JP2016117280A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having a top coat layer and/or a transparent resin layer containing a vesicle encapsulating an inorganic ultraviolet absorber and having excellent designability and weather resistance. To do. SOLUTION: The decorative sheet 1 is provided with an outermost top coat layer 2 and a transparent resin layer 3 on the lower surface of the top coat layer 2, wherein the top coat layer 2 and/or the transparent resin layer 3 is A decorative sheet containing an inorganic ultraviolet absorber, wherein the inorganic ultraviolet absorber is an inorganic ultraviolet absorber vesicle contained in an outer film. [Selection diagram]

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 containing a vesicled inorganic ultraviolet absorber and The present invention relates to a decorative sheet having a transparent resin layer.

  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.

  Thus, Patent Document 1 discloses that a topcoat layer made of a resin containing a triazine-based ultraviolet absorber is provided on the surface of a polyolefin sheet.

Japanese Patent No. 4032829

  However, organic ultraviolet absorbers such as triazines can maintain the transparency of the base resin, but change over time is unavoidable, and there is a problem in sustaining ultraviolet absorption performance over a long period of time. Based on this, when an inorganic ultraviolet absorber with little secular change is used, there is a problem that opaque particles are aggregated to lower transparency and impair the design of the decorative sheet itself.

  Further, when the blending amount of the ultraviolet absorber is increased in order to improve the weather resistance, the ultraviolet absorber is aggregated in the resin and bleed out occurs, which causes stickiness of the sheet surface and a decrease in adhesion.

  In addition, when an embossed pattern is formed to improve the design of the decorative sheet, the recessed portion of the embossed pattern is thinner than other portions, so the weather resistance is particularly low, and deterioration occurs from the recessed portion. Has started to cause whitening and breakage.

  An object of the present invention is to provide a decorative sheet having a top coat layer and / or a transparent resin layer containing a vesicle encapsulating an inorganic ultraviolet absorber and having excellent design and weather resistance.

  As a result of intensive studies, the present inventors have succeeded in dramatically improving the dispersibility of the inorganic ultraviolet absorber in the resin material by including the inorganic ultraviolet absorber in a state of being included in the vesicle. It has been found that the transparency required for the decorative sheet can be achieved.

  In order to achieve the above object, the decorative sheet according to the first aspect of the present invention is a decorative sheet comprising a top coat layer on the outermost layer and a transparent resin layer on the lower surface of the top coat layer, wherein the top coat layer The transparent resin layer contains an inorganic ultraviolet absorber, and the inorganic ultraviolet absorber is an inorganic ultraviolet absorber vesicle included in an outer film.

  The decorative sheet according to the second aspect of the present invention is characterized in that the outer film is a single-layer film.

  The decorative sheet of the third aspect of the present invention is characterized in that the inorganic ultraviolet absorbent vesicle is an inorganic ultraviolet absorbent liposome having an outer membrane made of phospholipid.

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

  The decorative sheet according to the fifth aspect of the present invention is characterized in that an embossed pattern is formed in the transparent resin layer, and the topcoat layer is embedded in at least a recess of the embossed pattern. .

  The decorative sheet according to the sixth aspect of the present invention is characterized in that an ink layer containing a light stabilizer is provided below the transparent resin layer.

  According to the decorative sheet of the present invention, by providing the top coat layer and / or the transparent resin layer containing the inorganic ultraviolet absorbent vesicle, it has excellent design properties and weather resistance over a long period of time. It is possible to provide a decorative sheet that achieves the above.

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

  The decorative sheet of the present invention is a decorative sheet comprising a top coat layer on the outermost layer and a transparent resin layer on the lower surface of the top coat layer, wherein the top coat layer and / or the transparent resin layer is an inorganic ultraviolet absorber. In particular, it is important that the inorganic ultraviolet absorber is a inorganic ultraviolet absorber vesicle included in the outer membrane.

  Such an inorganic ultraviolet absorbent vesicle has a structure in which an inorganic ultraviolet absorbent is encapsulated in a vesicular capsule having a membrane structure closed in a spherical shell shape. This inorganic ultraviolet absorber vesicle has extremely high dispersibility without particles being aggregated by the action of repelling each other's outer membranes. This action makes it possible to uniformly disperse the inorganic ultraviolet absorber in the resin composition constituting the top coat layer and the transparent resin layer.

  Examples of a method for obtaining an inorganic ultraviolet absorber vesicle (method of vesicle treatment) include, for example, Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase Evaporation method etc. are mentioned. Briefly explaining such a vesicle treatment method, in the Bangham method, chloroform or a chloroform / methanol mixed solvent is placed in a container such as a flask, and phospholipid is further dissolved therein. Thereafter, the solvent is removed using an evaporator to form a thin film composed of lipid, and after adding an additive dispersion, the mixture is hydrated and dispersed by a vortex mixer to obtain a vesicle. The extrusion method is a method of preparing a vesicle by preparing a thin phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method. The hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining vesicles by gently stirring and dispersing without using a mixer. In the reverse phase evaporation method, phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to make a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and then water is added. This is a method for obtaining vesicles. The freeze-thaw method is a method using cooling / heating as external perturbation, and is a method of obtaining vesicles by repeating this cooling / heating.

  In particular, as a method for obtaining an inorganic ultraviolet absorbent vesicle having an outer film composed of a single layer film, a supercritical reverse phase evaporation method can be mentioned. The supercritical reverse phase evaporation method is disclosed in JP-T-2002 / 032564, JP-A No. 2003-119120, JP-A No. 2005-298407 and JP-A No. 2008-063274 (provided by the present inventors). (Hereinafter referred to as “supercritical reverse phase evaporation method publications”), and can be carried out using the method and apparatus described in the supercritical reverse phase evaporation method publications. Specifically, supercritical reverse phase evaporation is a method in which a substance that forms the outer membrane of a vesicle is uniformly dissolved in carbon dioxide under supercritical conditions or temperature conditions or pressure conditions above the critical point. This is a method for forming a capsule-like vesicle including an inorganic ultraviolet absorbent as an encapsulating substance by adding a water phase containing an inorganic ultraviolet absorbent as a water-soluble or hydrophilic encapsulating substance. . In particular, an inorganic ultraviolet absorbent vesicle in which the outer membrane is composed of a substance containing a biological lipid such as phospholipid is referred to as an inorganic ultraviolet absorbent liposome. The supercritical carbon dioxide means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or more, and a temperature condition above the critical point. Carbon dioxide under lower or pressure conditions means carbon dioxide having only critical temperature or critical pressure exceeding the critical condition. By this method, a single-layer lamellar vesicle having a diameter of 50 to 800 nm containing an inorganic ultraviolet absorber can be obtained.

  Phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated yolk lecithin, soy lecithin, glycerophospholipid such as hydrogenated soy lecithin, sphingomyelin, Examples include sphingophospholipids such as ceramide phosphorylethanolamine and ceramide phosphorylglycerol.

  Other substances that form the outer membrane of vesicles include nonionic surfactants and dispersants such as a mixture of this with cholesterols or triacylglycerols. Among these, nonionic surfactants include polyglycerol ether, dialkyl glycerol, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene. -One or two of polyoxyethylene copolymer, polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. More than seeds can be used. As cholesterols, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate or cholecalciferol can be used.

  Moreover, you may make it form the outer membrane of a liposome from the mixture of a phospholipid and a dispersing agent. In the decorative sheet of the present invention, it is preferable that the inorganic ultraviolet absorbent vesicle is an inorganic ultraviolet absorbent liposome having an outer membrane made of phospholipid, and the outer membrane is made of phospholipid to thereby form a top coat. The compatibility between the resin material which is the main component of the layer and / or the transparent resin layer and the vesicle can be improved.

  Examples of inorganic ultraviolet absorbers include zinc oxide, titanium oxide, and ceria oxide. In particular, zinc oxide is preferable because it has a refractive index close to that of a resin material used as a main component in the topcoat layer and the transparent resin layer, 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. Such an inorganic ultraviolet absorber is preferably contained in the topcoat layer in a proportion of 0.5 to 20 parts by weight with respect to 100 parts by weight of the resin material as the main component of the topcoat layer. More preferably, it is contained in a proportion of 1 to 10 parts by weight, and more preferably, it is contained in a proportion of 3 to 5 parts by weight. Moreover, in the transparent resin layer, it is preferable to contain in the ratio of 100-50000 ppm with respect to the resin material which is a main component of a transparent resin layer, More preferably, it is contained in the ratio of 2000-30000 ppm. It is. By setting the inorganic ultraviolet absorber to the above content, a decorative sheet having particularly excellent weather resistance and design properties can be realized.

  In the decorative sheet of the present invention, it is important that an embossed pattern is formed in the transparent resin layer, and the topcoat layer is embedded at least in the concave portion of the embossed pattern. When providing on the surface of the layer, it is preferable to form the top coat layer in the recess by wiping.

  Further, it is important that an ink layer containing at least a light stabilizer is provided in the lower layer of 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, the binder resin itself that forms the ink layer and radicals generated by resin degradation of the other layer reduce the chemical component of the pigment in the ink, thereby fading the pigment. It can suppress and can hold a colorful picture over a long period of time.

  A specific embodiment of the decorative sheet of the present invention will be described below with reference to FIG.

  In the embodiment of the decorative sheet of the present invention, as shown in FIG. 1, an adhesive layer 4 is formed on a raw fabric resin sheet as a raw fabric layer 6 on which an ink layer 5 is applied, and inorganic ultraviolet rays are used. It can be obtained by laminating a transparent resin layer 3 containing an absorbent vesicle and an adhesive resin layer 3b co-pressed by dry lamination or extrusion lamination. In the present invention, as shown in FIG. 1, the top coat layer 2 is formed by applying a resin composition containing an inorganic ultraviolet absorbent vesicle to the recesses of the embossed pattern 3 a formed in the transparent resin layer 3. The resin composition is embedded by wiping by embedding the resin composition only in the recess by scraping the coating liquid with a squeegee or the like. Details of each layer will be described below.

  The top surface of the decorative sheet 1 is provided with a topcoat layer 2 that plays a role of protecting the surface and adjusting gloss. The main resin material is polyurethane, acrylic silicon, fluorine, epoxy. Resin materials such as those based on vinyl, vinyl, polyester, melamine, aminoalkyd, and urea can be appropriately selected and used. The form of the resin material is not particularly limited, such as aqueous, emulsion, solvent type. The curing method can be appropriately selected from a one-component type, a two-component type, an ultraviolet curing method, and the like. In this embodiment, the inorganic ultraviolet absorber vesicle is contained in a proportion of 0.5 to 20 parts by weight with respect to 100 parts by weight of the resin material. In particular, in the present embodiment, it is preferable to use an inorganic ultraviolet absorbent liposome having an outer membrane made of a phospholipid obtained by a supercritical reverse phase evaporation method as the inorganic ultraviolet absorbent vesicle.

  And in this embodiment, it is set as the structure which provides the topcoat layer 2 only in the recessed part of the embossed pattern 3a of the transparent resin layer 3, However, The embossed pattern should just be embedded and provided at least in the recessed part of the embossed pattern 3a. By forming 3a, it is possible to maintain high weather resistance even in a recess having a thin layer thickness. The topcoat layer 2 may be provided so as to cover the entire surface of the transparent resin layer 3, and the decorative sheet 1 having better weather resistance is provided by providing the topcoat layer 2 so as to cover the entire surface. be able to.

  As the resin material used as the main component of the topcoat layer 2, urethane-based materials using isocyanate are suitable from the viewpoints of workability, cost, cohesion of the resin itself, and the like. Isocyanates 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, isocyanurates and the like can be appropriately selected and used. Curing agents based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a molecular structure of 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 type and a photocurable type, it is possible to improve surface hardness, suppress curing shrinkage, and improve adhesion. Can be planned.

  A transparent resin layer 3 is provided on the lower surface of the top coat layer 2. The resin material used as the main component of the transparent resin layer 3 is preferably made of an olefin resin, and in addition to polypropylene, polyethylene, polybutene, etc., 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, 1-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) homopolymerized or copolymerized with two or more types, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / Like methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, etc. Examples include those obtained by copolymerizing ethylene or α-olefin and other monomers. Moreover, when improving the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene.

  In the present embodiment, the transparent resin layer 3 is composed of a resin composition containing the resin material as a main component and containing an inorganic ultraviolet absorbent vesicle obtained by a supercritical reverse phase evaporation method. The inorganic ultraviolet absorbent vesicle is preferably contained in a ratio of 1000 to 50000 ppm with respect to the resin material which is the main component of the transparent resin layer 3. In particular, in this embodiment, an inorganic ultraviolet absorbent liposome having an outer membrane made of phospholipid obtained by a supercritical reverse phase evaporation method is used as the inorganic ultraviolet absorbent vesicle.

  The resin composition constituting the transparent resin layer 3 includes various kinds of heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusting agents as necessary. A functional additive may be contained. These various functional additives can be appropriately selected from known ones and used.

  Further, an embossed pattern 3a is formed on the surface of the transparent resin layer 3 in order to improve the design. The embossed pattern 3a is formed by a method of forming the embossed pattern 3a by applying heat and pressure using an embossed plate having a concavo-convex pattern before forming the topcoat layer 2, or when forming a film using an extruder. The embossed pattern 3a can be formed simultaneously with the cooling of the sheet using a cooling roll having an uneven pattern. Further, it is possible to further improve the design by embedding ink or the like in the recesses of the embossed pattern 3a.

  When nonpolar polypropylene is used for the transparent resin layer 3, it is preferable to provide the adhesive resin layer 3 b when the adhesion between the transparent resin layer 3 and the resin layer disposed on the lower surface is low. As the adhesive resin layer 3b, those obtained by acid-modifying polypropylene, polyethylene, acrylic resin or the like are preferable, and the layer thickness is desirably 2 μm or more and 20 μm or less from the viewpoint of adhesion and heat resistance. The adhesive resin layer 3b is preferably formed by coextrusion laminating with the transparent resin layer 3 from the viewpoint of improving the adhesive strength.

  On the lower surface side of the transparent resin layer 3, as shown in FIG. 1, an adhesive layer 4 for further improving the adhesion between the ink layer 5 on the lower surface side and the transparent resin layer 3 is provided. The material of the adhesive layer 4 is not particularly limited, but can be appropriately selected from acrylic, polyester, polyurethane, epoxy, and the like. The coating method can be appropriately selected depending on the viscosity of the adhesive, etc., but generally, a gravure coat is used, and the gravure coat is applied to the raw fabric layer 6 side on which the ink layer 5 is applied. After that, it is laminated with the transparent resin layer 3 or the adhesive resin layer 3b. The adhesive layer 4 can be omitted when the adhesive strength between the transparent resin layer 3 and the ink layer 5 is sufficiently obtained.

  An ink layer 5 is provided on the lower surface side of the adhesive layer 4. The ink layer 5 includes a pattern layer 5a made of ink containing at least a light stabilizer. Further, by providing the solid ink layer 5b on the lower surface side of the picture pattern layer 5a, it is possible to provide concealment. For the ink, nitrified cotton as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, and the like can be appropriately selected and used. The binder is not particularly limited such as aqueous, solvent-based, or emulsion-based, and the curing method may be a one-component type or a two-component type using a curing agent. Furthermore, you may use the method of hardening ink by active energy ray irradiation, such as an ultraviolet-ray and an electron beam. In particular, a general method is a method in which urethane-based ink is used and is cured by isocyanate. In addition to these binders, coloring agents such as pigments and dyes, extender pigments, solvents, various additives, and the like that are included in ordinary inks are included. Examples of highly versatile pigments include pearls such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.

  In the solid ink layer 5b, basically, the same material as the ink used for the pattern layer 5a can be used. However, when the ink is a transparent material, an opaque pigment, titanium oxide, iron oxide, or the like is used. be able to. In addition to this, it is possible to provide concealment properties by adding metals such as gold, silver, copper, and aluminum. Generally, flaky aluminum is used.

  These ink layers 5 can be directly formed on the original fabric layer 6 by gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, or the like. Moreover, when concealing property is imparted by a metal, it is preferable to use a comma coater, knife coater, lip coater, metal vapor deposition or sputtering method.

  For the interface where the resin material or ink is laminated, the surface to be laminated is subjected to corona treatment, ozone treatment, plasma treatment, electron beam in consideration of its adhesiveness before applying the resin material or ink. Adhesion between layers can be improved by performing a lamination process after activating the surface by performing surface treatment such as treatment, ultraviolet treatment, or dichromic acid treatment.

  A raw fabric layer 6 is provided on the lower surface side of the ink layer 5. The raw fabric layer 6 is made of paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polystyrene, polybutylene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic or other synthetic resin, or These synthetic resin foams, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, aluminum, It can be arbitrarily selected from metal foils such as iron, gold and silver.

  In addition, when an olefin resin is used as the raw fabric layer 6, the surface is often in an inactive state, and therefore, the raw fabric layer 6 and the base material to which the decorative sheet 1 is attached are attached. It is preferable to provide a primer layer. In addition to this, in order to improve the adhesion between the raw fabric layer 6 made of an olefin resin and the substrate, the raw fabric layer 6 is subjected to corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet rays. It is preferable that treatment or dichromic acid treatment is performed.

  In addition, as a primer layer, although the same material as the ink layer 5 can be applied, in consideration of winding up the decorative sheet 1 in a web shape, in order to avoid blocking and to improve the adhesion to the adhesive. Inorganic fillers such as silica, alumina, magnesia, titanium oxide or barium sulfate are preferably contained.

  In the present embodiment, both the top coat layer 2 and the transparent resin layer 3 contain an inorganic ultraviolet absorbent vesicle, but either one contains an inorganic ultraviolet absorbent vesicle. A configuration may be adopted.

  In the decorative sheet 1 of the present embodiment, the raw fabric layer 6 is 20 μm to 150 μm in consideration of printing workability, cost, etc., the adhesive layer 4 is 1 μm to 20 μm, the transparent resin layer 3 is 20 μm to 200 μm, and the topcoat layer. 2 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.

  As described above, the decorative sheet 1 of the present invention having the top coat layer 2 and / or the transparent resin layer 3 containing the inorganic ultraviolet absorbent vesicle has a very uniform inorganic ultraviolet absorbent in the resin composition. Dispersed topcoat layer 2 and / or transparent resin layer 3 are realized, and as a result, it has excellent design properties without impairing transparency, and has high UV absorption performance even with a small content. It is possible to provide the decorative sheet 1 that can achieve the excellent weather resistance over a long period of time.

  In addition to this, by realizing high dispersibility of the inorganic ultraviolet absorber in the resin composition, there is no bleed out caused by the aggregated additive, and there is little stickiness on the surface The decorative sheet 1 can be provided.

  In addition, as in this embodiment, by using an inorganic ultraviolet absorber as an inorganic ultraviolet absorber vesicle, it is possible to meet the demand for containing a large amount of an inorganic ultraviolet absorber, and even more, It is possible to provide the decorative sheet 1 having excellent weather resistance. In addition, by using an inorganic ultraviolet absorber vesicle, the effect that the flexibility, impact strength, and flatness required for the decorative sheet can be maintained, and the raw material resin of the topcoat layer 2 is inorganic. It is possible to obtain an effect that the decorative sheet 1 having excellent design properties can be obtained by suppressing the thickening by adding a UV absorber and embedding the coating liquid to every corner of the concave portion of the embossed pattern 3a. .

  Furthermore, in this embodiment, the topcoat layer 2 and / or the transparent resin layer 3 are configured by using inorganic ultraviolet absorbent liposomes obtained by supercritical reverse phase evaporation as the inorganic ultraviolet absorbent vesicle. In the resin composition, it is possible to disperse the inorganic ultraviolet absorber very uniformly, and it is possible to realize more excellent transparency and ultraviolet absorption performance.

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

<Preparation 1 of Inorganic UV Absorber Vesicle>
First, a method for preparing an inorganic ultraviolet absorbent vesicle used in Examples 1 and 2 will be described. Preparation of the inorganic ultraviolet absorber vesicle is carried out by supercritical reverse phase evaporation. Specifically, 100 parts by weight of 2-propanol and oxidation as an inorganic ultraviolet absorber in a high-pressure stainless steel container kept at 60 ° C. 70 parts by weight of zinc and 5 parts by weight of phosphatidylcholine as a phospholipid are sealed, and carbon dioxide is injected so that the pressure in the container becomes 20 MPa to make a supercritical state. Injecting 100 parts by weight of the mixture, stirring and mixing for 15 minutes while maintaining the temperature and pressure, discharging carbon dioxide and returning to atmospheric pressure, thereby obtaining a zinc oxide liposome having a monolayer outer membrane composed of phospholipids It was.

<Example 1>
In Example 1, it was set as the decorative sheet 1 which comprised the transparent resin layer 3 containing the zinc oxide liposome prepared in the above-mentioned <Preparation 1 of an inorganic type ultraviolet absorber vesicle>.

Specifically, a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) is 500 ppm, a zinc oxide liposome is 500,1000,2000,30000,50000,150,000 ppm, a hindered amine light stabilizer. A resin added with 2000 ppm (Kimasorb 944; manufactured by BASF) was melt-extruded using an extruder to form a sheet-like transparent resin layer 3 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm, Both surfaces of the obtained transparent resin layer 3 were subjected to corona treatment, and the wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, a hindered amine light is applied to the two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) on the surface of a 70 μm polyethylene sheet (raw fabric layer 6) having a concealing property. A pattern printing layer 5a is provided by printing with a gravure printing method using an ink to which 0.5% by weight of a stabilizer (Kimasorb 944; manufactured by BASF) is added, and the back side of the original fabric layer 6 is provided. Primer coating was applied. Thereafter, the transparent resin layer 3 is dry laminated on the surface of the pattern layer 5a of the original fabric layer 6 via an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m ² ). Bonded by the method. After embossed pattern 3a is applied to the surface of transparent resin layer 3 of the laminated sheet, a two-component urethane topcoat (W184; manufactured by DIC Graphics) is applied at a coating thickness of 3 g / m ² to form a topcoat. Layer 2 was formed to obtain a decorative sheet 1 of the present invention shown in FIG. 1 having a total thickness of 154 μm.

<Example 2>
In Example 2, the decorative sheet 1 was provided with the topcoat layer 2 and the transparent resin layer 3 each containing the zinc oxide liposome prepared in <Preparation 1 of inorganic ultraviolet absorbent vesicle> described above.

Specifically, a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) is 500 ppm, zinc oxide liposome is 2000 ppm, and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) is 2000 ppm in a homopolypropylene resin. The added resin is melt-extruded using an extruder to form a sheet-like transparent resin layer 3 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm, and both sides of the obtained transparent resin layer 3 are formed. Corona treatment was performed, and the wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, a hindered amine light is applied to the two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) on the surface of a 70 μm polyethylene sheet (raw fabric layer 6) having a concealing property. A pattern printing layer 5a is provided by printing with a gravure printing method using an ink to which 0.5% by weight of a stabilizer (Kimasorb 944; manufactured by BASF) is added, and the back side of the original fabric layer 6 is provided. Primer coating was applied. Thereafter, the transparent resin layer 3 is dry laminated on the surface of the pattern layer 5a of the original fabric layer 6 via an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m ² ). Bonded by the method. After embossed pattern 3a is applied to the surface of transparent resin layer 3 of the bonded sheet, 0.1 part by weight of zinc oxide is added to 100 parts by weight of two-component urethane topcoat (W184; manufactured by DIC Graphics). A topcoat coating solution to which zinc oxide liposomes were added was applied at a coating thickness of 3 g / m ² to provide a topcoat layer 2, and the topcoat coating solution was embedded by wiping into the recesses of the embossed pattern 3a, resulting in a total thickness of 150 μm. The decorative sheet of the present invention was obtained.

<Comparative Example 1>
In the comparative example 1, it was set as the decorative sheet | seat which comprised the transparent resin layer 3 containing a zinc oxide as an inorganic type ultraviolet absorber which has not been vesicled.

  Specifically, 500 ppm of hindered phenol antioxidant (Irganox 1010; manufactured by BASF), 2000 ppm of zinc oxide, and 2000 ppm of hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to homopolypropylene resin. The obtained resin was melt extruded using an extruder to form a sheet-like transparent resin layer 3 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm. A sheet was obtained.

<Comparative Example 2>
In the comparative example 2, it was set as the decorative sheet | seat which comprised the transparent resin layer 3 containing the inorganic type ultraviolet absorber which gave the nano-ized process by the solid-phase method.

  Specifically, zinc oxide nano-treated by a solid phase method was used as the inorganic ultraviolet absorber. Specifically, 100 g of isopropyl alcohol and 50 g of zinc oxide are used for 60 minutes in a bead mill and 30 μm of stabilized zirconia beads are used to obtain zinc oxide that has been subjected to nano-treatment with an average particle diameter of about 1 nm to 150 nm. Homopolypropylene resin, hindered phenol antioxidant (Irganox 1010; manufactured by BASF), 500 ppm, nano-treated zinc oxide obtained by the above-mentioned solid phase method, 2000 ppm, hindered amine light stabilizer ( Except that a resin added with 2000 ppm of Kimasorb 944 (manufactured by BASF) was melt-extruded using an extruder to form a sheet-like transparent resin layer 3 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm. A decorative sheet was obtained in the same manner as in Example 1.

<Comparative Example 3>
In the comparative example 3, it was set as the decorative sheet | seat which comprised the transparent resin layer 3 containing a benzotriazole type material as an ultraviolet absorber which has not been vesicled.

  Specifically, a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) is 500 ppm, a benzotriazole ultraviolet absorber (BASF) is 2000 ppm, a hindered amine light stabilizer (Kimasorb). 944; manufactured by BASF Co., Ltd.) was added with 2000 ppm of resin, melt-extruded using an extruder, and formed a sheet-like transparent resin layer 3 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm, A decorative sheet was obtained in the same manner as in Example 1.

For each decorative sheet 1 of Examples 1 and 2 and Comparative Examples 1 to 3, using a weather resistance tester (Sunshine Weather Meter: manufactured by Suga Test Instruments Co., Ltd.), carbon arc weather resistance according to JIS B 7753 The UV absorption ability was calculated by conducting a property test. The test conditions were as follows: weather resistance time of 4000 hours. About the ultraviolet absorptivity, about the transparent layer which consists of the topcoat layer 2 and the transparent resin layer 3 of each decorative sheet 1, the difference before and after the weather resistance test of the ratio of ultraviolet absorption between 340 nm and 500 nm (340 nm / 500 nm) It was calculated (in Table 1, it is described as the ultraviolet absorbing ability). Moreover, the haze value after a weather resistance test was evaluated. Furthermore, the color difference (ΔE) of each decorative sheet 1 before and after the weather resistance test and the appearance change after the weather resistance test were evaluated. The contents of the appearance change symbols are as follows. The obtained evaluation results are shown in Table 1.
<Appearance change symbol>
◯: No change △: Slight whitening ×: Severe whitening and partial destruction / breakage

  In the decorative sheet 1 in Example 1, as shown in Table 1, the decorative sheet 1 having the transparent resin layer 3 having a zinc oxide liposome content of 1000 to 50000 ppm has a very small value of ultraviolet absorbing ability. Therefore, it is understood that the ultraviolet absorption performance almost unchanged before and after the weather resistance test is maintained, and the high transparency is maintained from the value of the haze value after the weather resistance test. Furthermore, from the value of the color difference (ΔE) before and after the weather resistance test, almost no color change was observed, and good results were also obtained in the visual appearance change evaluation, which is high over a long period of time. It became clear that it is the decorative sheet 1 which can implement | achieve a weather resistance and the outstanding design property.

  However, the decorative sheet 1 having the transparent resin layer 3 having a zinc oxide liposome content of 500 ppm in Example 1 has a small haze value, a value of ultraviolet absorption and a color difference before and after the weather resistance test (ΔE). The value of indicates a large value. This is because the content of zinc oxide liposomes is extremely small, and the white turbidity of the resin composition due to the additive is small, but sufficient UV absorption performance is not obtained, and tree material deterioration and decoloration occur. is there. Therefore, the decorative sheet 1 including the transparent resin layer 3 containing zinc oxide liposomes at a ratio of 500 ppm is extremely excellent in design, and can be applied to indoor applications that do not require high weather resistance compared to outdoor applications. Conceivable.

  Moreover, about the decorative sheet 1 which comprises the transparent resin layer 3 in which the content of the zinc oxide liposome in Example 1 is 150,000 ppm, the haze value is large, and the color difference (ΔE) before and after the ultraviolet ray absorption ability and the weather resistance test. The value of indicates a small value. This is because the content of the zinc oxide liposome is too large, and the whitening of the resin composition resulting from the additive is large, but high UV absorption performance is obtained, and deterioration of the resin material is suppressed. It is. Therefore, the decorative sheet 1 having the transparent resin layer 3 containing zinc oxide liposomes at a rate of 150,000 ppm can be applied to applications where the transparent resin layer 3 does not require high transparency.

  From the result of Example 1, it became clear that it is preferable for the transparent resin layer 3 to contain zinc oxide liposomes in the range of 1000 to 50000 ppm.

  In the decorative sheet 1 in Example 2, as shown in Table 1, the decorative sheet 1 is provided with a top coat layer 2 and a transparent resin layer 3 containing zinc oxide liposomes, and has ultraviolet absorbing ability. It can be seen that the value is extremely small, and the ultraviolet absorption performance almost unchanged before and after the weather resistance test is maintained. Moreover, high transparency was maintained from the haze value after a weather resistance test. Furthermore, the color difference (ΔE) before and after the weather resistance test was almost unchanged, and good results were also obtained in visual appearance change evaluation. From this evaluation result, the transparent layer composed of the top coat layer 2 and the transparent resin layer 3 can continue to exhibit excellent ultraviolet absorption performance over a long period of time. It became clear that it was possible to prevent whitening and maintain excellent transparency over a long period of time.

  In the decorative sheets 1 in Comparative Examples 1 to 3, the value of the ultraviolet absorbing ability was large, and a difference was observed in the ultraviolet absorbing ability before and after the weather resistance test. Moreover, also about the haze value, the value was large except the comparative example 3 which used the organic type ultraviolet absorber, and transparency was impaired. From the evaluation results of the color difference (ΔE) before and after the weather resistance test and the visual appearance change after the weather resistance test, whitening and cracks are recognized, and the decorative sheets 1 of Comparative Examples 1 to 3 are inferior in weather resistance. It became clear.

  From the above results, it was clarified that the decorative sheets of Examples 1 and 2 were the decorative sheet 1 having excellent weather resistance and transparency required for the decorative sheet.

  From the evaluation results of the decorative sheets 1 in Examples 1 and 2 and Comparative Examples 1 to 3 described above, the top coat layer 2 and / or the transparent resin layer 3 containing zinc oxide liposomes as inorganic ultraviolet absorbent vesicles were provided. It became clear that the use of the decorative sheet 1 can provide a decorative sheet having excellent weather resistance over a long period of time.

<Preparation of inorganic ultraviolet absorber vesicle 2>
A method for preparing the inorganic ultraviolet absorbent vesicle used in Examples 3 and 4 will be described. Preparation of the inorganic ultraviolet absorber vesicle is carried out by a supercritical reverse phase evaporation method. Specifically, with respect to a high-pressure stainless steel container maintained at 60 ° C., 100 parts by weight of hexane and an inorganic ultraviolet absorber are used. 70 parts by weight of zinc oxide (average particle size 20 nm) and 5 parts by weight of phosphatidylcholine as a phospholipid are sealed and carbon dioxide is injected so that the pressure in the container becomes 20 MPa. Injecting 100 parts by weight of ethyl acetate while stirring and mixing, stirring and mixing for 15 minutes while maintaining the temperature and pressure, and then removing the carbon dioxide and returning to atmospheric pressure to provide a single-layer outer membrane made of phospholipid Zinc oxide liposomes were obtained.

<Example 3>
In Example 3, it was set as the decorative sheet 1 provided with the topcoat layer 2 containing the zinc oxide liposome prepared in <Preparation 2 of inorganic ultraviolet absorber vesicle> described above. The zinc oxide liposome content is 0.05, 0.54, 1.07, 5.35, 10.70, 21.100 with respect to 100 parts by weight of the resin material as the main component of the top coat layer 2. 40, 48.20 parts by weight (of which the zinc oxide content is 0.05, 0.5, 1.0, 5.0, 10.0, 20.0, 40.0 parts by weight) It was.

Specifically, a resin obtained by adding 500 ppm of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and 2000 ppm of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) to a highly crystalline homopolypropylene resin. Is melt-extruded using an extruder to form a sheet-like transparent resin layer 3 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm, and corona treatment is performed on both surfaces of the obtained transparent resin layer 3. The wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, pattern printing is performed on the surface of a 70 μm polyethylene sheet (raw fabric layer 6) with concealment by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) to 3 μm. And a primer coat of 1 μm was applied to the back surface of the raw fabric layer 6. Thereafter, on the surface of the pattern layer 5a of the original fabric layer 6, the transparent resin layer 3 is coated with an adhesive for dry lamination having a thickness of 3 μm (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m ² ). Then, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 6, the pattern layer 5a, the trilaminate adhesive, the primer coat, and the transparent resin layer 3 was obtained. After the embossed pattern 3a is applied to the surface of the transparent resin layer 3 of this laminated resin sheet, the supercritical reverse phase evaporation method described above is applied to 100 parts by weight of a two-component urethane topcoat (W184; manufactured by DIC Graphics). The zinc oxide liposome obtained by the above was added at a ratio of 0.05, 0.54, 1.07, 5.35, 10.70, 21.40 or 48.20 parts by weight to a coating thickness of 3 g / m ² . Then, the top coat layer 2 was formed to obtain the decorative sheet 1 of the present invention shown in FIG. 1 having a total thickness of 160 μm.

<Example 4>
In Example 4, a cosmetic comprising the topcoat layer 2 containing the zinc oxide liposome prepared in <Preparation 2 of inorganic ultraviolet absorbent vesicle> and the pattern layer 5a containing a light stabilizer. Sheet 1 was obtained. The content of the zinc oxide liposome is 1.07, 5.35, 10.70 parts by weight with respect to 100 parts by weight of the resin material which is the main component of the top coat layer 2 (of which the content of zinc oxide is Is 1.0, 5.0, 10.0 parts by weight.).

  Specifically, 0.5% by weight of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) is added to the binder resin component composed of a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.). A decorative sheet 1 was obtained in the same manner as in Example 3 except that the pattern layer 5a was formed using the ink prepared.

<Comparative example 4>
In the comparative example 4, it was set as the decorative sheet 1 provided with the topcoat layer 2 containing the zinc oxide which has not been vesicled. The zinc oxide content was 0.5 or 1.0 part by weight with respect to 100 parts by weight of the resin material that is the main component of the topcoat layer 2. The top coat layer 2 has the same configuration as that of the decorative sheet 1 described in Example 3 except that the top coat layer 2 has the above configuration.

<Comparative Example 5>
In the comparative example 5, it was set as the decorative sheet 1 which comprised the topcoat layer 2 containing the nano-ized zinc oxide which gave the nano-ized process by the solid-phase method. In addition, content of nano-ized zinc oxide was 0.5 or 1.0 weight part with respect to 100 weight part of resin materials which are the main components of the topcoat layer 2. FIG. The top coat layer 2 has the same configuration as that of the decorative sheet 1 described in Example 3 except that the top coat layer 2 has the above configuration.

<Comparative Example 6>
In the comparative example 6, it was set as the decorative sheet 1 which comprised the topcoat layer 2 containing the triazine type ultraviolet absorber which is an organic type ultraviolet absorber. The content of the triazine-based ultraviolet absorber was 0.5 parts by weight with respect to 100 parts by weight of the resin material that is the main component of the topcoat layer 2. The top coat layer 2 has the same configuration as that of the decorative sheet 1 described in Example 3 except that the top coat layer 2 has the above configuration.

<Comparative Example 7>
In the comparative example 7, it was set as the decorative sheet 1 which comprised the topcoat layer 2 and the transparent resin layer 3 which do not contain an inorganic type ultraviolet absorber. About another structure, it is the structure similar to the decorative sheet 1 of Example 3. FIG.

For each decorative sheet 1 of Examples 3 and 4 and Comparative Examples 4 to 7, as in Examples 1 and 2 and Comparative Examples 1 to 3, calculation of ultraviolet absorption ability, measurement of haze value after weather resistance test The color difference (ΔE) of each decorative sheet 1 before and after the weather resistance test and the appearance change after the weather resistance test were evaluated. The contents of the appearance change symbols are as follows. The obtained evaluation results are shown in Table 2.
<Appearance change symbol>
◎: No change ○: Slight change △: Slight whitening and cracks ×: Severe whitening and partial destruction / breakage

  In the decorative sheet 1 in Example 3, as shown in Table 2, the zinc oxide liposome content is 0.54 to 21.40 parts by weight (of which zinc oxide is 0.50 to 20.00 parts by weight). The decorative sheet 1 having the top coat layer 2 has a low UV absorption value and a color difference (ΔE) value before and after the weather resistance test, and realizes a haze value of 15% or less even after the weather resistance test. It was revealed that the decorative sheet 1 can maintain excellent transparency over a long period of time.

  However, the content of zinc oxide liposomes in Example 3 was 0.05 parts by weight (of which zinc oxide was 0.05 parts by weight. The other components were very small and outside the effective numerical range. The decorative sheet 1 having the top coat layer 2 defined as) has a small haze value, and a large value for the UV absorption ability and the color difference (ΔE) before and after the weather resistance test. This is because the content of zinc oxide liposomes is extremely small, and the white turbidity of the resin composition due to the additive is small, but sufficient UV absorption performance is not obtained, and the resin material is deteriorated and decolored. is there. Therefore, the decorative sheet 1 comprising the top coat layer 2 containing 0.05 parts by weight of zinc oxide liposomes with respect to 100 parts by weight of the resin material as the main component is extremely excellent in design, and is used outdoors. It can be applied to indoor applications where high weather resistance is not required.

  Moreover, about the decorative sheet 1 which comprises the topcoat layer 2 in which content of the zinc oxide liposome in Example 3 was 45.20 parts by weight (of which zinc oxide was 40.00 parts by weight), the haze value was large. In addition, the value of the ultraviolet absorbing ability and the value of the color difference (ΔE) before and after the weather resistance test are small values. This is because the content of the zinc oxide liposome is too large, and the whitening of the resin composition resulting from the additive is large, but high UV absorption performance is obtained, and deterioration of the resin material is suppressed. It is. Therefore, the decorative sheet 1 including the topcoat layer 2 containing zinc oxide liposomes in a proportion of 45.20 parts by weight with respect to 100 parts by weight of the resin material as the main component requires high transparency for the topcoat layer 2. Application to unusable applications is conceivable.

  From the results of Example 3, with respect to the topcoat layer 2, the zinc oxide liposome is within a range of 0.54 to 21.40 parts by weight (of which zinc oxide is 0.5 to 20.00 parts by weight). It became clear that it was preferable to contain.

  In the decorative sheet 1 in Example 4, as shown in Table 2, the decorative sheet 1 was provided with a top coat layer 2 containing zinc oxide liposomes and a pattern layer 5a containing a light stabilizer. As for the value of the ultraviolet absorbing ability, the smaller the zinc oxide liposome content, the smaller the value. Moreover, in the case of all content, the value of the haze value after a weather resistance test was small, and high transparency was maintained. Furthermore, the color difference (ΔE) before and after the weather resistance test was almost unchanged, and good results were also obtained in visual appearance change evaluation. From this evaluation result, in the decorative sheet 1 of Examples 3 and 4, as the content of the zinc oxide liposome is increased, it is possible to continue to exhibit excellent ultraviolet absorption performance over a long period of time. It was revealed that the resin can be prevented from fading and whitening by the ultraviolet absorption performance, and excellent transparency can be maintained over a long period of time. Furthermore, since the decorative sheet 1 in Example 4 is a pattern layer 5a containing a light stabilizer, the content of zinc oxide liposomes in Example 3 is 1.00 to 10.00 parts by weight. Compared with the decorative sheet 1 having the top coat layer 2 formed, the color difference (ΔE) before and after the weather resistance test is extremely small, and the light stabilizer suppresses the decoloration of the pattern layer 5a. Thus, it has been clarified that a decorative sheet capable of realizing a colorful design for a longer period of time can be obtained.

  As shown in Table 2, it can be seen that the decorative sheet 1 in Comparative Examples 4 and 5 has an ultraviolet absorbing performance that has a small value of ultraviolet absorbing ability and is not changed within the test time. However, it can be seen that the haze value after the weather resistance test is large and the transparency of the transparent layer is poor. Moreover, whitening and a crack were recognized from the color difference ((DELTA) E) after a weather resistance test, and the external appearance change evaluation result after a weather resistance test. From this evaluation result, it was revealed that the decorative sheets 1 of Comparative Examples 4 and 5 were inferior in design and weather resistance.

  Further, in the decorative sheet 1 in Comparative Example 6, as shown in Table 2, the value of the ultraviolet absorbing ability is large, and the weather resistance is inferior from the evaluation result of the color difference (ΔE) after the weather resistance test and the visual appearance change. I understand that About a haze value, the small value is shown and it turns out that it has the outstanding transparency. From this evaluation result, it became clear that the organic ultraviolet absorber is inferior in ultraviolet absorption performance over a long period of time, although it can maintain high transparency of the transparent layer.

  In the decorative sheet 1 in Comparative Example 7, as shown in Table 2, the haze value after the weather resistance test showed a low value, and the transparent layer composed of the top coat layer 2 and the transparent resin layer 3 was excellent. It can be seen that the transparency is maintained. However, the value of the UV absorbing ability is very large, and from the evaluation result of the color difference (ΔE) after the weather resistance test and the change in appearance by visual observation, remarkable fading is observed in the pattern layer 5a provided in the lower layer of the transparent layer. It was. From this evaluation result, it became clear that the decorative sheet 1 to which the ultraviolet absorber is not added is inferior in weather resistance to the top coat layer 2 and the transparent resin layer 3.

  From the evaluation results of the decorative sheets 1 in Examples 3 and 4 and Comparative Examples 4 to 7 described above, in particular, with respect to 100 parts by weight of the resin material mainly composed of zinc oxide liposomes as the inorganic ultraviolet absorbent vesicle, 0 By providing the decorative sheet 1 having the top coat layer 2 contained in a ratio of .54 to 21.40 parts by weight, a decorative sheet having excellent weather resistance over a long period of time and excellent design properties is provided. You can see that you can.

  The decorative sheet 1 of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the characteristics of the invention.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Top coat layer 3 Transparent resin layer 3a Embossed pattern 3b Adhesive resin layer 4 Adhesive layer 5 Ink layer 5a Pattern pattern layer 5b Solid ink layer 6 Original fabric layer

Claims (6)

A decorative sheet comprising a top coat layer on the outermost layer and a transparent resin layer on the lower surface of the top coat layer,
The top coat layer and / or the transparent resin layer contains an inorganic ultraviolet absorber,
A decorative sheet, wherein the inorganic ultraviolet absorbent is an inorganic ultraviolet absorbent vesicle contained in an outer membrane.   The decorative sheet according to claim 1, wherein the outer film is a single layer film.   The decorative sheet according to claim 1 or 2, wherein the inorganic ultraviolet absorbent vesicle is an inorganic ultraviolet absorbent liposome having an outer membrane made of phospholipid.   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 transparent resin layer,
The decorative sheet according to any one of claims 1 to 4, wherein the top coat layer is embedded in at least the concave portion of the embossed pattern.   The decorative sheet according to any one of claims 1 to 5, wherein an ink layer containing a light stabilizer is provided under the transparent resin layer.