JP2018144436A - Decorative sheet and method for producing decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in designability and weather resistance over a long period of time by addition of vesicle separately formed of an organic ultraviolet absorber and an inorganic ultraviolet absorber using a supercritical reverse phase evaporation method to a top coat layer 5 and/or a transparent resin layer 4.SOLUTION: There are provided a decorative sheet 1 which has a top coat layer 5 on the outermost surface layer and has a transparent resin layer 4 on the lower layer of the top coat layer 5, where the top coat layer 5 and/or the transparent resin layer 4 are formed by addition of an organic ultraviolet absorber and an inorganic ultraviolet absorber, and the organic ultraviolet absorber and the inorganic ultraviolet absorber are an organic ultraviolet absorber vesicle and an inorganic ultraviolet absorber vesicle which are separately included in vesicles having outer films having single layer films; and a method for producing the decorative sheet 1.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet used for a building interior material, a building exterior member such as a front door, a surface of a joinery, a surface material of home appliances, etc., and a topcoat layer formed by adding a vesicle-shaped ultraviolet absorber and The present invention relates to a decorative sheet having a transparent resin layer and a method for producing the decorative sheet.

  In recent years, many decorative sheets using olefinic resins have been proposed as decorative sheets that replace vinyl chloride decorative sheets. In addition, in order to improve the scratch resistance of a flexible polyolefin sheet made of an olefin resin generally used as a decorative sheet, there is a problem that it is inferior in weather resistance when a resin having high crystallinity and high isotacticity is used. It was.

  As a technique for improving the weather resistance of a polyolefin-based resin, as disclosed in Patent Document 1, it is disclosed that a topcoat layer made of a resin containing a triazine-based organic ultraviolet absorber is provided on the surface of a polyolefin sheet. ing.

Japanese Patent No. 4032829 JP 2002/032564 gazette

  However, when a triazine-based UV absorber, which is an organic UV absorber, is added, the transparency of the base resin can be maintained, but the change over time is unavoidable, and there is a problem with the sustainability of UV absorption performance over a long period of time. Had.

  In addition, when zinc oxide, which is an inorganic UV absorber, is added, the UV absorption performance over a long period is good with little change over time, but when added in a large amount, the transparency decreases and the decorative sheet itself has a good design. There was a problem of losing.

  Furthermore, in both organic and inorganic ultraviolet absorbers, if the amount added is increased to improve the weather resistance, the ultraviolet absorber aggregates in the resin and bleed out occurs, causing stickiness on the sheet surface. There was a problem of causing a decrease in adhesion.

  In addition to this, when an embossed pattern is formed on the transparent resin layer in order to improve the design of the decorative sheet, the concave portion of the embossed pattern is thinner than other parts, so that the layer thickness is thinner, so that the weather resistance Is particularly low, and there is a problem in that deterioration starts from the concave portion and whitening or breakage occurs.

  As a result of intensive studies, the present inventors have used organic UV absorbers and inorganic UV absorbers vesicled by the supercritical reverse phase evaporation method, respectively. It was found that excellent weather resistance can be obtained.

  Note that the supercritical reverse phase evaporation method refers to Patent Document 2, Japanese Patent Application Laid-Open No. 2003-119120, Japanese Patent Application Laid-Open No. 2005-298407, and Japanese Patent Application Laid-Open No. 2008-063274 (hereinafter referred to as the following). (Referred to as "Supercritical Reverse Phase Evaporation Method Publications"), which was carried out using the method and apparatus described in the Supercritical Reverse Phase Evaporation Method Publications.

  In the present invention, the organic UV absorber and the inorganic UV absorber are separately vesicled using the supercritical reverse phase evaporation method, and added to the topcoat layer and / or the transparent resin layer. An object of the present invention is to provide a decorative sheet excellent in designability and weather resistance over a long period of time and a method for producing the decorative sheet.

  In order to achieve the above object, a decorative sheet comprising a top coat layer as an outermost layer and a transparent resin layer under the top coat layer, wherein the top coat layer and / or the transparent resin layer is made of an organic ultraviolet ray. An organic ultraviolet ray formed by adding an absorbent and an inorganic ultraviolet absorber, wherein the organic ultraviolet absorber and the inorganic ultraviolet absorber are separately encapsulated in vesicles each having a single-layer outer film. It is characterized by being an absorbent vesicle and an inorganic ultraviolet absorbent vesicle.

  In such a decorative sheet according to the first aspect of the present invention, the organic ultraviolet absorber vesicle having excellent transparency and the inorganic ultraviolet light having excellent weather resistance with respect to the topcoat layer and / or the transparent resin layer. Since both of the absorbent vesicles are added, it is possible to provide a decorative sheet capable of realizing both excellent design properties and long-term weather resistance. In addition, organic UV absorber vesicles and inorganic UV absorber vesicles are added separately in the form of vesicles, so the amount of both UV absorber vesicles added depending on the function to be added to the product Can be easily changed. More specifically, when transparency is important, the addition amount of the organic ultraviolet absorbent vesicle is increased by decreasing the addition amount of the inorganic ultraviolet absorbent vesicle. In order to prolong the service life, the addition amount of the organic ultraviolet absorbent vesicle is decreased by decreasing the addition amount of the organic ultraviolet absorbent vesicle.

  The decorative sheet according to the second aspect of the present invention is characterized in that the outer membrane of the vesicle is made of phospholipid.

  In such a decorative sheet according to the second aspect of the present invention, the compatibility with the resin composition that is the main component of the topcoat layer and the transparent resin layer can be improved, so that the resin composition It is possible to achieve high dispersibility of vesicles with respect to an object and to suppress the occurrence of secondary aggregation.

  The decorative sheet according to the third aspect of the present invention is characterized in that the organic ultraviolet absorber is benzotriazole or triazine.

  In the decorative sheet according to the third aspect of the present invention, it is possible to provide a decorative sheet that maintains high transparency and is excellent in design.

  The decorative sheet according to the fourth aspect of the present invention is characterized in that the inorganic ultraviolet absorber is zinc oxide.

  In such a decorative sheet according to the fourth aspect of the present invention, it is possible to provide a decorative sheet excellent in functionality while maintaining an ultraviolet absorbing ability over a long period of time.

  In the decorative sheet according to the fifth aspect of the present invention, an embossed pattern is formed on the surface of the transparent resin layer on the topcoat layer side, and the topcoat layer is embedded in a recess of the embossed pattern. It is provided.

  In such a decorative sheet of the fifth aspect of the present invention, the organic ultraviolet absorbent vesicle and the embossed pattern in which the film thickness of the transparent resin layer is reduced by forming the embossed pattern Since the top coat layer to which the inorganic ultraviolet absorber vesicle is added is embedded, a decorative sheet can be provided that provides weather resistance comparable to other parts.

  The method for producing a decorative sheet according to the first aspect of the present invention is a method for producing a decorative sheet comprising a top coat layer made of a resin as an outermost layer, and a transparent resin layer made of a transparent olefin resin as a lower layer of the top coat layer. An organic ultraviolet absorber and an inorganic ultraviolet ray are applied to a vesicle having a single-layer outer film by supercritical reverse phase evaporation for the resin constituting the topcoat layer and / or the transparent resin layer. An organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle each containing an absorbent separately are added.

  In such a method for producing a decorative sheet according to the first aspect of the present invention, the compatibility with the resin composition that is the main component of the topcoat layer and the transparent resin layer can be improved. High dispersibility of vesicles with respect to the resin composition can be realized, and secondary aggregation can be suppressed. Furthermore, since the organic UV absorber vesicles and inorganic UV absorber vesicles are added separately in the vesicle state, the amount of both UV absorber vesicles added depending on the function to be added to the product. Can be easily changed. More specifically, when transparency is important, the addition amount of the organic ultraviolet absorbent vesicle is increased by decreasing the addition amount of the inorganic ultraviolet absorbent vesicle. In order to prolong the service life, the addition amount of the organic ultraviolet absorbent vesicle is decreased by decreasing the addition amount of the organic ultraviolet absorbent vesicle.

  According to the decorative sheet of the present invention, a cosmetic having excellent design and weather resistance can be obtained by forming a top coat layer and / or a transparent resin layer to which an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle are added. It is possible to provide a sheet.

  Further, according to the method for producing a decorative sheet of the present invention, the compatibility between the resin composition that is the main component of the top coat layer and the transparent resin layer, and the organic ultraviolet absorbent and the inorganic ultraviolet absorbent is good. Therefore, it is possible to realize high dispersibility of vesicles with respect to the resin composition and to suppress the occurrence of secondary aggregation.

Sectional drawing which shows embodiment of the decorative sheet of this invention

  The decorative sheet of the present invention is a decorative sheet provided with a top coat layer on the outermost layer and a transparent resin layer made of a transparent olefin resin under the top coat layer, the top coat layer and / or transparent The resin layer is formed by adding an organic ultraviolet absorbent and an inorganic ultraviolet absorbent, and the organic ultraviolet absorbent and the inorganic ultraviolet absorbent are separately provided in vesicles each having a single-layer outer film. It is important that the organic ultraviolet absorbent vesicles and the inorganic ultraviolet absorbent vesicles are encapsulated.

  And in the manufacturing method of the decorative sheet of this invention, with respect to the resin which comprises the said topcoat layer and / or the said transparent resin layer, an organic ultraviolet absorber and inorganic are provided in the vesicle which comprises the outer membrane of a single layer film It is important that they are added as organic ultraviolet absorbent vesicles and inorganic ultraviolet absorbent vesicles each containing a separate ultraviolet absorbent. This makes it possible to finely set the amount of organic UV absorber vesicles and inorganic UV absorber vesicles with different absorption wavelengths and lifetimes depending on the use of the decorative sheet. It is possible to provide.

  The organic ultraviolet absorber can be selected from at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate. In particular, a benzotriazole-based or triazine-based organic ultraviolet absorber has a high ultraviolet-absorbing ability and is excellent in heat resistance, volatilization resistance, and resin compatibility.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2'- And methylenebis (4-tert-octyl-6-benzotriazolyl) phenol. Examples of triazine-based ultraviolet absorbers include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2 -[4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4 -Bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) ) Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) ) Hexy And l) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine. Examples of the benzophenone-based UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). ) And the like. Examples of the benzoate-based ultraviolet absorber include phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3 ′, 5′-ditertiarybutyl-4′-hydroxybenzoate, 2,4-ditertiary Examples include amylphenyl-3 ′, 5′-ditert-butyl-4′-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate, and the like. Examples of cyanoacrylate-based ultraviolet absorbers include ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and the like.

  As the inorganic ultraviolet absorber, zinc oxide, titanium oxide, ceria oxide, or the like can be used. Among these, zinc oxide is preferable because it has a refractive index close to that of the transparent olefin resin and the topcoat layer resin and can maintain high transparency even when the zinc oxide is added. In addition, it is preferable to use the thing of the particle size of an inorganic type ultraviolet absorber within the range of 1 nm-200 nm.

  It is important that the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle of the present invention are prepared by a supercritical reverse phase evaporation method. Here, the supercritical reverse phase evaporation method will be described in detail. In the supercritical reverse phase evaporation method, a substance that forms the outer membrane of a vesicle is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure conditions above the supercritical point to form a mixture, and water is dissolved in the mixture. Organic UV absorber or inorganic UV as an encapsulating material in a single layer (single layer film) by adding an aqueous phase containing an organic or inorganic UV absorber as a hydrophilic or hydrophilic encapsulating material Capsule-shaped organic ultraviolet absorbent vesicles and inorganic ultraviolet absorbent vesicles each containing an absorbent are prepared. The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher. Carbon dioxide under pressure means carbon dioxide under a condition where only the critical temperature or the critical pressure exceeds the critical condition. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained.

  Phospholipids that form the outer membrane of vesicles include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, etc. And sphingophospholipids such as glycerophospholipid, sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

  As a substance that forms the outer membrane of the vesicle, in addition to the phospholipid, a nonionic surfactant or a dispersant such as a mixture of this with cholesterols or triacylglycerol can be employed.

  More specifically, nonionic surfactants include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxy Such as propylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. 1 type (s) or 2 or more types can be used. As cholesterols, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate or cholecalciferol can be used.

  The outer membrane of the vesicle may be formed from a mixture of a phospholipid and a dispersant. In the method for producing a decorative sheet of the present invention, it is important that the outer membrane is a vesicle formed from phospholipid, and the compatibility with the resin composition that is the main component of the topcoat layer and the transparent resin layer is good. Can be.

  When such an organic ultraviolet absorber vesicle and an inorganic ultraviolet absorber vesicle are added to the topcoat layer, the organic ultraviolet absorber vesicle is organic to 100 parts by weight of the resin composition as the main component of the topcoat layer. It is preferable to add 0.5 to 20 parts by weight of the ultraviolet absorber vesicle and 0.5 to 20 parts by weight of the inorganic ultraviolet absorber vesicle. At this time, if the addition amount of both ultraviolet absorbers is less than 0.5 parts by weight, the effect of ultraviolet absorbing ability is low, and if it is more than 20 parts by weight, the possibility of blocking increases. More preferably, 1 to 10 parts by weight of the organic ultraviolet absorbent vesicle and 1 to 10 parts by weight of the inorganic ultraviolet absorbent vesicle are added, and further preferably 3 to 5 parts by weight of the organic ultraviolet absorbent vesicle. 3 to 5 parts by weight of an inorganic ultraviolet absorbent vesicle.

  Moreover, when adding with respect to a transparent resin layer, 0.1-5 weight part of organic type ultraviolet absorber vesicles, inorganic type ultraviolet ray with respect to 100 weight part of resin compositions which are the main components of a transparent resin layer It is preferable to add 0.1 to 5 parts by weight of an absorbent vesicle. At this time, if the addition amount of both UV absorbers is less than 0.1 parts by weight, the effect of UV absorbing ability is low, and if it is more than 5 parts by weight, the possibility of bleeding out increases. More preferably, 0.2 to 3 parts by weight of an organic ultraviolet absorbent vesicle and 0.2 to 3 parts by weight of an inorganic ultraviolet absorbent vesicle are added.

  In the decorative sheet of the present invention, it is important that an embossed pattern is formed on the transparent resin layer, and that a topcoat layer is embedded at least in the recesses of the embossed pattern. More preferably, it is preferable to form the top coat layer in the recess by wiping.

  In addition, it is important that an ink layer formed of an ink to which at least a light stabilizer is added is provided below the transparent resin layer. As the light stabilizer, it is preferable to use a hindered amine material. By adding a light stabilizer to the ink layer, it is possible to suppress the fading of the pigment due to the radicals generated by the resin degradation of the ink layer binder resin itself and other layers reducing the chemical components of the pigment in the ink. .

  Below, the specific Example of the manufacturing method of the decorative sheet and decorative sheet of this invention is described using FIG.

  FIG. 1 shows a specific configuration of the decorative sheet 1 of the present invention, which is composed of a plurality of resin layers. In the decorative sheet 1 of the present invention, from the surface layer side, a top coat layer 5, a transparent resin layer 4, an adhesive layer 7 (consisting of a heat sensitive adhesive, an anchor coat, a dry laminating adhesive, etc.), an ink layer 3, an original fabric layer 2, the concealing layer 8 and the primer layer 6 are laminated and used by adhering to the base material B. In addition, an embossed pattern 4a is formed on the surface of the transparent resin layer 4 on the topcoat layer 5 side in order to improve the design, and the topcoat layer 5 is formed by wiping in the concave portion of the embossed pattern 4a. It is formed so that a part of the resin composition to be embedded is embedded.

  The top coat layer 5 is formed by adding an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle to a resin composition that plays a role of protecting the surface and adjusting gloss.

  The resin composition as the main component of the topcoat layer 5 is appropriately selected from polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like. Can be used. The form of the resin composition is not particularly limited, such as aqueous, emulsion, solvent type. As for the curing method, a one-component type, a two-component type, an ultraviolet curing method or the like can be appropriately selected and used. In particular, urethane resins using isocyanate as the resin composition are suitable from the viewpoints of workability, cost, cohesive strength of the resin itself, and the like. Examples of the isocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis (isocyanate methyl) cyclohexane ( HXDI), trimethylhexamethylene diisocyanate (TMDI) and other derivatives such as adducts, burettes, and isocyanurates can be appropriately selected and used. However, in consideration of weather resistance, linear molecules It is preferable to use a curing agent based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a structure. In addition to this, in order to improve the surface hardness, it is preferable to use a resin curable with active energy rays such as ultraviolet rays and electron beams. These resins can be used in combination with each other. For example, by using a hybrid type of a thermosetting resin and a photocurable resin, surface hardness is improved, curing shrinkage is suppressed, and a transparent resin layer is used. It is possible to improve the adhesion.

  In addition, functional additives such as antibacterial agents and fungicides can be optionally added to impart various functions to the top coat layer 5. Furthermore, in order to improve the design of the surface, the gloss may be adjusted by adding alumina, silica, silicon nitride, silicon carbide, glass beads or the like. Further, when alumina, silica, silicon nitride, silicon carbide, glass beads, or the like is added to the top coat layer 5, the surface wear resistance can be improved.

  As the transparent resin layer 4, it is preferable to use an olefin resin as a main component. Specifically, in addition to polypropylene, polyethylene, polybutene, and the like, α-olefin (for example, propylene, 1-butene, 1-pentene, 1 -Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1 -Nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 -Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, -Methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) homopolymerized or copolymerized with two or more kinds, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate Copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, etc. The thing which copolymerized alpha olefin and the monomer other than that is mentioned. Moreover, when improving the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene.

  In the decorative sheet 1 of the present invention, it is more preferable that the transparent resin layer 4 is formed by adding an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle, respectively. Thereby, it becomes possible to provide weather resistance also in the transparent resin layer 4, and it can suppress that the olefin resin composition which is a main component of the transparent resin layer 4 deteriorates, or the pattern of the ink layer 3 located in the lower layer. Printing can be prevented from fading by ultraviolet rays, and excellent design can be maintained over a long period of time.

  In addition, various additives such as a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjusting agent are added to the transparent resin layer 4 as necessary. You may make it do. Phenol, sulfur, phosphorus, hydrazine, etc. as heat stabilizers, benzotriazole, benzoate, benzophenone, triazine, etc. as ultraviolet absorbers, hindered amines, etc. as light stabilizers In general, they are added in any combination.

  Although it does not specifically limit as the adhesive bond layer 7, It can select suitably from an acrylic type, a polyester type, a polyurethane type, an epoxy type, etc., and can be used. The coating method can be appropriately selected according to the viscosity of the adhesive and the like. Generally, a gravure coat is used, and after applying the gravure coat to the upper surface of the ink layer 3, a transparent resin layer is used. 4 to be laminated. The adhesive layer 7 can be omitted when the adhesive strength between the transparent resin layer 4 and the ink layer 3 is sufficiently obtained.

  The ink layer 3 is a pattern print formed on the raw fabric layer 2 using ink, and nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc. as a binder These can be used alone or selected from the respective modified products. These may be water-based, solvent-based, or emulsion-type, and may be one-component type or two-component type using a curing agent. Furthermore, you may use the method of hardening ink by irradiation of an ultraviolet-ray, an electron beam, etc. Among them, the most common method is to use urethane-based ink and is a method of curing with isocyanate. In addition to these binders, colorants such as pigments and dyes contained in ordinary inks, extender pigments, solvents, various additives, and the like are added. Examples of highly versatile pigments include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica. In addition to the ink application, the design can be applied by vapor deposition or sputtering of various metals.

  Further, in the decorative sheet 1 of the present invention, it is preferable that a light stabilizer is added to the ink layer 3 to prevent the ink from being photodegraded to impair the design, and to make up for a long period of time. The excellent designability of the sheet 1 can be maintained.

  As the raw fabric layer 2, paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and other synthetic resins, Alternatively, foams of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber It can be arbitrarily selected from rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, metal foil such as aluminum, iron, gold and silver.

  When it is desired to impart concealability to the decorative sheet 1, concealment is imparted by making the original fabric layer 2 a colored sheet, or the original fabric layer 2 remains a transparent sheet, and an opaque concealment layer 8 is separately provided. It can be provided to provide concealment.

  The hiding layer 8 can be basically composed of the same material as the ink layer 3, but it is intended to have hiding properties, so that an opaque pigment, titanium oxide, iron oxide or the like is used as the pigment. It is preferable to do. It is also possible to add metals such as gold, silver, copper, and aluminum in order to improve concealment. In general, flaky aluminum is often added.

  Further, when an olefin-based resin is used as the raw fabric layer 2, the surface is often in an inactive state. Therefore, a primer layer 6 is provided between the raw fabric layer 2 and the base material B. It is preferable. In addition, in order to improve the adhesion between the raw material layer 2 made of an olefin-based material and the base material B, the raw material layer 2 is subjected to corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment. It is desirable to carry out a dichromic acid treatment.

  As the primer layer 6, basically, the same material as that of the ink layer 3 described above can be used. However, in consideration of performing winding in a web shape because it is applied to the back surface of the decorative sheet 1, blocking is performed. In order to avoid and enhance the adhesion with the adhesive, an inorganic filler such as silica, alumina, magnesia, titanium oxide, barium sulfate may be added.

  In forming the decorative sheet 1 of the present invention, the laminating method is not particularly limited, and it is appropriately selected from generally used methods such as a method using hot pressure, an extrusion laminating method and a dry laminating method. be able to. In the case of forming the embossed pattern 4a, a method is used in which the embossed pattern 4a is laminated by the laminating method and then the embossed pattern 4a is put by hot pressure, or a concavo-convex pattern is provided on the cooling roll and the embossed pattern 4a is formed simultaneously with extrusion lamination. be able to.

  In the decorative sheet 1 of this embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability, cost, etc., the adhesive layer 7 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, and the topcoat layer. 5 is preferably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 250 μm.

  Such a decorative sheet 1 of the present embodiment is formed by adding an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle to the top coat layer 5 and / or the transparent resin layer 4. In addition to maintaining high transparency and excellent design, it is possible to achieve excellent weather resistance over a long period of time. Furthermore, since there is no bleed out or white turbidity of the resin composition due to the agglomerated additive in the resin composition, it is possible to achieve adhesion and design without causing stickiness on the sheet surface. Can do.

  Moreover, in the manufacturing method of the decorative sheet 1 of the present embodiment, since it is added as an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle, it achieves high dispersibility in the resin composition as a main component, The decorative sheet 1 that exhibits high ultraviolet absorption performance and realizes excellent weather resistance can be obtained without increasing the addition amount of the ultraviolet absorber. In particular, by making the both vesicles into vesicles having an outer membrane made of phospholipid, the compatibility with the resin composition which is the main component of the topcoat layer 5 and the transparent resin layer 4 is extremely good. Can do.

  In addition, in the decorative sheet 1 of the present embodiment, the top coat layer 5 is embedded in the concave portion of the embossed pattern 4a, so that high weather resistance is maintained even in the concave portion where the layer thickness is thin. can do.

  Furthermore, by forming the ink layer 3 with ink added with a light stabilizer, fading of the ink layer 3 can be suppressed by ultraviolet rays, so that the design property that maintains beautiful color printing for a long period of time is possible. It is possible to provide a decorative sheet 1 that is superior to the above.

<Preparation of organic UV absorber vesicles and inorganic UV absorber vesicles>
Below, the detailed preparation method of the organic type ultraviolet absorber vesicle using the supercritical reverse phase evaporation method in this invention or an inorganic type ultraviolet absorber vesicle is demonstrated.

  The vesicle was prepared by adding 100 parts by weight of hexane and a triazine-based UV absorber 2- (4,6-bis (2,4-dimethyl) as an organic UV absorber to a high-pressure stainless steel container kept at 60 ° C. Phenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl as a main component, 70 parts by weight of hydroxyphenyl triazine (TINUVIN 400; manufactured by BASF Japan Ltd.) or as an inorganic ultraviolet absorber 70 parts by weight of zinc oxide (average particle size 20 nm) and 5 parts by weight of phosphatidylcholine as phospholipid are sealed and carbon dioxide is injected so that the pressure in the container becomes 20 MPa to make a supercritical state. Inject 100 parts by weight of ethyl acetate while stirring and mixing, and stir and mix for 15 minutes while maintaining temperature and pressure, and then discharge carbon dioxide. Then, the pressure was returned to atmospheric pressure to obtain an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle having a single-layer outer membrane made of phospholipid.

  Below, the specific Example of the manufacturing method of the decorative sheet 1 and the decorative sheet 1 of this invention is described.

<Examples 1-5>
In Examples 1 to 5, the organic ultraviolet absorbent vesicles 0.5, 1.0, and 5 prepared by the above-described method with respect to the urethane resin as the resin composition that is the main component of the top coat layer 5. 0.0, 10.0, 20.0 parts by weight, and 0.5, 1.0, 5.0, 10.0, 20.0 parts by weight of the inorganic ultraviolet absorbent vesicle prepared by the above method. The added decorative sheet 1 was obtained.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. The resin added with 0.2 parts by weight was melt extruded using an extruder to form a transparent highly crystalline polypropylene sheet having a thickness of 80 μm as the transparent resin layer 4. Both surfaces of the highly crystalline polypropylene sheet were subjected to corona treatment, so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, on one side of the 70 μm polyethylene sheet with concealment as the raw fabric layer 2, pattern printing is performed by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.). Then, a 3 μm ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry lamination (Takelac A540; Mitsui Chemical Co., Ltd.) as an adhesive layer 7 having a transparent resin layer 4 formed to a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet. And a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of this laminated resin sheet, an organic ultraviolet absorber is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). The topcoat layer 5 was formed by applying vesicles and inorganic ultraviolet absorber vesicles added in the combinations shown in Table 1 to obtain decorative sheets 1 of Examples 1 to 5 having a total thickness of 160 μm.

<Examples 6 to 10>
In Examples 6 to 10, the organic ultraviolet absorbent vesicles 0.1 and 0.5 prepared by the above-described method were used for the crystalline homopolypropylene resin as the resin composition that is the main component of the transparent resin layer 4. 1.0, 2.5, 5.0 parts by weight, and the inorganic ultraviolet absorbent vesicles 0.1, 0.5, 1.0, 2.5, 5.0 prepared by the above-described method. The decorative sheet 1 was added with parts by weight.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. Thickness as a transparent resin layer 4 is obtained by melt-extruding 0.2 parts by weight of a resin in which an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle are added in combinations of Table 2 using an extruder. A transparent high crystalline polypropylene sheet having a thickness of 80 μm was formed. Both surfaces of the highly crystalline polypropylene sheet were subjected to corona treatment, so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, on one side of the 70 μm polyethylene sheet with concealment as the raw fabric layer 2, pattern printing is performed by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.). Then, a 3 μm ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry lamination (Takelac A540; Mitsui Chemical Co., Ltd.) as an adhesive layer 7 having a transparent resin layer 4 formed to a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet. And a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, and then a two-component urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ) is applied to the topcoat layer 5 The decorative sheet 1 of Examples 6 to 10 having a total thickness of 160 μm was obtained.

<Example 11>
In Example 11, 1.25 parts by weight of the organic ultraviolet absorbent vesicle prepared by the above-described method is used for the urethane-based resin as the resin composition which is the main component of the top coat layer 5 by the above-described method. While adding 1.25 parts by weight of the prepared inorganic ultraviolet absorbent vesicle, the organic ultraviolet light prepared by the above-described method with respect to the crystalline homopolypropylene resin as the resin composition as the main component of the transparent resin layer 4 The decorative sheet 1 was obtained by adding 1.25 parts by weight of the absorbent vesicle and 1.25 parts by weight of the inorganic ultraviolet absorbent vesicle prepared by the above-described method.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. The resin added with 0.2 part by weight, 1.25 parts by weight of the organic ultraviolet absorbent vesicle and 1.25 parts by weight of the inorganic ultraviolet absorbent vesicle is melt-extruded using an extruder to obtain the transparent resin layer 4. A transparent highly crystalline polypropylene sheet having a thickness of 80 μm was formed. Both surfaces of the highly crystalline polypropylene sheet were subjected to corona treatment, so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, on one side of the 70 μm polyethylene sheet with concealment as the raw fabric layer 2, pattern printing is performed by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.). Then, a 3 μm ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry lamination (Takelac A540; Mitsui Chemical Co., Ltd.) as an adhesive layer 7 having a transparent resin layer 4 formed to a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet. And a laminate resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the primer layer 6, the adhesive layer 7, and the transparent resin layer 4 was obtained. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of this laminated resin sheet, an organic ultraviolet absorber is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). A topcoat layer 5 was formed by applying 1.25 parts by weight of a vesicle and 1.25 parts by weight of an inorganic ultraviolet absorber vesicle to obtain a decorative sheet 1 of Example 11 having a total thickness of 160 μm.

<Comparative Examples 1 and 2>
In Comparative Examples 1 and 2, 0.5 or 50.0 parts by weight of an organic ultraviolet absorber that is not vesicles is added to the urethane resin as the resin composition that is the main component of the topcoat layer 5. At the same time, a decorative sheet 1 to which 0.5 or 50.0 parts by weight of an inorganic ultraviolet absorber that was not vesicled was added was obtained. Other configurations are the same as those of the decorative sheet 1 of Examples 1 to 5.

<Comparative Examples 3 and 4>
In Comparative Examples 3 and 4, with respect to the crystalline homopolypropylene resin as the resin composition that is the main component of the transparent resin layer 4, 0.5 or 50.0 parts by weight of an organic ultraviolet absorber that is not vesicled is added. While adding, it was set as the decorative sheet 1 which added 0.5 or 50.0 weight part of inorganic type ultraviolet absorbers which were not vesicled. Other configurations are the same as those of the decorative sheet 1 of Examples 6 to 10.

<Comparative Example 5>
In Comparative Example 5, 0.5 part by weight of an organic ultraviolet absorber that is not vesicled, an inorganic ultraviolet ray that is not vesicled, relative to the urethane resin as the resin composition that is the main component of the topcoat layer 5 0.5 part by weight of an absorbent is added, and 0.5 part by weight of an organic ultraviolet absorbent that is not vesicles is added to the crystalline homopolypropylene resin as the resin composition that is the main component of the transparent resin layer 4. The decorative sheet 1 was prepared by adding 0.5 part by weight of an inorganic ultraviolet absorber that was not vesicled. Other configurations are the same as those of the decorative sheet 1 of Example 11.

<Comparative Example 6>
In the comparative example 6, it was set as the decorative sheet 1 which does not add an ultraviolet absorber with respect to any resin layer. Other configurations are the same as those of the decorative sheet 1 of the first embodiment.

For each decorative sheet 1 of Examples 1 to 11 and Comparative Examples 1 to 6 obtained by the above method, using a weather resistance tester (Sunshine Weather Meter: manufactured by Suga Test Instruments Co., Ltd.), JIS B A carbon arc weather resistance test according to 7753 was conducted to calculate the ultraviolet absorption ability. The test conditions were as follows: weather resistance time of 4000 hours. As for the ultraviolet absorption ability, the ultraviolet absorption rate of the transparent layer composed of the top coat layer 5 and the transparent resin layer 4 of each decorative sheet 1 is measured, and the weather resistance of the ratio of ultraviolet absorption rate between 340 nm and 500 nm (340 nm / 500 nm). The difference between before and after the sex test is calculated. About the haze value, the value after a weather resistance test was measured. For the color difference (ΔE), the color difference (ΔE) of each decorative sheet 1 before and after the weather resistance test was calculated. Furthermore, the results of visual evaluation of the appearance change after the weather resistance test are indicated by the following symbols, respectively. The evaluation results obtained are shown in Table 1 for Examples 1 to 5 and Comparative Examples 1 and 2, Table 2 for Examples 6 to 10 and Comparative Examples 3 and 4, and Tables for Example 11 and Comparative Examples 5 and 6. 3 respectively.
<Appearance change symbol>
◎: No change ○: Slight change △: Slight whitening and cracks ×: Severe whitening and partial destruction / breakage

  First, the case where an ultraviolet absorber is added to the top coat layer 5 will be described. As shown in Table 1, the evaluation results are as follows: 0.5 to 20.0 parts by weight of the organic ultraviolet absorbent vesicle and 0.5 to 20.0 parts by weight of the inorganic ultraviolet absorbent vesicle with respect to the topcoat layer 5 For the decorative sheets 1 of Examples 1 to 5 added, the UV absorption performance is small even after the weather resistance test for 4000 hours and almost the same as before the test in any addition amount. It can be seen that In addition, since the haze value after the test is small and the color difference (ΔE) value before and after the weather resistance test is also small, it has high transparency even after the weather resistance evaluation for 4000 hours, and almost no color change appears. I understand that. In the visual evaluation, excellent evaluation results were obtained. On the other hand, the decorative sheet 1 of Comparative Example 1 in which 0.5 parts by weight of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent that are not vesicled with respect to the top coat layer 5 is added, has ultraviolet absorbing ability. The value is 1.54, the haze value is 17.20%, and the color difference (ΔE) value is 7.43, showing a large value, and the UV absorption rate decreases during the 4000-hour weather resistance test and is transparent. It can be seen that the layer is degraded and the transparency is impaired. Also in the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because organic UV absorbers and inorganic UV absorbers that are not vesicles are used, resulting in poor dispersibility with respect to the resin composition as the main component, resulting in secondary aggregation, and sufficient UV absorption performance. It is thought that the cause was not. In addition, the decorative sheet of Comparative Example 2 in which 50.0 parts by weight of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent that were not vesicled with respect to the top coat layer 5 were added, had a value of ultraviolet absorbing ability of 0. 0. Although it was as small as 01, the haze value was very large at 21.79% due to the addition of a large amount of an ultraviolet absorber, and severe whitening was observed in visual evaluation. This is considered to be caused by the occurrence of blocking due to excessive addition of both UV absorbers and white turbidity.

  Next, the case where an ultraviolet absorber is added to the transparent resin layer 4 will be described. As shown in Table 2, the evaluation results are as follows: 0.1 to 5.0 parts by weight of an organic ultraviolet absorbent vesicle and 0.1 to 5.0 parts by weight of an inorganic ultraviolet absorbent vesicle are added to the transparent resin layer 4 For the decorative sheets 1 of Examples 6 to 10, in any addition amount, the value of the ultraviolet absorbing ability is extremely small, and the ultraviolet absorptance is almost the same as that before the test even after the 4000 hour weather resistance test. It can be seen that In addition, since the haze value after the test is small and the color difference (ΔE) value before and after the weather resistance test is also small, it has high transparency even after the weather resistance evaluation for 4000 hours, and almost no color change appears. I understand that. In the visual evaluation, excellent evaluation results were obtained. On the other hand, the decorative sheet 1 of Comparative Example 3 in which 0.5 parts by weight of an organic ultraviolet absorber and an inorganic ultraviolet absorber that are not vesicled with respect to the transparent resin layer 4 are added, has an ultraviolet absorbing ability. The value is 1.32, the haze value is 16.30%, and the color difference (ΔE) value is 6.21, showing a large value, and the UV absorption rate decreases during the 4000-hour weather resistance test and is transparent. It can be seen that the layer is degraded and the transparency is impaired. Also in the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because organic UV absorbers and inorganic UV absorbers that are not vesicles are used, resulting in poor dispersibility with respect to the resin composition as the main component, resulting in secondary aggregation, and sufficient UV absorption performance. It is thought that the cause was not. In addition, the decorative sheet of Comparative Example 4 in which 50.0 parts by weight of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent that were not vesicled with respect to the transparent resin layer 4 were added, had a UV absorption value of 0. Although it was as small as 01, the haze value was very large at 26.75% due to the addition of a large amount of ultraviolet absorber, and severe whitening was observed in visual evaluation. It is considered that this is because the amount of both UV absorbers added was too large and bleedout occurred and the solution became cloudy.

  And the case where a ultraviolet absorber is added to both the topcoat layer 5 and the transparent resin layer 4 is described. The evaluation results are as shown in Table 3. The decorative sheet of Example 11 was obtained by adding 1.25 parts by weight of an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle to the topcoat layer 5 and the transparent resin layer 4. No. 1 shows an extremely small value of 0.09 for the UV absorption capacity, 7.22% for the haze value, and 0.25 for the color difference (ΔE), and a 4000 hour weather resistance test was conducted. However, it can be seen that the decorative sheet 1 has excellent ultraviolet absorption performance and high design with high transparency. On the other hand, for the decorative sheet 1 of Comparative Example 5 in which 0.5 parts by weight of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent that are not vesicled with respect to the topcoat layer 5 and the transparent resin layer 4 are added, The values of the ultraviolet absorbing ability, haze value, and color difference (ΔE) are all large, indicating that the ultraviolet absorbing performance and the design are inferior to the decorative sheet 1 of Example 11. This is because the use of an ultraviolet absorber that was not vesicles resulted in inferior dispersibility in the resin composition as the main component, resulting in secondary agglomeration and failure to exhibit sufficient ultraviolet absorption performance. Conceivable.

  Moreover, about the decorative sheet 1 of the comparative example 6 which did not add an ultraviolet absorber with respect to any resin layer, the value of an ultraviolet absorptivity is 10.80, a haze value is 6.47%, and a color difference ((DELTA) E). The value of was 12.20. From the results of visual evaluation, it can be seen that remarkable whitening and cracks occur after the weather resistance test, and that the weather resistance is poor.

  Moreover, the decorative sheet 1 of Example 3 and Example 11 is compared with the following. The decorative sheet 1 of Example 3 in which 5.0 parts by weight of both UV absorber vesicles were added to the top coat layer 5, and 1.25 parts by weight of the top coat layer 5 and the transparent resin layer 4 respectively. When compared with the decorative sheet 1 of Example 11 to which the ultraviolet absorbent vesicle was added, the decorative sheet 1 of Example 11 was superior in all evaluation results, and a large amount of the ultraviolet absorbent vesicle was applied only to the top coat layer 5. Even if it does not add, it turns out that the decorative sheet 1 which has the more outstanding ultraviolet-absorbing performance is obtained by adding a ultraviolet absorber vesicle little by little with respect to the topcoat layer 5 and the transparent resin layer 4. FIG.

  From the above evaluation results, as shown in the decorative sheets 1 of Examples 1 to 5 of the present invention, 0.5 to 20.0 parts by weight of the organic ultraviolet absorbent vesicle and the inorganic ultraviolet light with respect to the top coat layer 5. It has been clarified that by adding the absorbent vesicle, a decorative sheet 1 having excellent weather resistance and designability can be obtained over a long period of time.

  Moreover, as shown in the decorative sheet 1 of Examples 6 to 10 of the present invention, 0.1 to 5.0 parts by weight of an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle with respect to the transparent resin layer 4 It became clear that the decorative sheet 1 excellent in weather resistance and designability can be obtained over a long period of time by adding.

  Further, as shown in the decorative sheet 1 of Example 11 of the present invention, an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle are added to both the top coat layer 5 and the transparent resin layer 4. Thus, it has been clarified that the decorative sheet 1 having excellent ultraviolet absorption performance can be obtained without adding a large amount of ultraviolet absorber to either the top coat layer 5 or the transparent resin layer 4.

  As described above, one of the technical features of the decorative sheet 1 of the present invention is that “a resin in a state where an organic ultraviolet absorber and an inorganic ultraviolet absorber are encapsulated in a vesicle having an outer film of a single layer film. The top coat layer 5 and the transparent resin layer 4 are formed by adding to the material ”. This is because when the decorative sheet 1 of the present invention is produced, an organic ultraviolet absorber and an inorganic ultraviolet absorber are added to the resin material in a state where they are encapsulated in a vesicle, whereby an organic ultraviolet absorber for the resin material is added. In addition, the dispersibility of the inorganic ultraviolet absorber can be dramatically improved. However, in specifying the decorative sheet 1 of the present invention thus obtained as an invention, it is possible to quantify the degree of dispersion of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent, It is technically very difficult to analyze and identify the structure, and it can be said that it is impractical because it takes an enormous amount of time for analysis.

  To explain this difficulty more specifically, vesicles are formed in nano-order and are considered to be very uniformly dispersed in the resin. For this reason, in order to measure the dispersion degree of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent which are included in the vesicle and added from the cross-section of the obtained decorative sheet 1, analysis in nano to micro order Will be forced. Usually, analysis and observation of the ultra-fine world requires extremely high technology, and in some cases, it becomes necessary to create analysis and observation technology. In order to specify the structure and characteristics of the decorative sheet 1 of the present invention, it is considered that an advanced analysis technique that is not normally used and an enormous amount of time are required. It can be said that it is impractical to clarify the structure and characteristics of 1 in terms of cost and time.

  The decorative sheet 1 and the manufacturing method of the decorative sheet 1 of the present invention are not limited to the above-described embodiments and examples, and various modifications are possible within a range that does not impair the features of the invention.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Original fabric layer 3 Ink layer 4 Transparent resin layer 4a Embossed pattern 5 Top coat layer 6 Primer layer 7 Adhesive layer 8 Concealing layer B Base material

Claims (6)

A decorative sheet comprising a topcoat layer on the outermost layer and a transparent resin layer on the lower layer of the topcoat layer,
The top coat layer and / or the transparent resin layer is formed by adding an organic ultraviolet absorber and an inorganic ultraviolet absorber,
The organic ultraviolet absorbent and the inorganic ultraviolet absorbent are an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle separately encapsulated in a vesicle having a single-layer outer film, respectively. A decorative sheet.   The decorative sheet according to claim 1, wherein the outer membrane of the vesicle is made of phospholipid.   The decorative sheet according to claim 1 or 2, wherein the organic ultraviolet absorber is benzotriazole or triazine.   The decorative sheet according to any one of claims 1 to 3, wherein the inorganic ultraviolet absorber is zinc oxide. An embossed pattern is formed on the surface of the transparent resin layer on the topcoat layer side,
The decorative sheet according to any one of claims 1 to 4, wherein the embossed pattern is provided with the top coat layer embedded therein. A method for producing a decorative sheet comprising a top coat layer made of a resin on the outermost layer, and a transparent resin layer made of a transparent olefin resin on the lower layer of the top coat layer,
With respect to the resin constituting the top coat layer and / or the transparent resin layer, an organic ultraviolet absorber and an inorganic ultraviolet absorber are respectively applied to vesicles having a single-layer outer film by supercritical reverse phase evaporation. A method for producing a decorative sheet, comprising adding an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle separately encapsulated.