer having a vinyl chloride-containing component exceeding 60% by mass is treated as a vinyl chloride resin in the requirements of the present invention. Examples of copolymer components include α-olefins having 2 to 30 carbon atoms, acrylic acid and esters thereof, methacrylic acid and esters thereof, maleic acid and esters thereof, vinyl acetate, vinyl propionate, and alkyl vinyl ether. Compound etc. are mentioned. The soft vinyl chloride resin layer may contain various arbitrary amounts of known additives for soft vinyl chloride resin. As stabilizers for soft vinyl chloride resin, calcium zinc composite, barium zinc composite, organic tin Stabilizers such as laurate, organotin mercaptite, and epoxy can be used alone or in combination. Transparency of soft vinyl chloride resin layers such as light-resistant stabilizers, UV absorbers, antioxidants, antibacterial agents, antifungal agents, colorants (pigments), optical brighteners, antistatic agents, waxes, etc. (Visibility of Japanese paper-like appearance of the base material) can be included within a range not hindering.

  As a method for forming a soft vinyl chloride resin layer on a base material such as a flame retardant Japanese paper or a flame retardant nonwoven fabric, 1) a suspension polymerization type vinyl chloride resin (100 parts by mass) and a cyclohexanedicarboxylic acid dialkyl ester ( 1] group) 15 to 60 parts by mass, and a compound (composition) using 5 to 40 parts by mass of a phosphate, and a film (sheet) formed by the calender method to a thickness of 0.05 to 1.0 mm, or T A film (sheet) extruded to a thickness of 0.05 mm to 1.0 mm by a die method is laminated on a base material having a porosity of 5 to 35% by a bridge lamination or an adhesive by a heat lamination method. Adhesives include known emulsion adhesives (for example, vinyl chloride resin-based, urethane-based, vinyl acetate-based), known solvent-based adhesives (for example, urethane-based in combination with isocyanate-based curing agents), and paste-like soft chloride A vinyl resin composition can be used. 2) Paste sol composition in which 15-60 parts by mass of cycloalkylenedicarboxylic acid dialkyl ester (group of [Chemical Formula 1]) and 5-40 parts by mass of phosphate are combined with emulsion polymerization type vinyl chloride resin (100 parts by mass) A substrate having a porosity of 0 to less than 5% and a coating film formed (heat-gelled) to a thickness of 0.01 mm to 0.2 mm by a coating method, or a substrate having a porosity of less than 0 to 5% The material was immersed in a paste sol composition bath, pulled up and simultaneously squeezed with two rolls to form a coating film on both sides of the substrate simultaneously (heated gelation) to a thickness of 0.01 mm to 0.2 mm Can be illustrated. The paste sol composition can contain an adhesive, and a reactive group-containing compound such as a diisocyanate compound, a triisocyanate compound, or an oxazoline compound can be used as the adhesive.

  On the soft vinyl chloride resin layer, there is provided an antifouling layer in which an inorganic colloidal material having a primary particle size of 3 nm to 150 nm is supported on a binder component containing a hydrolysis condensate of a silane coupling agent. Colloidal materials include photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and composite oxide ( Zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) is preferably at least one metal oxide selected from sols. This not only provides anti-fouling properties such as increased wiping and removal of dust dirt and oil stains attached to the surface of the composite sheet obtained, or a self-cleaning effect due to a photocatalytic substance, but also manifests an antistatic effect. It also makes it possible to provide an anti-adhesion effect for allergenic dust such as pollen and mite carcasses.

  A fluororesin layer is formed on the soft vinyl chloride resin layer, and the fluororesin constituting the fluororesin layer is vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene (TrEE), tetrafluoroethylene. (TFE), chlorotrifluoroethylene (CTFE), a polymer obtained by homopolymerizing one type of monomer selected from hexafluoropropylene (HFP), or a copolymer obtained by copolymerizing two or more types of these monomers, Or it is preferable that it is 1 or more types chosen from the copolymer formed by copolymerizing these 1 or more types of monomers with a vinyl monomer. As a result, it is possible to develop antifouling properties such as increasing the wiping and removing properties such as dust dirt and oil stains adhering to the surface of the composite sheet obtained, and it can be used for a long time.

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.
(1) Flame retardance of sheet (sheet having a mass of 450 g / m ² or less)
The test was conducted in accordance with Article 4 of the Fire Service Law Enforcement Regulations (JIS L-1091: A-1 Law Category 3: 1 minute heating) and evaluated according to the following criteria.
1: Carbonization area 30 cm ² or less, after flame time 3 seconds or less,
Residual dust time is 5 seconds or less and combustion length is 20 cm or less. 2: One or more items of carbonization area, afterflame time, residual dust time, carbonization distance are
Greater than standard values (2) Flame retardancy of the sheet (sheet exceeding weight 450 g / ^{m 2)}
Tests were conducted in accordance with Article 4 of the Fire Service Law Enforcement Regulations (JIS L-1091: A-2 Law Category 3: Heating for 2 minutes) and evaluated according to the following criteria.
1: Carbonization area 40 cm ² or less, after flame time 5 seconds or less,
Residual dust time is 20 seconds or less and combustion length is 20 cm or less. 2: One or more items of carbonization area, afterflame time, residual dust time, carbonization distance
(3) Flame retardant stability (plasticizer bleed suppression effect)
A sample of 25 cm width × 35 cm length was rolled up in the length direction to have a roll inner diameter of 2 cm, and this was left to stand at 35 ° C. × 720 hours, and the sample which was taken out and spread out was subjected to the above difficulty (1) or (2). Flammability evaluation was performed. (Judgment criteria are the same)
(4) Japanese paper-like appearance and Japanese paper-like appearance at the time of light transmission 1: Both good 2: Lack of the image of Japanese paper tone at the time of light transmission 3: Both lack the image of Japanese paper

[Example 1]
<Flame-retardant Japanese paper: Base material 1>
Unryu-sushi-made Japanese paper (33 g / m ² per unit area: porosity 12%) is immersed in an aqueous solution bath of 3% by weight boric acid + 78% by weight ethyl cellosolve, and borated for 30 minutes to the hydroxyl group of Japanese paper (cellulose). This was dried at 100 ° C. to obtain a substrate 1. The increase in mass before and after boric acid esterification of Japanese paper was 3 g / m ² .
<Japanese paper composite sheet>
Using a soft vinyl chloride resin compound according to the following [Composition 1], this was applied to a calender molding machine to obtain a film having a thickness of 0.12 mm. This film is laminated on both sides of the substrate 1 with a laminator while softening the film under a hot roll condition of 170 ° C., and a Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 360 g / m ² by bridging the gaps. Got.
* [Composition 1] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl (plasticizer) 25 parts by mass * Product name: Hexamol DINCH ( (Made by BASF)
20 parts by mass of cresyl diphenyl phosphate (flameproof plasticizer) (also known as CDP: cresyl diphenyl phosphate)
Epoxidized soybean oil (plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass

[Example 2]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 359.5 g / m ² was obtained in the same manner as in Example 1 except that the base material 1 of Example 1 was changed to the following base material 2.
<Flame-retardant Japanese paper: Base material 2>
Unryu-Japanese paper (weighing 33 g / m ² : porosity 12%) is dipped in an aqueous solution bath of 3% by mass phosphoric acid + 78% by mass ethyl cellosolve, and is subjected to phosphoric esterification treatment for hydroxyl groups of Japanese paper (cellulose) for 30 minutes. This was dried at 100 ° C. to obtain a substrate 1. The increase in mass of Japanese paper before and after the phosphoric acid esterification treatment was 2.5 g / m ² .

[Example 3]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 359.5 g / m ² was obtained in the same manner as in Example 1 except that the base material 1 of Example 1 was changed to the following base material 3.
<Flame-retardant Japanese paper: Base material 3>
Unryu-saki-made Japanese paper (33 g / m ² per unit area: 12% porosity) is immersed in an aqueous solution bath of 3% by mass silicic acid + 78% by mass ethyl cellosolve and treated for 30 minutes with silicic acid esterification of hydroxyl groups on Japanese paper (cellulose). This was dried at 100 ° C. to obtain a substrate 1. The increase in mass of Japanese paper before and after silicic acid treatment was 2.5 g / m ² .

[Example 4]
<Flame-retardant nonwoven fabric: Base material 4>
Japanese paper-style spunbonded nonwoven fabric (weight per unit: 36 g / m ² : porosity: 12%) using a polyester fiber melt-spun from a pellet in which 6% by mass of cresyl diphenyl phosphate (CDP) as an aromatic phosphate ester is blended with polyethylene terephthalate resin It was.
<Japanese paper composite sheet>
A soft vinyl chloride resin compound according to the following [Composition 2] was used, and this was applied to a calender molding machine to obtain a film having a thickness of 0.12 mm. This film is laminated on both sides of the substrate 4 with a laminator in a state where the film is softened under a heat roll condition of 170 ° C., and a Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 360 g / m ² by bridging the gap. Got.
* [Composition 2] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl (plasticizer) 25 parts by mass * Product name: Hexamol DINCH ( (Made by BASF)
20 parts by mass of tricresyl phosphate (flameproof plasticizer) (also known as TCP: tricresyl phosphate)
Epoxidized soybean oil (plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass

[Example 5]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 360 g / m ² was obtained in the same manner as in Example 4 except that the base material 4 of Example 4 was changed to the base material 5 described below.
<Flame-retardant nonwoven fabric: Base material 5>
In the copolymerization of ethylene glycol and terephthalic acid, an aromatic phosphate compound having a chemical formula of (C ₆ H ₅ ) ₂ P═O (C ₆ H ₃ ) (— OCH ₂ CH ₂ OH) ₂ is used as the third substance. Is a Japanese paper spunbonded nonwoven fabric (weight per unit area: 36 g / m ² : porosity: 12%) made of polyester fiber melt-spun from a polyester resin pellet obtained by carrying out a polycondensation reaction with a phosphorus atom mass of 10,000 ppm. Using.

[Example 6]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 360 g / m ² was obtained in the same manner as in Example 4 except that the base material 4 of Example 4 was changed to the following base material 6.
<Flame-retardant nonwoven fabric: Base material 6>
Using a Japanese paper-style spunbonded nonwoven fabric (weighing 33 g / m ² : porosity 12%) made of polyester fiber melt-spun from polyester resin pellets, this nonwoven fabric was immersed in a toluene solution bath of 10% by mass of vinylphosphonate for 3 minutes. It dried at 100 degreeC and obtained the base material 6 of 36 g / m < ² >.

[Example 7]
<Flame-retardant Japanese paper: Base material 7>
Unryu-Japanese paper (weighing 50 g / m ² : porosity 0%) is dipped in an aqueous solution bath of 3% by weight boric acid + 78% by weight ethyl cellosolve, and borated for 30 minutes to the hydroxyl group of Japanese paper (cellulose). This was dried at 100 ° C. to obtain a substrate 7. The mass increase of the Japanese paper before and after the boric acid esterification treatment was 5 g / m ² .
<Japanese paper composite sheet>
Using the soft vinyl chloride resin paste sol according to the following [Composition 3] on both surfaces of the base material 7, the base material 7 is coated to a thickness of 0.1 mm by knife coating, and gelled at 170 ° C., A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 325 g / m ² was obtained.
* [Composition 3] Soft vinyl chloride resin paste composition Emulsion-polymerized polyvinyl chloride resin (degree of polymerization 1700) 100 parts by mass 1,2-cyclohexanedicarboxylate diisononyl (plasticizer) 30 parts by mass * Product name: Hexamol DINCH (BASF (Made by company)
25 parts by mass of cresyl diphenyl phosphate (flameproof plasticizer) (also known as CDP: cresyl diphenyl phosphate)
Epoxidized soybean oil (plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass

[Example 8]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 324 g / m ² was obtained in the same manner as in Example 7 except that the base material 7 of Example 7 was changed to the following base material 8.
<Flame-resistant Japanese paper: Base material 8>
Unryu-saki-made Japanese paper (50 g / m ² per unit area: 0% porosity) is immersed in an aqueous solution bath of 3% by mass phosphoric acid + 78% by mass ethyl cellosolve, and is subjected to phosphoric esterification treatment for hydroxyl groups of Japanese paper (cellulose) for 30 minutes. This was dried at 100 ° C. to obtain a substrate 8. The increase in mass of Japanese paper before and after the phosphoric esterification treatment was 4 g / m ² .

[Example 9]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 324 g / m ² was obtained in the same manner as in Example 7 except that the base material 7 of Example 7 was changed to the following base material 9.
<Flame-retardant Japanese paper: Base material 9>
Unryu-saki-made Japanese paper (50 g / m ² per unit area: 0% porosity) is immersed in an aqueous solution bath of 3% by mass silicic acid + 78% by mass ethyl cellosolve, and treated for 30 minutes with a silicate esterification of hydroxyl groups on Japanese paper (cellulose). This was dried at 100 ° C. to obtain a substrate 9. The increase in mass of the Japanese paper before and after the silicic acid esterification treatment was 4 g / m ² .

[Example 10]
<Flame-retardant nonwoven fabric: Base material 10>
Japanese paper-style spunbond nonwoven fabric (weight per unit area: 50 g / m ² : porosity 0%) using polyester fiber melt-spun from pellets containing 6% by mass of cresyl diphenyl phosphate (CDP) as an aromatic phosphate ester in polyethylene terephthalate resin It was.
<Japanese paper composite sheet>
Using the soft vinyl chloride resin paste sol according to the following [Composition 4] on both surfaces of the base material 10, this is coated on the base material 7 to a thickness of 0.1 mm by knife coating, gelled at 170 ° C., A Japanese paper composite sheet having a thickness of 0.28 mm and a mass of 320 g / m ² was obtained.
* [Formulation 4] Soft vinyl chloride resin paste composition Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1700) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl (plasticizer) 30 parts by mass * Product name: Hexamol DINCH (BASF (Made by company)
25 parts by mass of tricresyl phosphate (flameproof plasticizer) (also known as TCP: tricresyl phosphate)
Epoxidized soybean oil (plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass

[Example 11]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 320 g / m ² was obtained in the same manner as in Example 10 except that the base material 10 of Example 10 was changed to the following base material 11.
<Flame-retardant nonwoven fabric: Base material 11>
In the copolymerization of ethylene glycol and terephthalic acid, an aromatic phosphate compound having a chemical formula of (C ₆ H ₅ ) ₂ P═O (C ₆ H ₃ ) (— OCH ₂ CH ₂ OH) ₂ is used as the third substance. Is a Japanese paper-type spunbonded nonwoven fabric (weight per unit area: 50 g / m ² : porosity 0%) made of polyester fibers melt-spun from polyester resin pellets obtained by adding a phosphorus atom mass of 10,000 ppm to carry out a polycondensation reaction. Using.

[Example 12]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 323 g / m ² was obtained in the same manner as in Example 10 except that the base material 10 of Example 10 was changed to the following base material 12.
<Flame-retardant nonwoven fabric: Base material 12>
Using a Japanese paper-like spunbonded nonwoven fabric (weighing 50 g / m ² : porosity 0%) made of polyester fiber melt-spun from polyester resin pellets, this nonwoven fabric was immersed in a toluene solution bath of 10% by mass of vinylphosphonate for 3 minutes. It dried at 100 degreeC and obtained the base material 12 of 53 g / m < ² >.

[Examples 13 to 24]
The antifouling layer by the following [Formulation 5] was formed on each surface and the back surface of the Japanese paper composite sheets obtained in Examples 1 to 12. The total adhesion mass of the front and back antifouling layers was 2.6 g / m ² . Examples 13 to 24 obtained in this way, antifouling properties such as increasing the wiping and removing properties such as dust stains and oil stains adhering to the surface of each composite sheet (hydrolytic condensation with silica sol and vinyltriethoxysilane) In addition to the self-cleaning effect of the photocuring substance (titanium oxide particles) and the anti-static effect (effect of the polyethylene glycol-type nonionic active agent), the dead body of pollen and mites The anti-adhesion effect of allergic dust such as was also confirmed.
<Anti-fouling layer>
The substrates of Examples 1 to 12 were applied to a coating machine under 80 mesh gravure roll coating conditions, and double-sided coating was performed on the soft vinyl chloride resin layer with the antifouling composition of [Formulation 5], and hot air at 120 ° C. Dry in oven for 3 minutes.
[Formulation 5] 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 Titanium oxide particles (particle size 15 nm) (photocatalytically active type) 0.5 parts by weight Polyethylene glycol type nonionic active agent (antistatic agent) 1 part by weight Diluent (water) 100 parts by weight

[Examples 25 to 36]
An adhesive layer (2.2 g / m ² ) according to the following [Formulation 6] is formed on one side of each of the Japanese paper-like composite sheets obtained in Examples 1 to 12, and the polyvinylidene fluoride having a thickness of 50 μm is interposed via the adhesive layer. A ride (PVdF) transparent film was thermally laminated at 180 ° C., and an antifouling layer comprising a fluororesin layer was provided on one side of the sheet. The mass of the antifouling layer was 72 g / m ² . Examples 25-36 obtained in this way, exhibiting excellent antifouling properties such as increasing the wiping and removing properties such as dust stains and oil stains adhering to the surface of each composite sheet, and providing for long-term use Made it possible.
<Adhesive layer>
The Japanese paper-like composite sheet obtained in Examples 1 to 12 was applied to a coating machine under 80 mesh gravure roll coating conditions, and coated with the adhesive composition of [Formulation 6] on the soft vinyl chloride resin layer, and 120 ° C. For 3 minutes.
[Formulation 6] Adhesive composition Acrylic resin grafted with polyethyleneimine as a reactive group
(Solid content concentration 30% by mass, amine equivalent: 1400 g / eq) 100 parts by mass Bisphenol A type epoxy resin (epoxy equivalent: 200 g / eq) 7 parts by weight Benzotriazole compound (ultraviolet absorber) 0.5 parts by mass Methyl ethyl ketone 100 parts by mass Part

[Comparative Example 1]
Example 1 except that 20 parts by mass of phosphate (cresyl diphenyl phosphate) used in [Formulation 1] of Example 1 was omitted and 25 parts by mass of diisononyl 1,2-cyclohexanedicarboxylate was increased to 45 parts by mass. In the same manner, a Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 360 g / m ² was obtained. The obtained Japanese paper-like composite sheet is incompatible with Article 4 of the Fire Service Law Enforcement Regulations (JIS L-1091: A-1 law classification 3: 1 minute heating) because the soft vinyl chloride resin layer does not contain phosphate. Met.

[Comparative Example 2]
Except that 25 parts by mass of diisononyl 1,2-cyclohexanedicarboxylate used in [Formulation 1] of Example 1 was changed to 25 parts by mass of di-2-ethylhexyl phthalate (also known as dioctyl phthalate: DOP). As in Example 1, a Japanese paper-type composite sheet having a thickness of 0.28 mm and a mass of 360 g / m ² was obtained. The resulting Japanese paper-like composite sheet does not contain diisononyl 1,2-cyclohexanedicarboxylate in the soft vinyl chloride resin layer, so that the bleed suppressing effect of the plasticizer is poor, and di-2-ethylhexyl oozed out on the sheet surface The phthalate component became a combustion source and became incompatible with Article 4 of the Fire Service Law Enforcement Regulations (JIS L-1091: A-1 Law Category 3: 1 minute heating).

[Comparative Example 3]
Example 1 except that the base material 13 used in the base material 1 used in Example 1 was a Yun-rye-made Japanese paper with a boric acid esterification treatment omitted (weight per unit area: 33 g / m ² : porosity 12%). In the same manner, a Japanese paper composite sheet having a thickness of 0.28 mm and a mass of 357 g / m ² was obtained. The obtained Japanese paper-like composite sheet is based on Article 4 of the Fire Service Act Enforcement Regulations (JIS L-1091: A-1 law classification 3: 1 minute heating) by omitting the boric acid esterification treatment on the base Japanese paper. It became nonconforming.

[Comparative Example 4]
A Japanese paper-like composite sheet having a thickness of 0.28 mm and a mass of 360 g / m ² was obtained in the same manner as in Example 5 except that the base material 5 used in Example 5 was changed to the following base material 14. The resulting paper regulating composite sheet, nonwoven fabric _{(C 6 H 5) 2 P} = O (C 6 H 3) of the base (- _OCH 2 CH 2 _OH) completely free ₂ formula of the aromatic phosphoric acid compound Failure to do so resulted in incompatibility with Article 4 of the Fire Service Law Enforcement Regulations (JIS L-1091: A-1 Law Category 3: 1 minute heating).
<Nonwoven fabric: base material 14>
A Japanese paper-type spunbonded nonwoven fabric (weighing 36 g / m ² : porosity 12%) made of polyester fiber melt-spun from a polyester resin pellet obtained by copolymerizing ethylene glycol and terephthalic acid was used.

  According to the present invention, the soft vinyl chloride resin layer contains cyclohexanedicarboxylic acid dialkyl esters and phosphates, so that the flameproofness and flexibility are stably maintained for a long period of time, and the Japanese paper-like appearance and light transmission are maintained. A composite sheet that sometimes exhibits a Japanese paper-like appearance can be obtained, especially light ceiling membranes, lighting shades, blinds, partitions, indoor wall materials, shojis / furnitures, bathroom / greenhouse curtains, electric signs, row lamp-type display objects, projection screens Suitable for use in bags, pouches, stationery, sundries, etc.

Claims (9)

A flame retardant flexible laminate having an irregular shade in light transmittance, comprising a flame retardant Japanese paper or a flame retardant nonwoven fabric as a base material, and a soft vinyl chloride resin layer provided on at least one surface of the base material The soft vinyl chloride resin layer mainly contains 100 parts by mass of vinyl chloride resin and 15 to 60 parts by mass of cycloalkyldicarboxylic acid dialkyl ester (group of [Chemical Formula 1]), and further contains 5 to 40 phosphates. A Japanese paper-like composite sheet containing a mass part.
  The flame-retardant flexible laminate is composed of the base material having a porosity of 5 to 35% and a soft vinyl chloride resin film or sheet having a thickness of 0.05 to 0.5 mm formed on the surface thereof. The Japanese paper-like composite sheet according to claim 1.   The flame-retardant flexible laminate has a thickness of 0. 5% formed by the base material having a porosity of 0 to less than 5%, soft vinyl chloride resin paste sol coating on the surface, and heat gelation. The Japanese paper-like composite sheet according to claim 1, comprising a soft vinyl chloride resin layer having a thickness of 01 to 0.2 mm.   In the flame-retardant Japanese paper, the hydroxyl group of cellulose of natural fibers forming the Japanese paper is subjected to any one chemical modification treatment selected from boric acid esterification, phosphoric acid esterification, and silicic acid esterification. The Japanese paper-like composite sheet according to any one of claims 1 to 3.   The flame retardant nonwoven fabric is 1) a dispersion containing a flame retardant in a synthetic fiber forming a nonwoven fabric, and 2) a copolymer polymer obtained by copolymerizing a phosphorus compound with a raw material polymer of a synthetic fiber forming a nonwoven fabric. 3) The Japanese paper according to any one of claims 1 to 3, which is any one selected from a surface of a synthetic fiber and a flame retardant adhered between the fibers by post-processing after the production of the nonwoven fabric. Toned composite sheet.   In the flame retardant Japanese paper, any one of 1) using dyed fibers as part of natural fibers, 2) using a plurality of types of natural fibers, and 3) using natural fiber bundles having different fiber diameters. The Japanese paper-like composite sheet according to claim 4, wherein the Japanese paper-like appearance is formed by one or more kinds.   In the flame retardant nonwoven fabric, 1) using colored fibers as part of the synthetic fibers, 2) using a plurality of types of synthetic fibers, and 3) using synthetic fiber bundles having different fiber bundle diameters. The Japanese paper-like composite sheet according to claim 5, wherein the Japanese paper-like appearance is formed by any one or more kinds.   On the soft vinyl chloride resin layer, an antifouling layer is provided in which an inorganic colloidal material having a primary particle size of 3 nm to 150 nm is supported on a binder component containing a hydrolysis condensate of a silane coupling agent, Inorganic colloidal materials include photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and composite oxide The Japanese paper-like composite sheet according to any one of claims 1 to 7, which is one or more metal oxides selected from (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol.   A fluororesin layer is formed on the soft vinyl chloride resin layer, and the fluororesin constituting the fluororesin layer is vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene (TrEE), tetrafluoroethylene ( A polymer obtained by homopolymerizing one monomer selected from TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), or a copolymer obtained by copolymerizing two or more of these monomers, or The Japanese paper-type composite sheet according to any one of claims 1 to 7, which is at least one selected from copolymers obtained by copolymerizing one or more monomers with a vinyl monomer.