JP6905706B2 - Decorative sheet and manufacturing method of decorative sheet - Google Patents

Description

The present invention relates to a decorative sheet used for building interior materials, building exterior members such as entrance doors, surfaces of fittings, surface materials of home appliances, etc., and includes a top coat layer formed by adding a vesicled ultraviolet absorber. / Or a method for manufacturing a decorative sheet and a decorative sheet having a transparent resin layer.

In recent years, many decorative sheets using olefin resins have been proposed as decorative sheets to replace vinyl chloride decorative sheets. Further, if a resin having high crystallinity and high isotacticity is used in order to improve the scratch resistance of a soft polyolefin sheet made of an olefin resin generally used as a decorative sheet, there is a problem that the weather resistance is inferior. rice field.

As a method for improving the weather resistance of a polyolefin-based resin, as described in Patent Document 1, it is disclosed that a top coat 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 Special Table 2002/032564

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 changes over time are unavoidable, and there is a problem in sustaining the UV absorption performance over a long period of time. Had had.

In addition, when zinc oxide, which is an inorganic ultraviolet absorber, is added, there is little change over time and the ultraviolet absorption performance for a long period of time is good, but when a large amount is added, the transparency decreases and the design of the decorative sheet itself is improved. There was a problem of damaging it.

Furthermore, when the amount of the organic or inorganic UV absorber added is increased in order to improve the weather resistance, the UV absorber aggregates in the resin and bleed-out occurs, resulting in stickiness on the sheet surface. It had 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 has a thinner layer thickness than the other portions, so that it has weather resistance. Is particularly low, and there is a problem that deterioration starts from the recess and whitening or breakage occurs.

As a result of diligent studies, the present inventors have used a vesicle of an organic UV absorber and an inorganic UV absorber together by the supercritical reverse phase evaporation method, so that the amount of addition is the same as before. We have found that exceptional weather resistance can be obtained.

The supercritical reverse phase evaporation method is described in 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 JP-A-2008-063274) proposed by the present inventors. It is disclosed in "Supercritical Reverse-Phase Evaporation Method Publications"), and the method and apparatus described in the Supercritical Reverse-Phase Evaporation Method Publications are used.

In the present invention, a supercritical reverse phase evaporation method is used to add an organic UV absorber and an inorganic UV absorber together in a vesicle to the topcoat layer and / or the transparent resin layer. An object of the present invention is to provide a decorative sheet having excellent design and weather resistance for a long period of time and a method for producing the decorative sheet.

In order to achieve the above object, the decorative sheet according to the first aspect of the present invention is a decorative sheet having a top coat layer on the outermost surface layer and a transparent resin layer under the top coat layer, and the top coat layer. And / or the transparent resin layer is formed by adding an organic ultraviolet absorber and an inorganic ultraviolet absorber, and the organic ultraviolet absorber and the inorganic ultraviolet absorber include an outer film of a single layer film. It is an organic / inorganic ultraviolet absorber vesicle that is encapsulated together with the vesicle, and the ratio of the ultraviolet absorption rate (340 nm / 500 nm) between 340 nm and 500 nm for the transparent layer composed of the top coat layer and the transparent resin layer. The total amount of the organic UV absorber and the inorganic UV absorber added is set to the top coat layer and / or so that the UV absorption capacity calculated for the difference before and after the 4000-hour weather resistance test is 0.08 or less. The transparent resin layer is adjusted to 2.0 parts by weight or more .

In such a decorative sheet according to the first aspect of the present invention, the top coat layer and / or the transparent resin layer is made of an organic ultraviolet absorber having excellent transparency and an inorganic ultraviolet absorber having excellent weather resistance. Since it is formed by adding both, it is possible to provide a decorative sheet capable of achieving both excellent designability and long-term weather resistance. Further, by using the organic / inorganic UV absorber vesicle in which both UV absorbers are encapsulated together in one vesicle, the resin composition which is the main component of the top coat layer and / or the transparent resin layer is extremely. Since high dispersibility can be realized, it is possible to provide a decorative sheet having better ultraviolet absorption performance. Further, the total amount of the organic ultraviolet absorber and the inorganic ultraviolet absorber added is adjusted to 2.0 parts by weight or more with respect to the top coat layer and / or the transparent resin layer, so that the top coat layer and / or the transparent resin layer are added. For the transparent layer made of a transparent resin layer, the difference between the ratio of the ultraviolet absorption rates of 340 nm and 500 nm (340 nm / 500 nm) before and after the 4000-hour weather resistance test was calculated so that the ultraviolet absorption capacity was 0.08 or less. Therefore, even if a weather resistance test of 4000 hours is performed, it has excellent ultraviolet absorption performance, and it is possible to provide a decorative sheet having high transparency and excellent design.

The decorative sheet according to the second aspect of the present invention is characterized in that the addition amounts of the organic ultraviolet absorber and the inorganic ultraviolet absorber are equal.

In the decorative sheet of the second aspect of the present invention as described above, since the addition amounts of the organic ultraviolet absorber and the inorganic ultraviolet absorber are equal, in addition to the first aspect, the top coat is further added. For the transparent layer composed of the layer and the transparent resin layer, the difference between the ratio of the ultraviolet absorption rate of 340 nm and 500 nm (340 nm / 500 nm) before and after the weather resistance test for 4000 hours was calculated so that the ultraviolet absorption capacity is 0.08 or less. Therefore, even if a weather resistance test of 4000 hours is performed, it has excellent ultraviolet absorption performance, and it is possible to provide a decorative sheet having high transparency and excellent design.

The decorative sheet according to the third aspect of the present invention is characterized in that the organic ultraviolet absorber is composed of at least one of benzotriazole-based, triazine-based, benzophenone-based, benzoate-based, and cyanoacrylate-based.

In such a decorative sheet according to the third aspect of the present invention, it is possible to provide a decorative sheet having excellent design while maintaining high transparency.

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 having excellent design while maintaining high transparency.

In the decorative sheet of 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 the recess of the embossed pattern. It is characterized in that it is provided.

In such a decorative sheet according to the fifth aspect of the present invention, organic / inorganic ultraviolet rays are absorbed even in the recesses of the embossed pattern in which the thickness of the transparent resin layer is thinned by forming the embossed pattern. Since the top coat layer to which the agent vesicle is added is embedded, it is possible to provide a decorative sheet having weather resistance comparable to that of other parts.

The method for producing a decorative sheet of the present invention is a method for producing a decorative sheet having a top coat layer on the outermost layer and a transparent resin layer under the top coat layer, wherein the top coat layer and / or the transparent resin is provided. To the layer, an organic / inorganic UV absorber vesicle containing an organic UV absorber and an inorganic UV absorber is added together with a vesicle having an outer film of a single layer film, and the top coat layer is described. And for the transparent layer composed of the transparent resin layer, the difference between the ratio of the ultraviolet absorption rate of 340 nm and 500 nm (340 nm / 500 nm) before and after the weather resistance test for 4000 hours was calculated so that the ultraviolet absorption capacity is 0.08 or less. The total amount of the organic ultraviolet absorber and the inorganic ultraviolet absorber added is 2.0 parts by weight or more with respect to the top coat layer and / or the transparent resin layer .

In the method for producing a decorative sheet according to the first aspect of the present invention, a top coat is used by using an organic / inorganic UV absorber vesicle in which both UV absorbers are encapsulated together in one vesicle. Since extremely high dispersibility can be realized in the resin composition which is the main component of the layer and / or the transparent resin layer, it is possible to provide a decorative sheet having more excellent ultraviolet absorption performance. Further, it has excellent ultraviolet absorption performance even after a weather resistance test of 4000 hours, and it is possible to provide a decorative sheet having high transparency and excellent design.

According to the decorative sheet of the present invention, a decorative sheet having excellent design and weather resistance is provided by forming a top coat layer and / or a transparent resin layer formed by adding an organic / inorganic ultraviolet absorber vesicle. Make it possible.

According to the method for producing a decorative sheet of the present invention, by adding as an organic / inorganic UV absorber vesicle, both UV absorbers are added in the resin composition which is the main component of the top coat layer and / or the transparent resin layer. It is possible to realize extremely high dispersibility.

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

The decorative sheet of the present invention is a decorative sheet having a top coat layer on the outermost layer and a transparent resin layer made of a transparent olefin resin under the top coat layer, and is the top coat layer and / or transparent. The resin layer is formed by adding an organic ultraviolet absorber and an inorganic ultraviolet absorber.

Then, in the decorative sheet of the present invention, in particular, the organic / inorganic ultraviolet absorber in which the organic ultraviolet absorber and the inorganic ultraviolet absorber are encapsulated together in a vesicle having an outer film of a monolayer film. It is important that it is a vesicle.

In the method for producing a decorative sheet of the present invention, an organic ultraviolet absorber and an inorganic ultraviolet absorber are included together with a vesicle having an outer film of a single layer film with respect to the top coat layer and / or the transparent resin layer. It is important to add the organic / inorganic UV absorber vesicles. By using such a method for producing a decorative sheet of the present invention, extremely high dispersibility can be realized in the resin composition which is the main component of the top coat layer and / or the transparent resin layer, which is more excellent. It is possible to provide a decorative sheet of the present invention provided with a top coat layer and / or a transparent resin layer having an ultraviolet absorbing performance.

As the organic ultraviolet absorber, at least one of benzotriazole-based, triazine-based, benzophenone-based, benzoate-based, and cyanoacrylate-based can be selected and used. In particular, it is preferable to select and use at least one of a benzotriazole-based or triazine-based organic ultraviolet absorber.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-ditertiary butylphenyl) benzotriazole, and the like. 2- (2'-Hydroxy-3', 5'-ditertiary butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-third butyl-5'-methylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-tertiary octylphenyl) benzotriazole, 2- (2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2'- Methylenebis (4-thioctyl-6-benzotriazolyl) phenol and the like can be mentioned. Examples of the triazine-based ultraviolet absorber 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) ) Hexyl) Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like. Benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). ) And so on. Examples of the benzoate-based ultraviolet absorber include phenylsalicylate, resorcinol monobenzoate, 2,4-ditertiary butylphenyl-3', 5'-ditertiary butyl-4'-hydroxybenzoate, and 2,4-dithird. Examples thereof include amylphenyl-3', 5'-ditertiary butyl-4'-hydroxybenzoate, hexadecyl-3,5-ditertiary butyl-4-hydroxybenzoate and the like. Examples of the cyanoacrylate-based ultraviolet absorber include ethyl-α-cyano-β, β-diphenyl acrylate, and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Further, as the inorganic ultraviolet absorber, zinc oxide, titanium oxide, ceria oxide and the like can be used. Of 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. The particle size of the inorganic ultraviolet absorber is preferably in the range of 1 nm to 200 nm.

It is important that the organic / inorganic ultraviolet absorber vesicle of the present invention is prepared by the 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 film of a vesicle is uniformly dissolved in carbon dioxide under a supercritical state or a temperature or pressure condition above the critical point to form a mixture, which is water-soluble in the mixture. Alternatively, an aqueous phase containing an organic ultraviolet absorber and an inorganic ultraviolet absorber as a hydrophilic encapsulant is added, and an organic ultraviolet absorber and an inorganic ultraviolet absorber as an encapsulant are absorbed by a single layer film (single layer film). It is designed to form a capsule-shaped organic / inorganic ultraviolet absorber vesicle containing the agent together. The supercritical carbon dioxide means carbon dioxide in a supercritical state above the critical temperature (30.98 ° C.) and the critical pressure (7.3773 ± 0.0030 MPa), and is at a temperature above the critical point or above the critical point. The carbon dioxide under the pressure condition means the carbon dioxide under the condition that only the critical temperature or only 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 the vesicle include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yellow egg lecithin, hydrogenated yellow egg lecithin, soybean lecithin, hydrogenated soybean lecithin, etc. Examples thereof include glycerophospholipids, sphingomierin, ceramide phosphorylethanolamine, ceramide phosphorylglycerol and other sphingolin lipids.

As the substance forming the outer membrane of the vesicle, a nonionic surfactant or a dispersant such as a mixture thereof with cholesterol or triacylglycerol can be adopted in addition to the above-mentioned phospholipid.

More specifically, examples of the nonionic surfactant include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene polyoxy. Propylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. One type or two or more types can be used. As cholesterols, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholic acid, choleciferol and the like can be used.

The outer membrane of the vesicle may also be formed from a mixture of phospholipids and dispersants. In the decorative sheet of the present invention, it is important that the outer film is a vesicle formed from phospholipids, and the compatibility with the resin composition which is the main component of the top coat layer and the transparent resin layer is good. be able to.

When such an organic UV absorber and an inorganic UV absorber are added to the top coat layer, the organic UV absorber is added to 100 parts by weight of the resin composition which is the main component of the top coat layer. It is preferable to add an organic / inorganic UV absorber vesicle prepared so that the absorber is in the range of 0.5 to 20 parts by weight and the inorganic UV absorber is in the range of 0.5 to 20 parts by weight. At this time, if the amount of both ultraviolet absorbers added is less than 0.5 parts by weight, the effect of the ultraviolet absorbing ability is low, and if it is more than 20 parts by weight, the possibility of blocking is high. More preferably, the amount of the organic UV absorber is in the range of 1 to 10 parts by weight and the amount of the inorganic UV absorber is in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the resin composition which is the main component of the top coat layer. The organic / inorganic UV absorber vesicles prepared as described above are added, more preferably in the range of 3 to 5 parts by weight of the organic UV absorber and 3 to 5 parts by weight of the inorganic UV absorber. It is the addition of the organic / inorganic UV absorber vesicles prepared to be inside.

When added to the transparent resin layer, the organic ultraviolet absorber is 0.1 to 5 parts by weight and the inorganic ultraviolet absorber is absorbed with respect to 100 parts by weight of the resin composition which is the main component of the transparent resin layer. It is preferable to add an organic / inorganic UV absorber vesicle prepared so that the agent is in the range of 0.1 to 5 parts by weight. At this time, if the amount of both ultraviolet absorbers added is less than 0.1 parts by weight, the effect of the ultraviolet absorbing ability is low, and if it is more than 5 parts by weight, the possibility of bleeding out increases. More preferably, the organic UV absorber is 0.2 to 3 parts by weight and the inorganic UV absorber is 0.2 to 3 parts by weight with respect to 100 parts by weight of the resin composition which is the main component of the transparent resin layer. Addition of organic / inorganic UV absorber vesicles prepared to be within the range.

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

Further, it is important that the lower layer of the transparent resin layer is provided with at least an ink layer formed by an ink to which a light stabilizer is added. As the light stabilizer, it is preferable to use a hindered amine-based 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 deterioration of the ink layer binder resin itself and the resin of the other layer reducing the chemical components of the pigment in the ink. ..

Hereinafter, specific examples of the decorative sheet of the present invention and the method for producing the decorative sheet will be described with reference to 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 primer adhesive, etc.), an ink layer 3, and a raw fabric layer 2. The concealing layer 8 and the primer layer 6 are laminated, and are used by adhering to the base material B or the like. Further, in order to improve the design, an embossed pattern 4a is formed on the surface of the transparent resin layer 4 on the topcoat layer 5 side, and the topcoat layer 5 is formed in the recess of the embossed pattern 4a by wiping. It is formed so that a part of the resin composition to be used is embedded.

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

The resin composition that is the main component of the top coat layer 5 is appropriately selected from polyurethane-based, acrylic silicon-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, urea-based, and the like. Can be used. The form of the resin composition is not particularly limited, such as aqueous, emulsion, and solvent-based. As for the curing method, a one-component type, a two-component type, an ultraviolet curing method and the like can be appropriately selected and used. In particular, a urethane-based resin composition using isocyanate is suitable from the viewpoints of workability, price, cohesive force 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), and bis (isocyanate methyl) cyclohexane ( It can be appropriately selected from curing agents such as adduct, buretto, and isocyanurate, which are derivatives such as HXDI) and trimethylhexamethylene diisocyanate (TMDI), but in consideration of weather resistance, it is a linear molecule. It is preferable to use a curing agent based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a structure. In addition to this, when improving the surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays and electron beams. These resins can be used in combination with each other. For example, by forming a hybrid type of a thermosetting resin and a photocurable resin, the surface hardness is improved, the curing shrinkage is suppressed, and the transparent resin layer is formed. It is possible to improve the adhesion with.

In addition to this, functional additives such as an antibacterial agent and an antifungal agent can be optionally added in order to impart various functions to the top coat layer 5. Further, in order to improve the design of the surface, alumina, silica, silicon nitride, silicon carbide, glass beads and the like may be added to adjust the gloss. Further, by adding alumina, silica, silicon nitride, silicon carbide, glass beads, or the like to the top coat layer 5, the abrasion resistance of the surface 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-olefins (for example, propylene, 1-butene, 1-pentene, 1) -Hexen, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-ethylene, 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, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) alone Polymerized or copolymerized with two or more types, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer Examples thereof include those obtained by copolymerizing ethylene or α-olefin with other monomers, such as a coalescence, an ethylene / methyl acrylate copolymer, an ethylene / ethyl acrylate copolymer, and an ethylene / butyl acrylate copolymer. Further, when improving the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene.

Further, in the decorative sheet 1 of the present invention, it is more preferable to add the organic / inorganic ultraviolet absorber vesicle to the transparent resin layer 4. As a result, the transparent resin layer 4 can also be provided with weather resistance, and it is possible to suppress deterioration of the olefin-based resin composition which is the main component of the transparent resin layer 4 and to prevent the deterioration of the olefin-based resin composition, or to suppress the deterioration of the pattern of the ink layer 3 located in the lower layer. It is possible to prevent the printing from fading due to ultraviolet rays and maintain excellent designability for a long period of time.

In addition, various additives such as a heat stabilizer, a light stabilizer, an anti-blocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster are added to the transparent resin layer 4 as necessary. You may try to do it. Heat stabilizers include phenol-based, sulfur-based, phosphorus-based, hydrazine-based, etc., UV absorbers include benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, etc., and light stabilizers include hindered amine-based agents. , It is common to add in any combination.

The adhesive layer 7 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 and the like, but generally, a gravure coat is used, and after being applied by the gravure coat to the upper surface of the ink layer 3, a transparent resin layer is used. It is designed to be laminated with 4. The adhesive layer 7 can be omitted if sufficient adhesive strength between the transparent resin layer 4 and the ink layer 3 can be obtained.

The ink layer 3 is a pattern printing formed on the raw fabric layer 2 using ink, and is a nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc. as a binder. Can be used alone or by appropriately selecting from each modified product. These may be water-based, solvent-based, emulsion type, one-component type, or two-component type using a curing agent. Further, a method of curing the ink by irradiation with ultraviolet rays, electron beams, or the like may be used. Among them, the most common method uses urethane-based ink and is a method of curing with isocyanate. In addition to these binders, pigments, colorants such as dyes, extender pigments, solvents, and various additives contained in ordinary inks 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. It is also possible to apply the design by vapor deposition or sputtering of various metals separately from the application of ink.

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 photodeteriorating and impairing the design property, and to make up for a long period of time. The excellent design of the sheet 1 can be maintained.

The raw fabric layer 2 includes thin leaf paper, titanium paper, resin-impregnated paper and other papers, 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. , Rubber such as polyurethane, organic or inorganic non-woven fabric, synthetic paper, metal foil such as aluminum, iron, gold, silver, etc. can be arbitrarily selected.

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

The concealing layer 8 can be basically composed of the same material as the ink layer 3, but since it is intended to have concealing properties, an opaque pigment, titanium oxide, iron oxide or the like is used as the pigment. It is preferable to do so. It is also possible to add metals such as gold, silver, copper and aluminum to improve the hiding power. Generally, 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, so a primer layer 6 is provided between the raw fabric layer 2 and the base material B. Is preferable. In addition to this, in order to improve the adhesiveness between the raw fabric layer 2 made of an olefin-based material and the base material B, the raw fabric layer 2 is subjected to corona treatment, plasma treatment, ozone treatment, electron beam treatment, and ultraviolet treatment. , It is desirable to perform treatment with heavy chromium acid.

As the primer layer 6, basically the same material as the ink layer 3 described above can be used, but considering that the primer layer 6 is wound on the back surface of the decorative sheet 1 in a web shape, blocking is performed. Inorganic fillers such as silica, alumina, magnesia, titanium oxide and barium sulfate may be added in order to avoid and enhance the adhesion to the adhesive.

In the method for producing the decorative sheet 1 of the present invention, the laminating method is not particularly limited, and the decorative sheet 1 is formed by appropriately selecting from commonly used methods such as a method applying heat pressure, an extruding laminating method, and a dry laminating method. can do. When forming the embossed pattern 4a, a method of once laminating by the laminating method and then inserting the embossed pattern 4a by heat pressure or a method of providing an uneven pattern on the cooling roll and forming the embossed pattern 4a at the same time as extruding is used. 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 top coat 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 400 μm.

In the decorative sheet 1 of the present embodiment as described above, since the organic / inorganic ultraviolet absorber vesicle is added to the top coat layer 5 and / or the transparent resin layer 4, it is formed with high transparency. It is possible to maintain excellent designability and to realize excellent weather resistance over a long period of time. Further, since bleed-out and white turbidity of the resin composition due to the aggregated additives do not occur in the resin composition, the sheet surface is not sticky and the makeup has excellent adhesion and design. It is possible to provide the sheet 1.

Further, in the method for producing the decorative sheet 1 of the present embodiment, since both ultraviolet absorbers are added as vesicles of organic / inorganic ultraviolet absorbers contained together, it is extremely in the resin composition as the main component. Achieves high dispersibility. As a result, it is possible to provide the decorative sheet 1 of the present invention which exhibits high ultraviolet absorption performance and has excellent weather resistance without increasing the amount of the ultraviolet absorber added. In particular, by making the vesicle a vesicle having an outer film made of a phospholipid, the compatibility with the resin composition which is the main component of the top coat layer 5 and the transparent resin layer 4 can be made extremely good. can.

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

Further, by forming the ink layer 3 using ink to which a light stabilizer is added, fading of the ink layer 3 due to ultraviolet rays can be suppressed, so that a design that maintains beautiful color pattern printing for a long period of time. It is possible to provide a decorative sheet 1 having excellent properties.

<Preparation of organic / inorganic UV absorber vesicles>
The detailed preparation method of the organic / inorganic ultraviolet absorber vesicle using the supercritical reverse phase evaporation method in the present invention will be described below.

The vesicles were prepared in a high-pressure stainless steel container kept at 60 ° C. with 100 parts by weight of hexane and triazine-based ultraviolet absorber 2- (4,6-bis (2,4-dimethyl)) as an organic ultraviolet absorber. Phyl) -1,3,5-triazine-2-yl) -5-Hydroxyphenyl-based hydroxyphenyl triazine (TINUVIN 400; manufactured by BASF) 35 parts by weight and zinc oxide as an inorganic ultraviolet absorber (TINUVIN 400; manufactured by BASF) 35 parts by weight (average particle size 20 nm) and 5 parts by weight of phosphatidylcholine as phospholipid are put and sealed, and carbon dioxide is injected so that the pressure in the container becomes 20 MPa to make it a supercritical state, and vigorously stirred and mixed. While injecting 100 parts by weight of ethyl acetate, stirring and mixing for 15 minutes while maintaining the temperature and pressure, carbon dioxide was discharged and returned to atmospheric pressure by a supercritical reverse phase evaporation method to form a vesicle having a phospholipid outer film. An organic / inorganic ultraviolet absorber vesicle was obtained.

Specific examples of the decorative sheet 1 of the present invention will be described below.

<Examples 1 to 5>
In Examples 1 to 5, the organic / inorganic ultraviolet absorber vesicle 1.07, which was prepared by the above method, was used with respect to the urethane resin as the resin composition which is the main component of the top coat layer 5. 13, 10.66, 21.32, 42.64 parts by weight (of which the addition ratio is 0.5, 1.0, 5.0, 10.0, 20.0 parts by weight for organic UV absorbers. The inorganic ultraviolet absorber was 0.5, 1.0, 5.0, 10.0, and 20.0 parts by weight) to prepare a decorative sheet 1.

Specifically, 0.05 parts by weight of a hindered phenol-based antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine-based photostabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. The resin added in an amount of 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 sides of the highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension of the sheet surface was 40 dyn / cm or more. Next, a pattern is printed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.), and the pattern is printed at 3 μm. The ink layer 3 of the above was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the raw fabric layer 2 to form a 1 μm primer layer 6. After that, an adhesive for dry lamination as an adhesive layer 7 in which a transparent resin layer 4 is formed with a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.). A laminated resin sheet having a thickness of 157 μm composed of a raw fabric layer 2, an ink layer 3, an adhesive layer 7, a primer layer 6 and a transparent resin layer 4 was obtained by laminating them by a dry laminating method. After embossing pattern 4a is applied to the surface of the transparent resin layer 4 of this laminated resin sheet, it is organic / inorganic with respect to ^{a two-component urethane top coat (W184; manufactured by DIC Graphics, coating thickness 3 g / m 2).} The topcoat layer 5 was formed by applying the UV absorber vesicles added in the combinations shown in Table 1, respectively, to obtain the 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 / inorganic ultraviolet absorber vesicle 0.21 prepared by the above method was used with respect to the crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. 1.07, 2.13, 5.33, 10.66 parts by weight (of which, the addition ratio is 0.1, 0.5, 1.0, 2.5, 5.0 parts by weight for organic UV absorbers. The amount of the inorganic ultraviolet absorber is 0.1, 0.5, 1.0, 2.5, and 5.0 parts by weight.) Was added to the decorative sheet 1.

Specifically, 0.05 parts by weight of a hindered phenol-based antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine-based light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. The resin to which 0.2 parts by weight and the organic / inorganic ultraviolet absorber vesicles were added according to the combination shown in Table 2 was melt-extruded using an extruder to obtain a transparent resin layer 4 having a thickness of 80 μm. A highly crystalline polypropylene sheet was formed. Both sides of the highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension of the sheet surface was 40 dyn / cm or more. Next, a pattern is printed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.), and the pattern is printed at 3 μm. The ink layer 3 of the above was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the raw fabric layer 2 to form a 1 μm primer layer 6. After that, an adhesive for dry lamination as an adhesive layer 7 in which a transparent resin layer 4 is formed with a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.). A laminated resin sheet having a thickness of 157 μm composed of a raw fabric layer 2, an ink layer 3, an adhesive layer 7, a primer layer 6 and a transparent resin layer 4 was obtained by laminating them by a dry laminating method. An embossed pattern 4a is applied to the surface of the transparent resin layer 4 of this laminated resin sheet, and then a two-component urethane top coat (W184; manufactured by DIC Graphics Corporation, coating thickness 3 g / m ² ) is applied to the top coat layer 5. A decorative sheet 1 of Examples 6 to 10 having a total thickness of 160 μm was obtained.

<Example 11>
In Example 11, 2.67 parts by weight of the organic / inorganic ultraviolet absorber vesicle prepared by the above method with respect to the urethane-based resin as the resin composition which is the main component of the top coat layer 5. The addition ratio is 1.25 parts by weight for the organic UV absorber and 1.25 parts by weight for the inorganic UV absorber), and the resin composition which is the main component of the transparent resin layer 4. 2.67 parts by weight of the organic / inorganic UV absorber vesicle prepared by the above method (of which the addition ratio is 1.25 parts by weight of the organic UV absorber). The amount of the inorganic ultraviolet absorber is 1.25 parts by weight) was added to the decorative sheet 1.

Specifically, 0.05 parts by weight of a hindered phenol-based antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine-based light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. A resin containing 0.2 parts by weight and 2.67 parts by weight of the organic / inorganic ultraviolet absorber vesicle is melt-extruded using an extruder to have a transparent high crystallinity with a thickness of 80 μm as the transparent resin layer 4. A polypropylene sheet was formed. Both sides of the highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension of the sheet surface was 40 dyn / cm or more. Next, a pattern is printed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.), and the pattern is printed at 3 μm. The ink layer 3 of the above was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the raw fabric layer 2 to form a 1 μm primer layer 6. After that, an adhesive for dry lamination as an adhesive layer 7 in which a transparent resin layer 4 is formed with a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.). A laminated resin sheet having a thickness of 157 μm composed of a raw fabric layer 2, an ink layer 3, an adhesive layer 7, a primer layer 6 and a transparent resin layer 4 was obtained by laminating them by a dry laminating method. After embossing pattern 4a is applied to the surface of the transparent resin layer 4 of this laminated resin sheet, it is organic / inorganic with respect to ^{a two-component urethane top coat (W184; manufactured by DIC Graphics, coating thickness 3 g / m 2).} A topcoat layer 5 was formed by applying an ultraviolet absorber vesicle to which 2.67 parts by weight was added 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 a non-vesicled organic ultraviolet absorber was added to the urethane resin as the resin composition which is the main component of the top coat layer 5. A decorative sheet 1 was prepared by adding 0.5 or 50.0 parts by weight of an inorganic ultraviolet absorber that was not vesicled. 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, 0.5 or 50.0 parts by weight of a non-vesicled organic ultraviolet absorber was added to the crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. A decorative sheet 1 was prepared by adding 0.5 or 50.0 parts by weight of a non-vesicled inorganic ultraviolet absorber. 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 parts by weight of a non-vesicled organic ultraviolet absorber was added to the urethane resin as the resin composition which is the main component of the top coat layer 5, and the non-vesicled inorganic ultraviolet rays. While adding 0.5 parts by weight of the absorbent, 0.5 parts by weight of a non-vesicled organic ultraviolet absorber is added to the crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. A decorative sheet 1 was prepared by adding 0.5 parts 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 Comparative Example 6, the decorative sheet 1 in which the ultraviolet absorber was not added to any of the resin layers was used. Other configurations are the same as those of the decorative sheet 1 of Example 1.

JIS B was used for each of the decorative sheets 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.). A carbon arc weather resistance test according to 7753 was performed to calculate the ultraviolet absorption capacity. The test conditions were weather resistant to 4000 hours. Regarding the ultraviolet absorption capacity, 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 was measured, and the weather resistance was the ratio of the ultraviolet absorption rates of 340 nm and 500 nm (340 nm / 500 nm). The difference before and after the sex test was calculated. As for the haze value, the value after the 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 shown by the following symbols. The obtained evaluation results 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 Table 2 for Examples 11 and Comparative Examples 5 and 6. It is shown in 3 respectively.
<Symbol of appearance change>
◎: No change at all ○: Slight change △: Slight whitening and cracks ×: Severe whitening and partial breakage / breakage

First, a case where an ultraviolet absorber is added to the top coat layer 5 will be described. As shown in Table 1, the evaluation results show that the decorative sheet 1 of Examples 1 to 5 in which 1.07 to 42.64 parts by weight of the organic / inorganic ultraviolet absorber vesicle was added to the top coat layer 5 It can be seen that the value of the ultraviolet absorbing ability is small regardless of the amount of addition, and the ultraviolet absorbing performance is almost the same as that before the test even after the weather resistance test for 4000 hours. In addition, since the haze value 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. You can see that. The visual evaluation also gave excellent evaluation results. On the other hand, the decorative sheet 1 of Comparative Example 1 in which 0.5 parts by weight of each of an organic ultraviolet absorber and an inorganic ultraviolet absorber that were not vesicled was added to the top coat layer 5 had an ultraviolet absorbing ability. The value is 1.54, the haze value is 17.20%, and the color difference (ΔE) value is 7.43, which are large values. It can be seen that the layer is deteriorated and the transparency is impaired. In the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because the organic UV absorber and the inorganic UV absorber that are not vesicles are used, so that the dispersibility in the resin composition as the main component is inferior and secondary aggregation occurs, so that sufficient UV absorption performance can be exhibited. It is probable that the cause was not. Further, in the decorative sheet of Comparative Example 2 in which 50.0 parts by weight of each of the organic ultraviolet absorber and the inorganic ultraviolet absorber that were not vesicled were added to the top coat layer 5, the value of the ultraviolet absorbing ability was 0. Although it was extremely small at 01, the haze value was very large at 21.79% due to the addition of a large amount of ultraviolet absorber, and severe whitening was also observed in the visual evaluation. It is considered that this is because the amount of both UV absorbers added was too large, causing blocking and clouding.

Next, a case where an ultraviolet absorber is added to the transparent resin layer 4 will be described. As shown in Table 2, the evaluation results show that the decorative sheet 1 of Examples 6 to 10 in which 0.21 to 10.66 parts by weight of the organic / inorganic ultraviolet absorber vesicles were added to the transparent resin layer 4 It can be seen that the value of the ultraviolet absorbing ability is extremely small regardless of the amount of addition, and the ultraviolet absorbing rate is almost the same as that before the test even after the weather resistance test for 4000 hours. In addition, since the haze value 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. You can see that. The visual evaluation also gave excellent evaluation results. On the other hand, the decorative sheet 1 of Comparative Example 3 in which 0.5 parts by weight of each of an organic ultraviolet absorber and an inorganic ultraviolet absorber that were not vesicled was added to the transparent resin layer 4 had an ultraviolet absorbing ability. The value is 1.32, the haze value is 16.30%, and the color difference (ΔE) value is 6.21. It can be seen that the layer is deteriorated and the transparency is impaired. In the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because the organic UV absorber and the inorganic UV absorber that are not vesicles are used, so that the dispersibility in the resin composition as the main component is inferior and secondary aggregation occurs, so that sufficient UV absorption performance can be exhibited. It is probable that the cause was not. Further, in the decorative sheet of Comparative Example 4 in which 50.0 parts by weight of each of the organic ultraviolet absorber and the inorganic ultraviolet absorber that were not vesicled were added to the transparent resin layer 4, the value of the ultraviolet absorbing ability was 0. Although it was extremely small at 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 also observed in the visual evaluation. It is considered that this is because the amount of both ultraviolet absorbers added was too large, causing bleed-out and clouding.

Then, the case where the ultraviolet absorber is added to both the top coat layer 5 and the transparent resin layer 4 will be described. As shown in Table 3, the evaluation results show that the decorative sheet 1 of Example 11 in which 2.67 parts by weight of each of the organic and inorganic ultraviolet absorber vesicles was added to the top coat layer 5 and the transparent resin layer 4 , The value of ultraviolet absorption ability is 0.07, the haze value is 5.88%, and the color difference (ΔE) value is 0.37, which are extremely small values, and it is excellent even after a 4000-hour weather resistance test. It can be seen that the decorative sheet 1 has an ultraviolet absorbing performance, has high transparency, and is excellent in design. On the other hand, regarding the decorative sheet 1 of Comparative Example 5 in which 0.5 parts by weight of each of the organic ultraviolet absorber and the inorganic ultraviolet absorber that were not vesicled were added to the top coat layer 5 and the transparent resin layer 4. , The value of the ultraviolet absorbing ability, the haze value and the value of the color difference (ΔE) all show large values, and it can be seen that the ultraviolet absorbing performance and the design are inferior to those of the decorative sheet 1 of Example 11. .. It is said that this is because the non-vesicled UV absorber was used, so that the dispersibility in the resin composition as the main component was poor and secondary agglutination occurred, and sufficient UV absorption performance could not be exhibited. Conceivable.

Further, in the decorative sheet 1 of Comparative Example 6 in which the ultraviolet absorber was not added to any of the resin layers, the ultraviolet absorbing ability value was 10.80, the haze value was 6.47%, and the color difference (ΔE). The value of was 12.20. From the results of the visual evaluation, it can be seen that the weather resistance is inferior due to significant whitening and cracks occurring after the weather resistance test.

Moreover, the decorative sheet 1 of Example 3 and Example 11 is compared with the following. 2.67 for the decorative sheet 1 of Example 3 in which 10.66 parts by weight of the organic / inorganic ultraviolet absorber vesicle was added to the top coat layer 5, and 2.67 for the top coat layer 5 and the transparent resin layer 4, respectively. Comparing with the decorative sheet 1 of Example 11 to which the heavy part of the organic / inorganic ultraviolet absorber vesicle was added, the decorative sheet 1 of Example 11 was superior in all the evaluation results, and the top coat layer 5 Even if a large amount of UV absorber vesicles is not added only to the top coat layer 5 and the transparent resin layer 4, the decorative sheet 1 having better UV absorption performance can be obtained by adding the UV absorber vesicles little by little to the top coat layer 5 and the transparent resin layer 4. It turns out that it can be obtained.

From the above evaluation results, as shown in the decorative sheet 1 of Examples 1 to 5 of the present invention, 1.07 to 42.64 parts by weight of the organic / inorganic ultraviolet absorber vesicle with respect to the top coat layer 5 ( Of these, 0.5 to 20.0 parts by weight of the organic UV absorber and 0.5 to 20.0 parts by weight of the inorganic UV absorber are added) for a long period of time. It has been clarified that a decorative sheet 1 having excellent weather resistance and design can be obtained.

Further, as shown in the decorative sheet 1 of Examples 6 to 10 of the present invention, 0.21 to 10.66 parts by weight of an organic / inorganic ultraviolet absorber vesicle with respect to the transparent resin layer 4 (of which, The organic UV absorber is said to be 0.1 to 5.0 parts by weight, and the inorganic UV absorber is said to be 0.1 to 5.0 parts by weight). It was also clarified that the decorative sheet 1 having excellent design can be obtained.

Further, as shown in the decorative sheet 1 of Example 11 of the present invention, by adding the organic / inorganic ultraviolet absorber vesicles to both the resin layers of the top coat layer 5 and the transparent resin layer 4, the top is topped. 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 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 "adding an organic / inorganic ultraviolet absorber to a resin material in a state of being encapsulated in a vesicle having an outer film of a monolayer film". To form the topcoat layer 5 and / or the transparent resin layer 4 ". This is achieved by adding an organic / inorganic UV absorber to the resin material in a state of being encapsulated in the vesicle at the time of manufacturing the decorative sheet 1 of the present invention. It is possible to dramatically improve the dispersibility of the. However, in identifying the decorative sheet 1 of the present invention thus obtained as an invention, the dispersity of the organic / inorganic ultraviolet absorber is quantified and its structure is analyzed from a cross-sectional image or the like. However, it is technically extremely difficult to identify, and it can be said that it is impractical because it takes an enormous amount of time for analysis and the like.

To explain this difficulty more specifically, it is considered that the vesicles are formed on the nano-order and are extremely uniformly dispersed in the resin. Therefore, in order to measure the dispersity of the organic / inorganic ultraviolet absorbers contained and added in the vesicle from the cross section of the obtained decorative sheet 1, analysis in the nano to micro order is unavoidable. NS. Usually, analysis / observation of the ultra-fine world requires extremely advanced technology, and in some cases, it becomes necessary to create analysis / 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 and an enormous amount of time, which are not normally used, are required. It can be said that it is unrealizable in terms of cost and time required to clarify the structure and characteristics of 1.

The decorative sheet 1 and the method for producing the decorative sheet 1 of the present invention are not limited to the above-described embodiments and examples, and various modifications can be made as long as the features of the invention are not impaired.

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 having a top coat layer on the outermost surface layer and a transparent resin layer under the top coat 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 / inorganic UV absorber vesicle in which the organic UV absorber and the inorganic UV absorber are encapsulated together in a vesicle having an outer film of a monolayer film .
For the transparent layer composed of the top coat layer and the transparent resin layer, the difference in the ratio of the ultraviolet absorption rates of 340 nm and 500 nm (340 nm / 500 nm) before and after the weather resistance test for 4000 hours was calculated to be 0.08 or less. The total amount of the organic ultraviolet absorber and the inorganic ultraviolet absorber added is adjusted to 2.0 parts by weight or more with respect to the top coat layer and / or the transparent resin layer so as to be. A characteristic cosmetic sheet. The decorative sheet according to claim 1, wherein the addition amounts of the organic ultraviolet absorber and the inorganic ultraviolet absorber are equal. The cosmetic sheet according to claim 1 or 2, wherein the organic ultraviolet absorber comprises at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate. 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 top coat layer side.
The decorative sheet according to any one of claims 1 to 4, wherein the top coat layer is embedded in the recess of the embossed pattern. A method for producing a decorative sheet having a top coat layer on the outermost surface layer and a transparent resin layer on the lower layer of the top coat layer.
An organic / inorganic UV absorber in which an organic UV absorber and an inorganic UV absorber are encapsulated together with a vesicle having an outer film of a single-layer film with respect to the top coat layer and / or the transparent resin layer. Add the agent vesicle ,
For the transparent layer composed of the top coat layer and the transparent resin layer, the difference in the ratio of the ultraviolet absorption rates of 340 nm and 500 nm (340 nm / 500 nm) before and after the weather resistance test for 4000 hours was calculated to be 0.08 or less. The total amount of the organic ultraviolet absorber and the inorganic ultraviolet absorber added is 2.0 parts by weight or more with respect to the top coat layer and / or the transparent resin layer. How to make a decorative sheet.

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