JP7130309B2 - makeup sheet - Google Patents

Description

The present invention relates to a decorative sheet used for building interior materials, building exterior materials such as entrance doors, the surface of fittings, the surface material of household appliances, etc., and relates to a transparent resin layer containing a vesicled ultraviolet absorber added. It relates to a cosmetic sheet provided.

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

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

Japanese Patent No. 4032829

When the method described in Patent Document 1 is applied to the transparent resin layer, since the olefin resin forming the transparent resin layer is a non-polar resin material represented by polyethylene and polypropylene, organic UV-absorbing material having polarity is used. It has poor compatibility with the agent, and it is necessary to add a large amount to obtain sufficient weather resistance, but if a large amount of organic UV absorber is added, aggregation will occur and the transparency of the transparent resin layer will be impaired. problem arises.

In particular, in the case of an organic UV absorber, the aggregated UV absorber bleeds out to cause stickiness on the surface of the decorative sheet, and problems such as reduced adhesion to the topcoat layer formed on the transparent resin layer. was causing

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a decorative sheet having a transparent resin layer to which an organic ultraviolet absorbent vesicle is added and having excellent design and weather resistance.

As a result of intensive studies, the inventors of the present invention have found that by using a vesicled organic UV absorber, exceptional weather resistance can be obtained even with the same addition amount as conventional.

In order to achieve the above objects, a decorative sheet according to a first aspect of the present invention is a decorative sheet comprising a transparent resin layer made of a transparent olefin resin, wherein the transparent resin layer contains an organic ultraviolet absorber. wherein the organic UV absorber is an organic UV absorber vesicle having an outer membrane consisting of a monolayer membrane formed by one lipid bilayer membrane , and the organic UV absorber vesicle has the action of dispersing particles without aggregating them by the action of the outer films repelling each other, and an opaque concealing material containing flake-like metal made of aluminum flakes in a layer below the transparent resin layer It is characterized by having a layer.

In such a decorative sheet according to the first aspect of the present invention, the outer membranes of the organic ultraviolet absorbent vesicles repel each other to disperse the particles without aggregating them. Since the organic ultraviolet absorber can be uniformly dispersed in the transparent resin layer, it is possible to provide a decorative sheet having high transparency, excellent design, and excellent weather resistance. Furthermore, since the opaque concealing layer below the transparent resin layer contains flake-shaped metal made of flake-shaped aluminum, the cosmetic is provided with a higher concealing property than when ordinary concealing materials are used. Make it possible to provide a sheet.

A decorative sheet according to a second aspect of the present invention is a decorative sheet comprising a transparent resin layer made of a transparent olefin resin, wherein the transparent resin layer contains an organic ultraviolet absorber, The UV absorber is an organic UV absorber vesicle having an outer membrane consisting of a single lipid bilayer membrane , and the organic UV absorber vesicles are attached to each other's outer membranes. have the effect of dispersing particles without aggregating them by the action of repelling each other, and the outer membrane of the organic ultraviolet absorbent vesicle is a mixture of phospholipids and nonionic surfactants or a mixture of phospholipids and nonionic surfactants and a mixture with at least one of cholesterols and triacylglycerols.

In such a decorative sheet according to the second aspect of the present invention, the outer membranes of the organic ultraviolet absorbent vesicles repel each other to disperse the particles without aggregating them. Since the organic ultraviolet absorber can be uniformly dispersed in the transparent resin layer, it is possible to provide a decorative sheet having high transparency, excellent design, and excellent weather resistance. Furthermore, the vesicle is a vesicle having an outer membrane comprising a mixture of a phospholipid and a nonionic surfactant or a mixture of a phospholipid and a nonionic surfactant and at least one of cholesterols and triacylglycerols , the compatibility between the resin composition, which is the main component of the transparent resin layer, and the vesicles is improved, and as a result, the organic ultraviolet absorber, which is the inclusion in the resin composition, which is the main component of the transparent resin layer, is added. It can be distributed more evenly.

A decorative sheet according to a third aspect of the present invention is characterized in that, in the first aspect, the outer membrane of the organic ultraviolet absorbent vesicle is a mixture of a phospholipid and a nonionic surfactant or a mixture of a phospholipid and a nonionic surfactant and cholesterol. and at least one of triacylglycerols .

In such a decorative sheet of the third aspect of the present invention, it is possible to provide a decorative sheet that exhibits the effects of the first and second aspects .

The decorative sheet according to the fourth aspect of the present invention is characterized in that the organic UV absorber comprises at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate.
In such a decorative sheet of the fourth aspect of the present invention, the decorative sheet is more excellent in design without impairing the transparency of the topcoat layer, as compared with the case of using an inorganic UV absorber. can be provided.

The decorative sheet of the fifth aspect of the present invention is characterized in that an ink layer containing a light stabilizer is provided under the transparent resin layer.
In such a decorative sheet according to the fifth aspect of the present invention, the radicals generated by the deterioration of the binder resin itself of the ink layer or the resin of other layers reduce the chemical components of the pigment in the ink, thereby preventing the discoloration of the pigment. It is possible to provide a decorative sheet capable of suppressing and realizing excellent design properties over a long period of time.

According to the decorative sheet of the present invention, it is possible to provide a decorative sheet excellent in design and weather resistance.

A cross-sectional view showing an embodiment of the decorative sheet of the present invention.

The decorative sheet of the present invention is a decorative sheet comprising a transparent resin layer made of a transparent olefin resin, wherein the transparent resin layer contains an organic ultraviolet absorber, and the organic ultraviolet absorber is used alone. It is important that the vesicle be an organic ultraviolet absorber vesicle having an outer membrane consisting of a layered film.

Such an organic UV absorber vesicle has a structure in which an organic UV absorber is enclosed in a vesicle-like capsule having a membrane structure closed in the form of a spherical shell. This organic ultraviolet absorber vesicle has extremely high dispersibility without the particles aggregating due to the mutual repulsion of the outer membranes. This action makes it possible to uniformly disperse the organic ultraviolet absorber in the resin composition constituting the transparent resin layer.

Techniques for obtaining organic ultraviolet absorbent vesicles (vesicle-forming treatment methods) include, for example, the Bangham method, extrusion method, hydration method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase evaporation method, and the like. . Briefly describing such a vesicle treatment method, in the Bangham method, chloroform or a mixed solvent of chloroform/methanol is put into a container such as a flask, and then phospholipid is added and dissolved. Thereafter, the solvent is removed using an evaporator to form a lipid thin film, a dispersion of additives is added, and vesicles are obtained by hydrating and dispersing with a vortex mixer. The extrusion method is a method of obtaining vesicles by preparing a thin film phospholipid solution and passing it through a filter instead of the mixer used as the 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 water is added. This is a method for obtaining vesicles by The freeze-thaw method is a method of using cooling and heating as external perturbation, and is a method of obtaining vesicles by repeating this cooling and heating.

In particular, as a method for obtaining an organic ultraviolet absorbent vesicle having an outer membrane consisting of a single layer, there is a supercritical reverse phase evaporation method. The supercritical reversed-phase evaporation method is proposed by the present inventors in JP-A-2002/032564, JP-A-2003-119120, JP-A-2005-298407 and JP-A-2008-063274 ( hereinafter referred to as "supercritical reversed-phase evaporation method publications"), and the method and apparatus described in the supercritical reversed-phase evaporation method publications can be used. Specifically, the supercritical reversed-phase evaporation method is a mixture in which a substance that forms the outer membrane of a vesicle is uniformly dissolved in carbon dioxide in a supercritical state or under temperature conditions above the critical point or under pressure conditions. A method of adding an aqueous phase containing an organic UV absorber as a water-soluble or hydrophilic encapsulating substance to form a capsule-like vesicle containing an organic UV absorber as an encapsulating substance with a single layer film. . In particular, an organic ultraviolet absorbent vesicle whose outer membrane is composed of a substance containing biological lipids such as phospholipids is called an organic ultraviolet absorbent liposome. In addition, carbon dioxide in a supercritical state means carbon dioxide in a supercritical state with a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and temperature conditions above the critical point Carbon dioxide under sub- or pressure conditions means carbon dioxide above the critical conditions only at the critical temperature or only at the critical pressure. By this method, unilamellar lamellar vesicles with a diameter of 50 to 800 nm encapsulating an organic ultraviolet absorber can be obtained.

Phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, glycerophospholipids such as hydrogenated soybean lecithin, sphingomyelin, Sphingophospholipids such as ceramide phosphorylethanolamine and ceramide phosphorylglycerol are included.

Other substances that form the outer membrane of vesicles include nonionic surfactants and dispersing agents such as mixtures of these with cholesterols or triacylglycerols. Among them, nonionic surfactants include polyglycerin ether, dialkylglycerin, 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-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. More than one species can be used. As cholesterols, cholesterol, α-cholestanol, β-cholestanol, cholestan, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, cholecalciferol and the like can be used.

Alternatively, the liposome outer membrane may be formed from a mixture of a phospholipid and a dispersing agent. In the decorative sheet of the present invention, the organic ultraviolet absorbent vesicle is preferably an organic ultraviolet absorbent liposome having an outer membrane made of phospholipids. The compatibility between the resin material, which is the main component of the layer, and the vesicle can be improved.

As the organic UV absorber, at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate can be selected and used. In particular, benzotriazole or triazine UV absorbers can be used. It is preferable to select and use at least one of the agents. It is preferably contained in a proportion of 0.1 to 10 parts by weight, more preferably in a proportion of 0.2 to 5 parts by weight, based on 100 parts by weight of the resin material that is the main component of the transparent resin layer. more preferred. If the content of the organic UV absorber is less than 0.1 parts by weight, sufficient UV absorption performance cannot be obtained, and if the content is more than 10 parts by weight, the possibility of bleeding out increases. .

Benzotriazole-based UV absorbers include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5 -chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3'.5'-dicumylphenyl)benzotriazole, 2,2'- methylenebis(4-tert-octyl-6-benzotriazolyl)phenol and the like. Triazine-based UV absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2 -[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4 -bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl ) oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2′-ethyl )hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and the like. Benzophenone UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone ) and the like. Benzoate-based UV absorbers include phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3′,5′-di-tert-butyl-4′-hydroxybenzoate, 2,4-di-tert-butylphenyl amylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and the like. Examples of cyanoacrylate-based UV absorbers include ethyl-α-cyano-β,β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate.

It is also important that an ink layer containing at least a light stabilizer is provided under the transparent resin layer. A hindered amine-based material is preferably used as the light stabilizer. By adding a light stabilizer to the ink layer, the radicals generated by the deterioration of the binder resin itself that forms the ink layer and the resin of other layers reduce the chemical components of the pigment in the ink, thereby preventing fading of the pigment. It is possible to suppress and maintain a colorful pattern for a long period of time.

A top coat layer may be provided on the upper surface of the transparent resin layer depending on the application and required properties. In particular, in applications requiring mechanical strength, it is important to provide a topcoat layer.

Specific examples of the decorative sheet of the present invention are described below 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, the raw fabric layer 2, the ink layer 3, and the adhesive layer 7 are arranged from the side facing the base material B such as wood boards, inorganic boards, or metal plates to which the decorative sheet 1 is laminated. (a heat-sensitive adhesive layer, an anchor coat layer, a dry lamination adhesive layer), a transparent resin layer 4 and a topcoat layer 5 are laminated. In addition, in order to improve the design, an embossed pattern 4a is formed on the surface of the transparent resin layer 4 on the side of the topcoat layer 5, and the topcoat layer 5 is formed by wiping in the recesses of the embossed pattern 4a. The resin composition is embedded and provided.

As the base fabric layer 2, paper such as thin paper, titanium paper, resin-impregnated paper, etc., synthetic resin such as polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, etc. Or 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, and the like.

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 preferred. In addition, corona treatment, plasma treatment, ozone treatment, electron beam treatment, and ultraviolet treatment are performed on the raw fabric layer 2 in order to improve the adhesiveness between the raw fabric layer 2 made of an olefin material and the base material B. , dichromic acid treatment, etc. are desirable.

The primer layer 6 can basically be made of the same material as the ink layer 3, which will be described later. Inorganic fillers such as silica, alumina, magnesia, titanium oxide, and barium sulfate may be added to avoid this and to enhance adhesion with the adhesive.

The ink layer 3 is a pattern printed on the raw fabric layer 2 using ink, and includes nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, and polyester as a binder. , etc. can be used alone or by appropriately selecting from each modified product. These may be water-based, solvent-based, or emulsion-type, and may be either one-liquid type or two-liquid type using a curing agent. Furthermore, 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 is to use urethane-based ink and cure it with isocyanate. In addition to these binders, pigments, coloring agents such as dyes, extender pigments, solvents, various additives, and the like, which are contained in ordinary inks, are added. Highly versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, pearl pigments such as mica, and the like. In addition to the application of ink, it is also possible to apply a design by vapor deposition or sputtering of various metals. In particular, in the present invention, it is preferable that a light stabilizer is added to the ink described above. can do.

As the transparent resin layer 4, a resin composition containing an olefin resin as a main component and an organic ultraviolet absorber vesicle can be used. Examples of olefin resins include polypropylene, polyethylene, polybutene, α-olefins (eg, 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, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.), homopolymerization or copolymerization of two or more types, and ethylene-vinyl acetate copolymer coalescence, ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, Examples thereof include those obtained by copolymerizing ethylene or α-olefin with other monomers, such as ethylene-butyl acrylate copolymer. In order to improve the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene.

The transparent resin layer 4 may contain various functional additives such as a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a luster adjusting agent, if necessary. may These various functional additives can be appropriately selected from well-known ones and used.

As the top coat layer 5, it is important to use a resin composition that plays a role of surface protection and gloss adjustment. The resin composition may be appropriately selected from among polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea and the like. The form of the resin composition is not particularly limited, and may be water-based, emulsion, solvent-based, or the like. As for the curing method, a one-liquid type, a two-liquid type, an ultraviolet curing method, or the like can be appropriately selected and used.

In the present invention, a urethane-based resin composition using isocyanate is particularly suitable from the viewpoints of workability, cost, cohesive strength of the resin itself, and the like. Examples of isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), methylhexane diisocyanate (HTDI), Methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI) and the like can be appropriately selected and used, but hexamethylene diisocyanate (HMDI) having a linear molecular structure is preferable in consideration of weather resistance. In addition, in order to improve 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 using a hybrid type of a thermosetting resin and a photocurable resin, the surface hardness can be improved, the effect shrinkage can be suppressed, and the transparent resin layer can be used. It is possible to improve the adhesion with.

In addition, the topcoat layer 5 may contain functional additives such as antibacterial agents and antifungal agents in order to impart various functions. Furthermore, alumina, silica, silicon nitride, silicon carbide, glass beads, etc., may be added for improving the design of the surface, for adjusting luster, or for further imparting abrasion resistance. .

The top coat layer 5 may be provided on the transparent resin layer 4 if it is required to improve design, scratch resistance, weather resistance, and the like.

Although the adhesive layer 7 is not particularly limited, it can be used by appropriately selecting from acrylic, polyester, polyurethane, epoxy, and the like. The coating method can be appropriately selected depending on the viscosity of the adhesive, etc., but in general, gravure coating is used, and after coating the upper surface of the ink layer 3 by gravure coating, the transparent resin layer is formed. 4 and laminated. The adhesive layer 7 can be omitted if sufficient adhesive strength can be obtained between the transparent resin layer 4 and the ink layer 3 .

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

The concealing layer 8 can basically be composed of the same material as the ink layer 3. However, since the object is to maintain concealing properties, opaque pigments such as titanium oxide and iron oxide are used as pigments. It is preferred to use It is also possible to add metals such as gold, silver, copper and aluminum in order to increase the hiding power. In general, flaky aluminum is often added.

In forming the decorative sheet 1 of the present invention, the lamination method is not particularly limited, and is appropriately selected from commonly used methods such as a method applying heat pressure, an extrusion lamination method, and a dry lamination method. be able to. In the case of forming the embossed pattern 4a, there is a method in which the embossed pattern 4a is formed by heat pressing after lamination by the lamination method described above, or a method in which a cooling roll is provided with an uneven pattern and the embossed pattern 4a is formed simultaneously with extrusion lamination. can be adopted.

In the decorative sheet of this embodiment, the original fabric layer 2 has a thickness of 20 μm to 150 μm, the adhesive layer 7 has a thickness of 1 μm to 20 μm, the transparent resin layer 4 has a thickness of 20 μm to 200 μm, and the top coat layer 5 has a thickness of 20 μm to 200 μm. The thickness is desirably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably within the range of 45 μm to 400 μm.

As described above, in the decorative sheet 1 of the present embodiment, by providing the transparent resin layer 4 containing the organic ultraviolet absorbent vesicles, the resin composition constituting the transparent resin layer 4 absorbs organic ultraviolet rays. A transparent resin layer 4 in which the agent is extremely uniformly dispersed is realized, and as a result, it has excellent weather resistance without unnecessarily increasing the amount of addition, and also realizes high transparency and excellent design. A sheet 1 can be provided.

In addition, as in the present embodiment, by using the organic UV absorber as an organic UV absorber vesicle, there is a demand for containing a large amount of the organic UV absorber without causing bleeding out. Therefore, it is possible to provide the decorative sheet 1 with even better weather resistance.

Furthermore, by forming the ink layer 3 containing a light stabilizer, it is possible to suppress the fading of the ink layer 3 by ultraviolet rays, and the makeup is excellent in design and maintains beautiful color pattern printing for a long period of time. A sheet 1 can be provided.

<Preparation of organic UV absorber vesicle>
A method for preparing the organic ultraviolet absorbent vesicle is described below. Preparation of the organic UV absorber vesicles was carried out by placing 100 parts by weight of 2-propanol in a high-pressure stainless steel container kept at 60°C, and a triazine UV absorber 2-(4,6-bis(2, 4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl 70 parts by weight of hydroxyphenyltriazine (TINUVIN 400; manufactured by BASF) and 5 parts by weight of phosphatidylcholine as a phospholipid 100 parts by weight of ion-exchanged water is injected while vigorously stirring and mixing, and the pressure inside the container is maintained at 15 MPa. After stirring and mixing for a minute, carbon dioxide was discharged and the pressure was returned to atmospheric pressure to obtain a triazine-based ultraviolet absorber liposome having a monolayer outer membrane composed of phospholipids.

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

<Method for producing laminated resin sheet>
0.05 parts by weight of a hindered phenolic antioxidant (Irganox 1010; manufactured by BASF) and 0.2 parts by weight of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a homopolypropylene resin. A resin to which a triazine-based UV absorber liposome or an organic UV absorber is added in the amount shown in Examples or Comparative Examples is melt-extruded using an extruder to obtain a transparent highly crystalline polypropylene having a thickness of 80 μm. A sheet-shaped transparent resin layer 4 was formed as a sheet, and both surfaces of the obtained transparent resin layer 4 were subjected to corona treatment to adjust the wetting tension of the sheet surface to 40 dyn/cm or more. On the other hand, on the surface of a 70 μm thick polyethylene sheet (original fabric layer 2) having opacifying properties, a two-liquid urethane ink (V180; manufactured by Toyo Ink Mfg. Co., Ltd.) was used to print a pattern by gravure printing. A layer 3 was provided and a primer coat was applied to the rear surface of the raw fabric layer 2 . Thereafter, an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc.; coating amount 2 g/m ² ) to obtain a laminated resin sheet consisting of a raw fabric layer 2, an ink layer 3, an adhesive layer 7 and a transparent resin layer 4 by lamination by a dry lamination method. Thereafter, an embossed pattern 4a was applied to the surface of the transparent resin layer 4 of the laminated resin sheet to obtain a decorative sheet 1 having a total thickness of 157 μm.

<Example 1>
In Example 1, 0.2, 1.0, 5.0 or 10.0 parts of the triazine-based UV absorber liposome prepared by the method described above was added to 100 parts by weight of the highly crystalline homopolypropylene resin as the main component. A decorative sheet 1 having a transparent resin layer 4 containing 0 parts by weight was prepared.

<Example 2>
In Example 2, 0.2 or 10.0 parts by weight of the triazine-based UV absorber liposome prepared by the method described above was added to 100 parts by weight of the highly crystalline homopolypropylene resin as the main component. and an ink layer 3 containing 0.2 parts by weight of a hindered amine light stabilizer (Kimasorb 044; manufactured by BASF) based on 100 parts by weight of ink. and

<Comparative Example 1>
In Comparative Example 1, 0.2, 1.0 or 10.0 parts by weight of a non-vesicled triazine-based UV absorber is contained with respect to 100 parts by weight of the highly crystalline homopolypropylene resin as the main component. The decorative sheet 1 is provided with a transparent resin layer 4 which has been laminated.

<Comparative Example 2>
In Comparative Example 2, the decorative sheet 1 was provided with a transparent resin layer 4 containing no organic ultraviolet absorber.

The decorative sheets 1 of Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to carbon arc weather resistance according to JIS B 7753 using a weather resistance tester (Sunshine Weather Meter: manufactured by Suga Test Instruments Co., Ltd.). A sex test was performed. In addition, the test conditions were 4000 hours of weather resistance. Regarding the transparent resin layer 4 of each decorative sheet 1, the difference in the ratio of UV absorption rate between 340 nm and 500 nm (340 nm/500 nm) before and after the weather resistance test (in Table 1, it is described as UV absorption capacity); And the haze value after the weather resistance test was evaluated. Also, 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 symbols for appearance change are as follows. Table 1 shows the obtained evaluation results.
<Symbol for appearance change>
◎: No change ○: Slight change △: Slight whitening and cracks ×: Severe whitening and partial destruction / breakage

In the decorative sheet 1 of Example 1, as shown in Table 1, for samples with any content, the value of the ultraviolet absorption capacity and the value of the color difference (ΔE) before and after the weather resistance test were small. It can be seen that it has excellent ultraviolet absorption performance and hardly changes in color due to deterioration. Further, the haze value after the weather resistance test revealed that the transparent resin layer 4 maintained the transparency required for the decorative sheet even after the test.

In addition, as shown in Table 1, the decorative sheet 1 of Example 2 has a small value of UV absorption capacity, and has almost the same UV absorption capacity before and after the weather resistance test. From the haze value after the weather resistance test, it became clear that the transparent resin layer 4 maintained the transparency required for the decorative sheet even after the test. In the decorative sheet 1 of Example 2, the value of the color difference (ΔE) before and after the weather resistance test is particularly small, indicating that the color change due to deterioration is extremely small. It is considered that this is because the ink layer 3 containing the light stabilizer was provided, so that decolorization of the ink layer was suppressed during the weather resistance test.

In the decorative sheet 1 of Comparative Example 1, as shown in Table 1, all of the values of the UV absorption capacity, the haze value after the weather resistance test, and the color difference (ΔE) before and after the weather resistance test were the same as in Examples 1 and 2. , indicating that sufficient ultraviolet absorption performance is not obtained. As a result of the change in appearance, whitening and cracking occurred after the weather resistance test. This is because the organic UV absorber that is not vesicled is used, and the organic UV absorber aggregates in the resin composition constituting the transparent resin layer 4, resulting in insufficient UV absorption performance. It is considered that the resin composition is greatly deteriorated and the transparency is lowered due to the aggregated ultraviolet absorber. As shown in Table 1, the decorative sheet 1 of Comparative Example 2 had extremely high UV absorption capacity and color difference (ΔE) before and after the weather resistance test, indicating that it had no UV absorption capacity at all. From the appearance change results, it can be seen that severe whitening and breakage occurred after the weather resistance test. The haze value after the weather resistance test shows a small value, but this is because the transparent resin layer 4 does not contain an organic UV absorber and does not become cloudy due to additives. is.

From this evaluation result, the decorative sheet 1 in Examples 1 and 2 of the present invention exhibited excellent ultraviolet absorption performance over a long period of time by providing the transparent resin layer 4 containing the organic ultraviolet absorbent liposomes. It has been clarified that this excellent ultraviolet absorption performance prevents whitening of the resin and maintains excellent transparency over a long period of time. Moreover, it has been clarified that the ink layer 3 containing the light stabilizer can prevent the ink from fading, which cannot be completely prevented by the ultraviolet absorber, and can maintain the decorative sheet 1 with excellent design properties for a long period of time. rice field.

The decorative sheet 1 of the present invention is not limited to the above embodiments and examples, and various modifications are possible without impairing the characteristics of the invention.

1 decorative sheet 2 raw 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 substrate

Claims (5)

A decorative sheet comprising a transparent resin layer made of a transparent olefin resin,
The transparent resin layer contains an organic ultraviolet absorber,
The organic UV absorber is an organic UV absorber vesicle having an outer membrane consisting of a single-layered lipid bilayer membrane ,
The organic ultraviolet absorber vesicle has a function of dispersing particles without aggregating them by repelling each other's outer membranes,
A decorative sheet comprising an opaque concealing layer containing flake-like metal made of flake-like aluminum below the transparent resin layer. A decorative sheet comprising a transparent resin layer made of a transparent olefin resin,
The transparent resin layer contains an organic ultraviolet absorber,
The organic UV absorber is an organic UV absorber vesicle having an outer membrane consisting of a single-layered lipid bilayer membrane ,
The organic ultraviolet absorber vesicle has a function of dispersing particles without aggregating them by repelling each other's outer membranes,
The outer membrane of the organic UV absorber vesicle comprises a mixture of phospholipid and nonionic surfactant or a mixture of phospholipid and nonionic surfactant and at least one of cholesterols and triacylglycerol. makeup sheet. The outer membrane of the organic UV absorber vesicle comprises a mixture of phospholipid and nonionic surfactant or a mixture of phospholipid and nonionic surfactant and at least one of cholesterols and triacylglycerol. The decorative sheet according to claim 1. 4. The method according to any one of claims 1 to 3, wherein the organic UV absorber is at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate. cosmetic sheet. 5. The decorative sheet according to any one of claims 1 to 4, wherein an ink layer containing a light stabilizer is provided under the transparent resin layer.

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