WO2017034021A1 - Decorative sheet and method for producing decorative sheet - Google Patents

Abstract

Provided are: a decorative sheet having excellent abrasion resistance and post-processing resistance while ensuring high transparency of a surface protective layer; and a method for producing the decorative sheet. A decorative sheet (1) according to one mode of the present invention has: one or more layers of an intermediate layer on one of the surfaces of a base material layer (6); and one or more layers of a surface protective layer (2) on the intermediate layer, wherein the main component of each layer of the surface protective layer (2) is a curable resin, the one layer or at least one of the more layers of the surface protective layer (2) contains a dispersant and inorganic nano particles, and the dispersant and the inorganic nano particles are enclosed together in vesicles.

Description

Decorative sheet and method for producing decorative sheet

The present invention relates to a decorative sheet and a method for manufacturing the decorative sheet.

Examples of techniques for adding sodium calcium aluminosilicate particles and colloidal silica to the surface protective layer forming the surface layer of the decorative sheet include those described in Patent Documents 1 and 2.
However, these decorative sheets are provided with a surface protective layer having high transparency from the viewpoint of design and excellent post-processing resistance that is not affected by post-processing such as surface scratch resistance and V-groove bending. There is a problem that there are few things to have.

Japanese Patent No. 5573986 JP 2012-187922 A

The present invention focuses on the above points, and provides a decorative sheet excellent in scratch resistance and post-processing resistance and a method for manufacturing the decorative sheet while ensuring transparency in the surface protective layer. Objective.

The inventors of the present invention have conducted intensive research, and by adding a nano-dispersed dispersant and inorganic nanoparticles to the surface protective layer, the dispersibility of these fine particles in the surface protective layer is significantly improved. The present invention has been completed by finding success and thereby exhibiting high transparency and excellent mechanical properties.
In order to solve the problem, the decorative sheet which is one embodiment of the present invention has one or two or more intermediate layers on one surface of the base material layer, and one or two layers on the intermediate layer. A decorative sheet having at least one surface protective layer, wherein the main component of the surface protective layer of each layer is a curable resin, and at least one of the one or two or more surface protective layers is dispersed. It contains an agent and inorganic nanoparticles, and both the dispersant and the inorganic nanoparticles are encapsulated in a vesicle.

According to one embodiment of the present invention, by adding a dispersant and inorganic nanoparticles to the surface protective layer, it is possible to ensure high transparency and further improve scratch resistance and post-processability. It becomes possible.
In particular, since both the dispersant and the inorganic nanoparticles are in a vesicle state by being encapsulated in a liposome having an outer membrane made of phospholipid, the dispersibility of the dispersant and the inorganic nanoparticles is significantly improved. Therefore, higher transparency can be secured. Further, since the inorganic particles are nano-sized, deterioration of the matte appearance over time can be suppressed.

It is a figure which shows the structure of the decorative sheet and decorative plate which concern on 1st Embodiment, 2nd Embodiment, and 3rd Embodiment of this invention.

Next, each embodiment of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. In other instances, well-known structures are shown in schematic form in order to simplify the drawing. In addition, each embodiment shown below exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of components are as follows. It is not something specific. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

(First embodiment)
(overall structure)
As shown in FIG. 1, the decorative sheet 1 of the present embodiment has a pattern layer 5, a transparent resin layer 3, and a surface on one surface (front surface) of the base material layer 6 constituting the raw fabric layer. The protective layer 2 is laminated in this order. Reference numeral 4 denotes an adhesive layer. In the present embodiment, the pattern layer 5 and the transparent resin layer 3 constitute an intermediate layer.
Moreover, the concealing layer 7 and the primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6. The concealing layer 7 may be formed between the base layer 6 and the pattern layer 5 or may be omitted.
Moreover, the decorative sheet 1 of this embodiment has illustrated the case where the embossed pattern 3a is formed between the surface protective layer 2 and the transparent resin layer 3. FIG. The embossed pattern 3 a may be formed on the upper surface of the surface protective layer 2.

The layer thickness of the decorative sheet 1 having the above configuration is 3 to 20 μm for the surface protective layer 2, 20 to 200 μm for the transparent resin layer 3, and 1 to 1 for the adhesive layer 4 in consideration of printing workability and cost. 20 μm, the pattern layer 5 is 3 to 20 μm, the base layer 6 is 20 to 150 μm, the masking layer 7 is 2 to 20 μm, the primer layer 8 is 0.1 to 20 μm, and the total thickness of the decorative sheet 1 is 49 Within the range of 450 μm.
In addition, in FIG. 1, the case where the decorative sheet 1 of this embodiment is affixed on the base material B and the decorative board is comprised is illustrated.

<Base material layer 6>
The base material layer 6 is comprised from paper, a resin sheet, foil, etc., for example. Examples of paper include thin paper, titanium paper, resin-impregnated paper, organic or inorganic nonwoven fabric, and synthetic paper. Examples of the resin of the resin sheet include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and other synthetic resins, foams of these synthetic resins, ethylene- Examples of the rubber include propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane. Examples of the foil include metal foils such as aluminum, iron, gold, and silver.

<Pattern pattern layer 5>
The pattern pattern layer 5 can be provided using a known printing method. When the base material layer 6 can be prepared in a wound state, printing for forming the pattern layer 5 can be performed with a roll-to-roll printing apparatus. The printing method is not particularly limited, but for example, a gravure printing method can be used in consideration of productivity and picture quality.
As for the design pattern, it is sufficient to adopt an arbitrary design pattern in consideration of the design properties according to the use place such as flooring or wall material, and various wood grain is often used if it is a wood type design, In addition to the grain, cork can be used as a pattern. For example, if it is an image of a stone floor such as marble, it may be used as a pattern such as a marble stone. In addition to the pattern made of natural materials, an artificial pattern such as an artificial pattern or a geometric pattern using these as a motif can also be used.

Although it does not specifically limit about printing ink, The ink corresponding to a printing system can be selected suitably. In particular, it is preferable to select in consideration of adhesion to the resin base material layer 6, printability, weather resistance as a decorative material, and the like.
To the printing ink, a colorant such as a pigment or a dye, an extender pigment, a solvent, and a binder, which are contained in a normal ink, are appropriately added. Examples of the pigment include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica. The binder may be water-based, solvent-based, or emulsion type, and the curing method is particularly limited, such as a one-component type, a two-component type consisting of a main agent and a curing agent, or a type that is cured by ultraviolet rays or electron beams. Not what you want. Among them, the most common method is a two-component type, which uses a urethane-based main agent and a curing agent made of isocyanate. In addition, the design may be applied by vapor deposition or sputtering of various metals.

<Adhesive layer 4>
The adhesive layer 4 is provided for the purpose of strengthening the adhesion between the base material layer 6 and the pattern / pattern layer 5 and the transparent resin layer 3. When this adhesion is strong, it is possible to give the decorative sheet 1 bending workability that follows a curved surface or a right angle surface. The adhesive layer 4 is preferably transparent.
For the adhesive layer 4, any material can be selected as an adhesion method, for example, a lamination method such as thermal lamination, extrusion lamination, dry lamination, etc., and the adhesive is, for example, acrylic, polyester, polyurethane, epoxy It can select suitably from systems etc. In general, it is desirable to use a urethane-based material obtained by a reaction with a polyol using an isocyanate as a two-component curing type because of its cohesive strength. The adhesive layer 4 may be omitted when the adhesive strength between the transparent resin layer 3 and the pattern layer 5 is sufficiently obtained.

<Transparent resin layer 3>
The transparent resin layer 3 is made of a transparent thermoplastic resin, and for example, a vinyl chloride resin, an acrylic resin, a polyolefin resin, or the like can be used. Of these, polyolefin resins can be preferably used in terms of environmental compatibility, processability, and cost. The transparent resin layer 3 allows the decorative sheet 1 to have an effect of increasing the thickness and depth in design, and can improve the weather resistance and wear resistance of the decorative sheet 1.
As the transparent polyolefin resin, for example, in addition to polypropylene, polyethylene, polybutene and the like, α-olefin (for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1- (Tradecene, etc.) homopolymerized or copolymerized with two or more kinds, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene・ Ethylene or α-olefin was copolymerized with other monomers such as butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, etc. Things.

In particular, when improving the surface strength of the decorative sheet 1, it is preferable to use a crystalline polypropylene resin.
At this time, it is preferable that a nucleating agent (nucleating agent vesicle) encapsulated in vesicles is added to the crystalline polypropylene resin. By adding a nucleating agent vesicle in which a nucleating agent is included in a vesicle having a single-layer outer membrane, a transparent resin layer 3 having better transparency, scratch resistance and post-processing property is obtained. be able to. The nucleating agent vesicle can be prepared by the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method and the like.

Examples of the nucleating agent include phosphoric acid ester metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue and talc. In particular, in order to obtain the maximum effect of nano-treatment, it is preferable to use a phosphoric acid ester metal salt, a benzoic acid metal salt, a pimelic acid metal salt, and a rosin metal salt that can be expected to be non-molten and have good transparency. When the material itself can be made transparent by nano-treatment, colored quinacridone, cyanine blue, talc and the like can also be used. Further, a molten benzylidene sorbitol may be appropriately mixed and used with a non-melting nucleating agent.

Further, the transparent resin layer 3 may be provided with, for example, an existing heat stabilizer, ultraviolet absorber, light stabilizer, anti-blocking agent, catalyst scavenger, colorant, light scattering agent, and gloss adjusting agent, if necessary. These various additives can also be added.
There are no particular restrictions on the method of laminating the transparent resin layer 3, but methods using hot pressure, such as extrusion laminating and dry laminating, are common. Moreover, when embossing pattern is given, there are a method of embossing a sheet once laminated by various methods by hot pressure later, and a method of providing an uneven pattern on a cooling roll and embossing at the same time as extrusion lamination. The embossing method is not particularly limited. For embossing, a known single-wafer or rotary embossing machine is used. Examples of the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like.
Further, there is a method of bonding the transparent resin layer 3 embossed simultaneously with the extrusion and the base material layer 6 by heat or dry lamination. The position where the pattern layer 5 and the adhesive layer 4 are applied may be on the base material layer 6 side as usual, or on the transparent resin layer 3 side.

<Surface protective layer 2>
The surface protective layer 2 may be a single layer, or a plurality of layers may be stacked to form the surface protective layer 2. In the decorative sheet 1 of this embodiment, as shown in FIG. 1, the case where the surface protection layer 2 is a single layer is illustrated.
The surface protective layer 2 has an important role in determining the superiority or inferiority in terms of surface protection, gloss adjustment, cleanability, and the like. The surface protective layer 2 contains a curable resin as a main component. That is, it is preferable that the resin component is substantially composed of a curable resin. “Substantially” means, for example, 80 parts by mass or more when the total resin is 100 parts by mass. And according to the kind of curable resin, application | coating and hardening of a coating film can be performed using a known coating apparatus, a heat drying apparatus, and an ultraviolet irradiation device.

The surface protective layer 2 may contain, for example, an anti-mold agent, a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye and a pigment, a solvent, and the like as necessary.
Here, unevenness may be formed on the surface protective layer 2 in order to impart a given design property. Usually, an uneven pattern (embossed pattern) is formed by embossing.
The material of the surface protective layer 2 can be appropriately selected from polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like. The form of the material is not particularly limited, such as aqueous, emulsion, solvent type. The curing method can be appropriately selected from a one-component type, a two-component type, an ultraviolet curing method, and the like.

In particular, as the main component of the surface protective layer 2, a urethane-based one using isocyanate is preferable from the viewpoint of workability, cost, cohesion 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 methylhexane diisocyanate (HTDI). ), Methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI) and the like, but considering weather resistance, hexamethylene diisocyanate (HMDI) having a linear molecular structure is preferred. . In addition, in order to improve the surface hardness, it is preferable to use a plurality of types of resins that are cured with active energy rays such as ultraviolet rays and electron beams. These resins can be used in combination with each other. For example, by using a hybrid type of a thermosetting type and a photocurable type, it is possible to improve surface hardness, suppress curing shrinkage, and improve adhesion. Can be planned.

The surface protective layer 2 contains a dispersant and inorganic nanoparticles.
Here, when the surface protective layer 2 is composed of a plurality of layers, a dispersant and inorganic nanoparticles are added to at least one of the plurality of layers. In this case, the dispersant and the inorganic nanoparticles are preferably added to the outermost surface protective layer.
Further, both the dispersant and the inorganic nanoparticles are included in the vesicle. For example, the dispersant and the inorganic nanoparticles are encapsulated in liposomes having an outer membrane made of phospholipid and are in a vesicle state. The dispersant preferably has a hydroxyl group or an amino group. Moreover, it is preferable that a dispersing agent has an unsaturated double bond.

<Inorganic nanoparticles>
The inorganic nanoparticles may be any inorganic particles that can be nanosized, and examples thereof include spherical particles such as α-alumina, silica, boehmite, iron oxide, and diamond. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like, and are not particularly limited. As the particle diameter of the inorganic nanoparticles, those having a primary particle diameter of 1 to 1000 nm are preferable, and those having a particle diameter of 10 to 50 nm are more preferable. When the primary particle diameter is larger than 1000 nm, there is a concern that transparency may deteriorate due to light scattering caused by inorganic nanoparticles. There is no need for the primary particle size of the inorganic nanoparticles to be used, and inorganic nanoparticles having different primary particle sizes can be mixed and used. A plurality of different types of inorganic nanoparticles may be mixed and used.

The amount of inorganic nanoparticles added is, for example, 0.005 to 20 parts by mass with respect to 100 parts by mass of the resin composition that is the main component of the surface protective layer 2.
In this case, the amount of the vesicle is 0.00535 to 21.4 parts by mass with respect to 100 parts by mass of the resin composition.
Here, the nano-ization of the inorganic particles can be obtained by a nano-ization method such as a sol-gel method, a reverse micelle method, or a hot soap method.
The sol-gel method is a method of making nanoparticles by performing a chemical reaction such as hydrolysis or polycondensation after making an alkoxide precursor into a sol state by heating or the like.
In the reverse micelle method, reverse micelles are produced by injecting one or two types of reactive raw material aqueous solutions together with a surfactant into an organic solvent, and a chemical reaction such as thermal decomposition is performed in the micelles. It is a method of making particles.
The hot soap method uses a surfactant as a solvent, injects an aqueous metal solution and vigorously stirs it to form minute water droplet micelles, and then performs thermal decomposition or reaction between two types of reactive raw materials to form nanoparticles. Is a method of synthesizing.
The nanoparticles thus produced are covered and protected with a surfactant.

<About dispersant>
The dispersant is used for the surface treatment of inorganic nanoparticles.
As the dispersant, a dispersant having an unsaturated bond, a dispersant having a hydroxyl group, or a dispersant having an amino group is preferable. Two or more kinds of inorganic nanoparticles treated with the respective dispersants can be mixed and used.
Examples of the dispersant having a hydroxyl group include 12-hydroxystearic acid, ricinoleic acid and the like combined with lithium, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, sorbitan fatty acid ester, alcohol-modified silicone oil, alcohol Examples include modified wax, oxidized wax, and carnauba wax.
Examples of the dispersant having an amino group include polycarboxylic acid alkylamine, alkylpolyamine, stearic acid amide, oleic acid amide, erucic acid amide, n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, n- 2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, di-n-butoxy bis (triethanolaminato) titanium, bis (4-aminobenzoato-O) (isooctadecanoato-O) (propan-2-olato) titanium, bis [2-[(2-aminoethyl) amino] ethanolato] [2-[(2-aminoethyl) amino] ethanolato-O] (propan-2-olato) titanate, amino-modified silico Oil and the like.

Examples of the dispersant having an unsaturated double bond include aliphatic surfactants such as aliphatic polyvalent polycarboxylic acids, polycarboxylic acid alkylamines, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, and olein. Fatty acid metal salts in which fatty acids such as acid, linoleic acid, γ-linolenic acid, and linolenic acid are combined with lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, aluminum, etc., vinyltrimethoxysilane, vinyltriethoxysilane P-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 Silane coupling agents such as acryloxypropyltrimethoxysilane, hydrogen tetrakis [2,2-bis [(allyloxy) methyl] butan-1-olato-O1] bis (ditridecylphosphito-O '') titanate (2-), Examples include titanate coupling agents such as Titanium, bis (isooctadecanoato-kO) bis (2-propanolato)-(9CI), waxes obtained by thermally decomposing polyolefins and further oxidizing them.

It should be noted that there are desirable combinations of curable resins and dispersants in terms of properties. When a dispersant having a hydroxyl group or an amino group is used, it is preferable to use a thermosetting resin, particularly an isocyanate compound, and the isocyanate compound and the hydroxyl group or amino group of the dispersant react to form a surface protective layer 2. Since a structure in which inorganic nanoparticles are immobilized on the surface is formed, the scratch resistance of the surface of the surface protective layer 2 can be dramatically improved. Similarly, when using a dispersant having an unsaturated double bond, it is preferable to use a photocurable resin alone or a mixed resin of a thermosetting resin and a photocurable resin. By reacting with the curable resin to form a structure in which inorganic nanoparticles are immobilized on the surface of the surface protective layer 2, the scratch resistance of the surface of the surface protective layer 2 can be dramatically improved.

<Vesicle formation of dispersant and inorganic nanoparticles>
The vesicle formation of the dispersant and the inorganic nanoparticles in this embodiment is performed by, for example, the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, and the supercritical reverse phase evaporation method. Is called. The form of the vesicle is a capsule form in which an object (dispersant and inorganic nanoparticles) is encapsulated with the vesicle. However, in the resin constituting the surface protective layer 2, the film constituting the vesicle may be broken and the inorganic nanoparticles may be in contact with the resin.
Briefly describing such a vesicle treatment, in the Bangham method, chloroform or a chloroform / methanol mixed solvent is placed in a container such as a flask, and phospholipid is further added to dissolve. Thereafter, the solvent is removed using an evaporator to form a thin film made of lipid, and after adding a dispersant and a dispersion of inorganic nanoparticles, the vesicle is obtained by hydrating and dispersing with a vortex mixer.

The extrusion method is a method of preparing a vesicle by preparing a thin phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method.
The hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining vesicles by gently stirring and dispersing without using a mixer.
In the reverse phase evaporation method, a phospholipid is dissolved in diethyl ether or chloroform, a solution containing a dispersant and inorganic nanoparticles is added to form a W / O emulsion, and the organic solvent is removed from the emulsion under reduced pressure. In this method, vesicles are obtained by adding water.
The freeze-thaw method is a method using cooling / heating as external perturbation, and is a method of obtaining vesicles by repeating this cooling / heating.

In particular, as a method for obtaining a vesicle having an outer film composed of a single layer film, a supercritical reverse phase evaporation method can be mentioned. Vesicleization by the supercritical reverse phase evaporation method means that the encapsulated substance is dissolved in a mixture in which the substance that forms the outer membrane of the vesicle is uniformly dissolved in carbon dioxide in a supercritical state or at a temperature or pressure condition above the critical point. And adding an aqueous phase containing inorganic nanoparticles and a dispersant as a capsule to form a capsule-like vesicle including the inorganic nanoparticles and the dispersant as an encapsulating material in a single layer.
A vesicle refers to a vesicle having a membrane structure closed like a spherical shell and containing a liquid phase inside. Phospholipids form stable vesicles (also called liposomes) consisting of a lipid bilayer phase in the aqueous phase.

Note that the carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher. The carbon dioxide under the temperature condition or pressure condition above the critical point means carbon dioxide under the condition that only the critical temperature or the critical pressure exceeds the critical condition. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained. For more detailed contents of the supercritical reverse phase evaporation method, JP 2002-032564 A, JP 2003-119120 A, JP 2005-298407 A and JP 2005-298407 proposed by the present inventors. No. 2008-063274 (hereinafter referred to as “supercritical reverse phase evaporation method publications”).

Examples of the phospholipid constituting the vesicle include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin. Glycerophospholipids such as sphingomyelin, sphingophospholipids such as ceramide phosphorylethanolamine and ceramide phosphorylglycerol.

<Hidden layer 7>
The concealing layer 7 is formed by printing, for example, in the same manner as the picture pattern layer 5 for the purpose of maintaining concealment. As the pigment to be included in the ink, it is preferable to use an opaque pigment, titanium oxide, iron oxide or the like. It is also possible to add metals such as gold, silver, copper, and aluminum in order to improve the concealing property. In general, flaky aluminum is often added. The masking layer 7 can be omitted when the base material layer 6 is opaque and has masking properties.

<Primer layer 8>
The primer layer 8 is formed in order to improve the adhesion with the base material B.
When the base material B is a wood base material B, the primer layer 8 is, for example, an ester resin, a urethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride-vinyl acetate copolymer, a polyvinyl butyral resin. And nitrocellulose-based resins. These resins can be used alone or mixed to form an adhesive composition, which can be formed using an appropriate application means such as a roll coating method or a gravure printing method. In this case, the resin constituting the primer layer 8 is preferably a urethane-acrylate resin. That is, it is particularly preferable to form the resin made of a copolymer of an acrylic resin and a urethane resin and an isocyanate.

<Base material B>
Examples of the base material B include wooden boards (woody base materials), inorganic boards (composite plates), metal plates, and the like.

"Production method of decorative sheet 1"
In the method for producing the decorative sheet 1 of the present embodiment, first, a transparent resin sheet 3 as the transparent resin layer 3 is formed by melt extrusion molding, and both surfaces of the obtained transparent resin sheet 3 are subjected to corona treatment to obtain a wetting tension. Is assumed to be 40 dyn / cm or more. Similarly, about the base material layer (original fabric resin sheet) 6 as an original fabric layer formed by melt extrusion molding, pattern printing is performed on one surface by a gravure printing method to form the pattern pattern layer 5. At the same time, the masking layer 7 and the primer layer 8 are sequentially stacked on the other surface. Then, an adhesive layer 4 is provided so as to overlap with the pattern layer 5, and the raw fabric resin sheet 6 and the transparent resin sheet 3 are bonded together via the adhesive layer 4 by a dry laminating method. Finally, after embossed pattern 3a is applied to the surface of transparent resin sheet 3, decorative sheet 1 is obtained by applying surface protective layer 2 so as to cover embossed pattern 3a.

In addition, the production method of the decorative sheet 1 is not limited to the above method. For example, for the pattern layer 5, the offset printing method, the screen printing method, the flexographic printing method, the ink jet printing method in addition to the gravure printing method. Etc. can be formed. About the bonding method of the raw fabric resin sheet 6 and the transparent resin sheet 3, in addition to the dry laminating method, a method using hot pressure or an extrusion laminating method can be used.

<Effects of First Embodiment>
(1) The decorative sheet 1 is composed of a single layer or a plurality of layers, and has at least one surface protective layer 2 to which a vesicle-dispersed dispersant and inorganic nanoparticles are added. In the nano-treatment (vesicle-treatment), Both the dispersant and the inorganic nanoparticles are vesicles such as encapsulated in liposomes.
According to this configuration, scratch resistance can be imparted by adding inorganic fine particles to the surface protective layer 2.

At this time, by using a dispersant and inorganic nanoparticles, light scattering caused by adding the particles can be suppressed.
Further, since both the dispersant and the inorganic nanoparticles are in a vesicle state by being encapsulated in a liposome having an outer membrane made of phospholipid, fine particles made of a nano-sized dispersant and inorganic nanoparticles Is significantly improved, and secondary aggregation of the inorganic nanoparticles can be suppressed and uniformly dispersed in the resin constituting the surface protective layer 2. As a result, higher transparency can be secured.

In addition, since the inorganic particles are nano-sized and uniformly dispersed, deterioration of the matte appearance over time can be suppressed.
As described above, by adding a nano-dispersed dispersant and inorganic nanoparticles to the surface protective layer 2, while suppressing secondary aggregation of the inorganic nanoparticles, the dispersibility in the surface protective layer 2 is improved. It is possible to significantly improve. Thereby, the surface protective layer 2 excellent in scratch resistance can be obtained without impairing the transparency of the surface protective layer 2.

(2) The dispersant may have a hydroxyl group or an amino group.
According to this configuration, since the hydroxyl group or amino group of the dispersant is firmly bonded to the thermosetting resin, the inorganic nanoparticles in the surface protective layer 2 are immobilized on the surface protective layer 2, whereby inorganic nanoparticles are obtained. It is possible to improve the deterioration of the scratch resistance due to the omission.
(3) The dispersant preferably has an unsaturated double bond.
According to this configuration, since the unsaturated double bond of the dispersant is firmly bonded to the photocurable resin, the inorganic nanoparticle of the surface protective layer 2 is immobilized on the surface protective layer 2, and thus the inorganic nanoparticle is fixed. It is possible to improve the deterioration of the scratch resistance due to the lack of particles.

(4) The resin composition that is the main component of the surface protective layer 2 is a curable resin.
According to this configuration, it is possible to provide a decorative sheet 1 including the surface protective layer 2 having high scratch resistance and flexibility optimal for post-processing by crosslinking of the resin composition constituting the surface protective layer 2. .
(5) It is preferable to add a nucleating agent subjected to nano-treatment to the transparent resin layer 3.
According to this configuration, by adding the nano-processed nucleating agent to the crystalline polypropylene resin as the resin composition, the average particle diameter of the spherulites in the crystal part of the crystalline polypropylene resin is optimized. By adjusting the size, it becomes possible to realize excellent transparency, scratch resistance and post-processing resistance in the transparent resin layer 3.

(6) Vesicle formation may be performed by nano-processing by a supercritical reverse phase evaporation method.
According to this configuration, by performing nano-treatment using the supercritical reverse phase evaporation method, the dispersibility of the inorganic nanoparticles contained in the surface protective layer 2 and the nucleating agent contained in the transparent resin layer 3 can be obtained. By significantly improving dispersibility, it is possible to impart scratch resistance performance while maintaining transparency.

[First embodiment]
Examples of the first embodiment will be described below.
In addition, the layer structure of the decorative sheet 1 described below is the same as that of the above-described embodiment.
<Example 1-1>
In Example 1-1, both the dispersant having no reactive group and inorganic nanoparticles were nano-treated by the Bangham method on the surface of the transparent resin layer 3 to which the nucleating agent liposome was not added. The surface protective layer 2 was formed by adding 0.05 parts by mass of liposomes encapsulated in phospholipid capsules to 100 parts by mass of the thermosetting resin constituting the surface protective layer 2.

Specifically, a highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, an MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3, Hindered phenol-based antioxidant (Irganox 1010: manufactured by BASF) 500 ppm, benzotriazole-based UV absorber (Tinuvin 328: manufactured by BASF) 2000 ppm, hindered amine-based light stabilizer (Kimasorb 944: manufactured by BASF) The resin added with 2000 ppm was extruded using a melt extruder to form a 100 μm thick transparent resin sheet made of highly crystalline polypropylene used as the transparent resin layer 3. Subsequently, both surfaces of the formed transparent resin sheet were subjected to corona treatment so that the surface wetting tension was 40 dyn / cm or more.

On the other hand, with respect to one side of a 70 μm polyethylene sheet (base material layer 6) having a concealing property, a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) is used with respect to the binder resin content of the ink. The pattern printing layer 5 was provided by performing pattern printing by a gravure printing method using an ink to which 0.5% by mass of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) was added. A primer layer 8 was provided on the other surface of the base material layer 6.
Thereafter, a transparent resin sheet is applied to one surface side of the base material layer 6 via an adhesive for dry laminating as an adhesive layer 4 (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m ² ). Bonding was performed by a dry laminating method. And after giving the embossed pattern 3a to the surface of a transparent resin sheet, the liposome containing the above-mentioned dispersing agent and inorganic nanoparticles with respect to 100 parts by mass of a two-component curable urethane topcoat (W184; manufactured by DIC Graphics) The surface protective layer 2 was formed by applying an ink containing 0.05 part by mass at an application thickness of 15 g / m ² . The total thickness of the decorative sheet 1 is 200 μm.

<Example 1-2>
In Example 1-2, the surface of the transparent resin layer 3 to which the nucleating agent liposomes were not added, both the dispersant having an amino group and the inorganic nanoparticles were nanonized by the Bangham method. The surface protective layer 2 was formed by adding 0.05 parts by mass of the liposomes encapsulated in the capsules composed of 100 parts by mass of the thermosetting resin constituting the surface resin layer.
Others were produced in the same manner as in Example 1-1 to obtain the decorative sheet 1 of Example 1-2.

<Example 1-3>
In Example 1-3, the surface of the transparent resin layer 3 to which the nucleating agent liposome was not added was both nanodispersed by the Bangham method with both the dispersant having an unsaturated double bond and inorganic nanoparticles. The surface protective layer 2 was formed by adding 0.05 parts by mass of liposomes encapsulated in phospholipid capsules to 100 parts by mass of the curable resin constituting the surface resin layer. As the curable resin, a mixed resin of a thermosetting resin and a photocurable resin was employed.
Others were produced in the same manner as Example 1-1 to obtain a decorative sheet 1 of Example 1-3.

<Example 1-4>
In Example 1-4, the surface of the transparent resin layer 3 to which the nucleating agent liposomes are added is composed of a phospholipid in which both the dispersant having an amino group and the inorganic nanoparticles are nanonized by the Bangham method. The liposome contained in the capsule was added to 0.05 part by mass with respect to 100 parts by mass of the thermosetting resin constituting the surface resin layer to form the surface protective layer 2.
Specifically, a resin composition for forming the transparent resin layer 3 described below was melt-extruded using an extruder to form a transparent resin sheet as a transparent highly crystalline polypropylene sheet having a thickness of 100 μm. Subsequently, the both sides of the transparent resin sheet were subjected to corona treatment, and the wet tension of the transparent resin sheet surface was set to 40 dyn / cm or more. Otherwise, the decorative sheet 1 of Example 1-4 was obtained in the same manner as Example 1-2.

Here, nucleation of the nucleating agent was performed as follows.
"Preparation of nucleating agent liposomes"
Hereinafter, vesicle formation of the nucleating agent added to the transparent resin layer 3 in the present embodiment will be described. The nucleating agent is vesicled by supercritical reverse phase evaporation, first 100 parts by mass of methanol and 82 parts by mass of a phosphate ester metal salt nucleating agent (ADK STAB NA-11, manufactured by ADEKA) as a nucleating agent. After putting 5 parts by mass of phosphatidylcholine as a substance constituting the outer membrane of the vesicle in a high-pressure stainless steel container kept at 60 ° C. and injecting carbon dioxide so as to have a pressure of 20 MPa, a supercritical state is obtained. Then, 100 parts by mass of ion-exchanged water is injected with vigorous stirring and mixing. A nucleating agent for a vesicle having a monolayer outer membrane made of phospholipid by stirring for 15 minutes while maintaining the temperature and pressure in a supercritical state and then discharging carbon dioxide to return to atmospheric pressure. A vesicle-containing nucleating agent (nucleating agent liposome) was obtained.

<Preparation and film-forming method of transparent resin layer 3 to which nucleating agent liposomes are added>
Hereinafter, the detailed preparation method of the resin composition which forms the transparent resin layer 3 which added said nucleating agent liposome and the film forming method of a transparent resin sheet are demonstrated.
The resin composition forming the transparent resin layer 3 has a high pentad fraction of 97.8%, MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and molecular weight distribution MWD (Mw / Mn) of 2.3. Hindered phenolic antioxidant (Irganox 1010: manufactured by BASF) 500 ppm, benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) 2000 ppm, and hindered amine light stabilization for crystalline homopolypropylene resin An agent (Kimasorb 944: manufactured by BASF) 2000 ppm and the above nucleating agent liposome 1000 ppm are used. Then, the resin composition was melted and extruded using a melt extruder to form a transparent resin sheet having a thickness of 100 μm to be used as the transparent resin layer 3.

<Example 1-5>
In Example 1-5, the surface of the transparent resin layer 3 to which the nucleating agent liposomes were added, both the dispersant having an amino group and the inorganic nanoparticles were nanonized by the supercritical reverse phase evaporation method. The surface protective layer 2 was formed by adding 0.05 parts by mass of liposomes encapsulated in phospholipid capsules to 100 parts by mass of the thermosetting resin constituting the surface resin layer. Otherwise, the decorative sheet 1 of Example 1-5 was obtained in the same manner as Example 1-4.
Here, the vesicle formation of the inorganic nanoparticles and the dispersant was performed as follows.

That is, vesicles were prepared by adding 100 parts by mass of hexane, 70 parts by mass of inorganic nanoparticles, 0.07 parts by mass of a dispersant, and 5 parts by mass of phosphatidylcholine as a phospholipid to a high-pressure stainless steel container maintained at 60 ° C. Put in and seal, inject carbon dioxide so that the pressure in the container becomes 20 MPa, make it supercritical, inject 100 parts by mass of ethyl acetate while stirring and mixing violently, and stir for 15 minutes while maintaining temperature and pressure After mixing, this was carried out by a supercritical reverse phase evaporation method in which carbon dioxide was discharged and returned to atmospheric pressure to obtain vesicles containing inorganic nanoparticles having a phospholipid outer membrane and a dispersing agent.
Here, when 0.01 part by mass is added as a filler, 0.0107 part by mass of vesicle is added.

<Comparative Example 1-1>
A decorative sheet of Comparative Example 1-1 was produced in the same manner as in Example 1-1, except that the dispersant and inorganic nanoparticles not having a vesicle were not used.
<Comparative Example 1-2>
Comparative Example 1-2 was carried out in the same manner as Example 1-1 except that inorganic nanoparticles encapsulated in phospholipid capsules (vesicles) and a dispersant having no vesicle reactive group were used. A decorative sheet was prepared.
<Comparative Example 1-3>
Comparative Example 1-3 was the same as Example 1-1 except that 4.5 μm silica particles (OK412: manufactured by Evonik) were used as inorganic particles encapsulated in phospholipid capsules (vesicles). A decorative sheet was prepared.

<Comparative Example 1-4>
Comparison was made in the same manner as in Example 1-1, except that 0.002 parts by mass of the liposome encapsulated in a phospholipid capsule (vesicle) was added to both the dispersant having no reactive group and the inorganic nanoparticles. A decorative sheet of Example 1-4 was prepared.
<Comparative Example 1-5>
Comparative Example 1 was carried out in the same manner as in Example 1-1, except that 50 parts by mass of the liposome encapsulated in the capsule (vesicle) made of phospholipid were added together with the dispersant having no reactive group and the inorganic nanoparticles. A decorative sheet of -5 was produced.

<Evaluation>
The decorative sheets 1 obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 were bonded to the wood base B using a urethane adhesive, and then visually. The surface transparency, the Hoffman scratch test and the steel wool rubbing test were used to determine the surface hardness and the V-groove bending workability test was evaluated. The obtained evaluation results are shown in Table 1.
Hereinafter, the test method of each evaluation test will be briefly described.

<Hoffman scratch test>
The Hoffman scratch test was performed by scratching the surface of each decorative sheet 1 bonded to the wooden base material B at a constant speed with a load of 1200 g using a Hoffman scratch hard tester (BYK-Gardner). The presence or absence of scratches on the surface of 1 was visually determined.

<Steel wool rubbing test>
In the steel wool rubbing test, the surface of each decorative sheet 1 bonded to the wooden base material B is fixed with a jig in a state where the steel wool is in contact, and a load of 500 g is applied to the jig. The surface of the decorative sheet 1 was visually checked for scratches by rubbing at a constant speed and a distance of 50 mm under 50 reciprocating conditions. For the steel wool, Bonstar # 0 (manufactured by Nippon Steel Wool Co., Ltd.) was used.

<V-groove bending test>
In the V-groove bending suitability test, each decorative sheet obtained by the above method is attached to one surface of a medium-quality fiberboard (MDF) as a base material using a urethane-based adhesive, With respect to the other surface of the base material, a V-shaped groove is inserted to the boundary where the base material and the decorative sheet are bonded together so that the opposite decorative sheet is not scratched. Next, the base material B is bent to 90 degrees along the V-shaped groove so that the face of the decorative sheet is mountain-folded, and whether or not the bent portion of the surface of the decorative sheet has been whitened or cracked is observed. Observe with an optical microscope and evaluate the superiority or inferiority of post-processing resistance.

Explanation of symbols in the evaluation results of Table 1 is as follows.
◎: Very good transparency, scratch resistance or post-processing resistance ○: Good transparency, scratch resistance or post-processing resistance ×: Transparency, scratch resistance or post-processing resistance Inferior

In the decorative sheets 1 of Examples 1-1 to 1-5, as shown in Table 1, the transparency was good, and good results were also obtained in the Hoffman scratch test, the steel wool test, and the V-groove bending test. Obtained.
This is because, in the decorative sheets 1 of Examples 1-1 to 1-5, the inorganic nanoparticles are uniformly dispersed by adding the vesicle encapsulating both the inorganic nanoparticles and the dispersant to the surface protective layer 2. Therefore, it is considered that the surface hardness is improved due to the inorganic nanoparticles while maintaining good transparency and suitability for post-processing required for the decorative sheet 1.

On the other hand, the decorative sheet 1 of Comparative Example 1-1 has the post-processing suitability required for the decorative sheet 1, but the reactive group in which the surface protective layer 2 is not vesicled. It is considered that the dispersibility of the inorganic nanoparticles was not sufficiently obtained due to the use of the dispersant and the inorganic nanoparticles having no odor, and the transparency and scratch resistance required for the decorative sheet could not be obtained. In addition, the decorative sheet 1 of Comparative Example 1-2 has a post-processing suitability required for the decorative sheet 1, but because a dispersant that is not subjected to vesicle formation on the surface protective layer 2 is used. It is considered that the dispersibility of the inorganic nanoparticles was not sufficiently obtained, and the transparency and scratch resistance required for the decorative sheet could not be obtained. Further, in the decorative sheet 1 of Comparative Example 1-3, since the particle size of the inorganic particles is too large, irregularities are formed on the surface of the surface protective layer 2 and the transparency is impaired. It is considered that the fine particles were not sufficiently bonded, resulting in poor scratch resistance and post-working resistance. Further, the decorative sheet 1 of Comparative Example 1-4 has the transparency and post-processing suitability required for the decorative sheet 1, but the vesicle encapsulates the dispersant and the inorganic nanoparticles in the capsule made of phospholipid. It was considered that the result was inferior in scratch resistance because the addition amount of was very small. In addition, for the decorative sheet 1 of Comparative Example 1-5, the amount of vesicles encapsulating the dispersant and the inorganic nanoparticles in the phospholipid capsule was very large, resulting in poor transparency and scratch resistance. It is considered that the property was inferior because the inorganic nanoparticles dropped off during friction and caused abrasive wear. In addition, it is considered that the thermosetting resin and the inorganic fine particles were not sufficiently bonded, resulting in poor post-processability.

From the above evaluation results, the decorative sheet 1 of the present invention shown in Examples 1-1 to 1-5 has the transparency required for the decorative sheet 1, and is extremely excellent in scratch resistance and post-processing resistance. It became clear that it was the decorative sheet 1.

[Reference example]
Hereinafter, a decorative sheet other than the decorative sheet described in the first embodiment will be briefly described as a reference example of the present invention.
Conventionally, a thermosetting resin (for example, a two-component curable resin) is used for the purpose of imparting physical properties such as scratch resistance, stain resistance, and impact resistance to a surface protective layer that forms a surface layer of a decorative sheet. Alternatively, a curable resin typified by an ionizing radiation curable resin that is cured by ionizing radiation such as ultraviolet rays or electron beams is used as a main component.
In addition, for the purpose of imparting a matte appearance to the decorative sheet, a matting agent such as silica fine particles is also contained in the surface protective layer.

Further, Patent Document 1 contains a matting agent and sodium calcium aluminosilicate particles in the surface protective layer in order to prevent wear of the matting agent exposed on the surface of the surface protective layer over time. Has also been proposed. However, even if the surface protective layer contains the matting agent and sodium calcium aluminosilicate particles, the matting agent and sodium calcium aluminosilicate particles are exposed on the surface of the surface protective layer. As time passes, the exposed part is worn out, and the matte appearance at the start of use may be impaired.

In order to solve this problem, Patent Document 2 proposes a decorative sheet in which colloidal silica is added to the surface protective layer. However, the use of the decorative sheet is expanding more and more, and improvement in scratch resistance, wear resistance and post-processing resistance is demanded.

(Second Embodiment)
(overall structure)
As shown in FIG. 1, the decorative sheet 1 of the present embodiment has a pattern layer 5, a transparent resin layer 3, and a surface on one surface (front surface) of the base material layer 6 constituting the raw fabric layer. The protective layer 2 is laminated in this order. Reference numeral 4 denotes an adhesive layer. In the present embodiment, the pattern layer 5 and the transparent resin layer 3 constitute an intermediate layer.
Moreover, the concealing layer 7 and the primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6. The concealing layer 7 may be formed between the base layer 6 and the pattern layer 5 or may be omitted.
Moreover, the decorative sheet 1 of this embodiment has illustrated the case where the embossed pattern 3a is formed between the surface protective layer 2 and the transparent resin layer 3. FIG. The embossed pattern 3 a may be formed on the upper surface of the surface protective layer 2.
That is, the decorative sheet 1 of the present embodiment has the same configuration as the decorative sheet 1 described in the first embodiment.
Hereinafter, each of the above layers will be described.

<Base material layer 6>
The base material layer 6 of the present embodiment is the same as the base material layer 6 described in the first embodiment. Therefore, description of the base material layer 6 is omitted here.

<Pattern pattern layer 5>
The pattern pattern layer 5 of this embodiment is substantially the same as the pattern pattern layer 5 described in the first embodiment. Therefore, description of the pattern layer 5 is omitted here. The binder contained in the pattern layer 5 may be a material such as nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, or the like alone or each modified product. .

<Adhesive layer 4>
The adhesive layer 4 of the present embodiment is the same as the adhesive layer 4 described in the first embodiment. Therefore, description of the adhesive layer 4 is omitted here.

<Transparent resin layer 3>
The transparent resin layer 3 of the present embodiment is the same as the transparent resin layer 3 described in the first embodiment. Therefore, description of the transparent resin layer 3 is omitted here.

<Surface protective layer 2>
The surface protective layer 2 of the present embodiment contains a dispersant having a hydroxyl group, an amino group or an unsaturated double bond, and inorganic nanoparticles having a particle diameter in the range of 10 nm to 50 nm. Here, the inorganic nanoparticles are encapsulated in a vesicle having a single-layer outer membrane containing the dispersant. That is, the surface protective layer 2 of the present embodiment contains so-called “inorganic nanoparticle vesicles”.
The inorganic nanoparticle vesicle can be prepared, for example, using the supercritical reverse phase evaporation method described in the first embodiment. Moreover, the form is a capsule shape and the outer membrane | film | coat as an outer shell of a capsule is made into the single layer film | membrane containing a dispersing agent. Further, in such a resin composition that forms the surface protective layer, such an inorganic nanoparticle vesicle breaks the outer membrane containing the dispersant, and the encapsulated inorganic nanoparticles are exposed to form a resin composition. In some cases, they may exist in contact.
In addition, since the said inorganic nanoparticle is as substantially the same as the inorganic nanoparticle demonstrated in 1st Embodiment, the description is abbreviate | omitted here.
Further, the dispersant is substantially the same as the dispersant described in the first embodiment. Therefore, description of the dispersant is omitted here.

It is preferable to use a curable resin as the main component of the surface protective layer 2 of the present embodiment. Specifically, a thermosetting resin and a photocurable resin can be used, but it is particularly preferable to use only a thermosetting resin or a mixed resin of a thermosetting resin and a photocurable resin. By using such a curable resin, surface hardness can be improved, curing shrinkage can be suppressed, and adhesion with inorganic fine particles can be improved.

The thermosetting resin can be appropriately selected from, for example, polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aluminoalkyd, urea, etc. It is preferable to use a two-component curable urethane-based one. Urethane-based thermosetting resins are suitable from the viewpoints of workability, cost, cohesive strength of the resin itself, and the like. As the urethane resin, a urethane resin obtained by reacting acrylic polyol and isocyanate may be used. In addition, since the said isocyanate is substantially the same as the isocyanate demonstrated in 1st Embodiment, the description is abbreviate | omitted here.
In addition, as the photocurable resin, for example, a polyester acrylate type, an epoxy acrylate type, a urethane acrylate type, an acrylic acrylate type, and the like can be appropriately selected and used. In particular, a urethane acrylate having good weather resistance (light) resistance. It is preferable to use a system and an acrylic acrylate system.

As for the mixed resin of the thermosetting resin and the photocurable resin, for example, a two-component curable urethane resin using isocyanate as the thermosetting resin, and a urethane-acrylate resin as the photocurable resin; It is preferable to mix and use. This is because an improvement in surface hardness, suppression of curing shrinkage, and post-processing resistance can be imparted. The form of the resin material is not particularly limited as in the first embodiment, such as aqueous, emulsion, and solvent systems.
In addition, since the preferable combination of the said curable resin and the said dispersing agent is the same as the preferable combination of curable resin and a dispersing agent demonstrated in 1st Embodiment, the description is abbreviate | omitted here.

In the decorative sheet according to the present embodiment as described above, light scattering caused by adding particles is suppressed by using inorganic nanoparticles having a minimum size of 10 to 50 nm. Further, the inorganic nanoparticles are added as inorganic nanoparticle vesicles encapsulated in a vesicle having a single-layer outer membrane containing a dispersant. For this reason, secondary aggregation of inorganic nanoparticles can be suppressed in the resin composition, and inorganic nanoparticles can be uniformly dispersed. By carrying out like this, the decorative sheet provided with the surface protection layer excellent in the outstanding transparency, scratch resistance, and post-processing property can be provided.

(Third embodiment)
(overall structure)
As shown in FIG. 1, the decorative sheet 1 of the present embodiment has a pattern layer 5, a transparent resin layer 3, and a surface on one surface (front surface) of the base material layer 6 constituting the raw fabric layer. The protective layer 2 is laminated in this order. Reference numeral 4 denotes an adhesive layer. In the present embodiment, the pattern layer 5 and the transparent resin layer 3 constitute an intermediate layer.
Moreover, the concealing layer 7 and the primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6. The concealing layer 7 may be formed between the base layer 6 and the pattern layer 5 or may be omitted.

Moreover, the decorative sheet 1 of this embodiment has illustrated the case where the embossed pattern 3a is formed between the surface protective layer 2 and the transparent resin layer 3. FIG. The embossed pattern 3 a may be formed on the upper surface of the surface protective layer 2.
That is, the decorative sheet 1 of the present embodiment has the same configuration as the decorative sheet 1 described in the first embodiment and the second embodiment.
Here, the decorative sheet 1 of the present embodiment is different from the decorative sheet 1 of the second embodiment only in the surface protective layer 2. Therefore, only the surface protective layer 2 of this embodiment will be described here.

<Surface protective layer 2>
The surface protective layer 2 of the present embodiment contains a dispersant having a hydroxyl group, an amino group or an unsaturated double bond, and inorganic nanoparticles having a particle diameter in the range of 10 nm to 50 nm. Here, the dispersant is encapsulated in a vesicle having a monolayer outer membrane made of phospholipid. That is, the surface protective layer 2 of this embodiment contains a so-called “dispersant vesicle”.
The dispersant vesicle can be prepared, for example, using the supercritical reverse phase evaporation method described in the first embodiment. In the dispersant vesicle, the outer membrane, which is the outer shell of the capsule, is a monolayer membrane made of phospholipid, and the monolayer membrane contains the dispersant. In the resin composition forming the surface protective layer, such a dispersant vesicle is formed so that the outer membrane made of phospholipid is broken and the encapsulated dispersant is exposed to come into contact with the resin composition. It may exist.

In addition, about the above-mentioned inorganic nanoparticle, a dispersing agent, phospholipid, and curable resin, the thing similar to 1st Embodiment can be used. Therefore, the description thereof is omitted here.
In the decorative sheet according to the present embodiment as described above, light scattering caused by adding particles is suppressed by using extremely small inorganic nanoparticles of 10 to 50 nm. Further, the dispersant is added together with the inorganic nanoparticles as a dispersant vesicle encapsulated in a vesicle having a monolayer outer membrane made of phospholipid. For this reason, since the dispersing agent vesicle is uniformly dispersed in the resin composition, secondary aggregation of the inorganic nanoparticles in the resin composition can be suppressed and the inorganic nanoparticles can be uniformly dispersed in the resin composition. . By carrying out like this, the decorative sheet provided with the surface protection layer excellent in the outstanding transparency, scratch resistance, and post-processing property can be provided.

"Production method of decorative sheet 1"
Hereinafter, a method for producing the decorative sheet 1 of the second embodiment and the third embodiment will be briefly described.
In the method for producing the decorative sheet 1 of each embodiment, first, the transparent resin sheet 3 as the transparent resin layer 3 is formed by melt extrusion molding, and both surfaces of the obtained transparent resin sheet 3 are subjected to corona treatment to obtain a wetting tension. Is assumed to be 40 dyn / cm or more. Similarly, about the base material layer (original fabric resin sheet) 6 as an original fabric layer formed by melt extrusion molding, pattern printing is performed on one surface by a gravure printing method to form the pattern pattern layer 5. At the same time, the masking layer 7 and the primer layer 8 are sequentially stacked on the other surface. Then, an adhesive layer 4 is provided so as to overlap with the pattern layer 5, and the raw fabric resin sheet 6 and the transparent resin sheet 3 are bonded together via the adhesive layer 4 by a dry laminating method. Finally, after embossed pattern 3a is applied to the surface of transparent resin sheet 3, decorative sheet 1 is obtained by applying surface protective layer 2 so as to cover embossed pattern 3a.

In addition, the production method of the decorative sheet 1 is not limited to the above method. For example, for the pattern layer 5, the offset printing method, the screen printing method, the flexographic printing method, the ink jet printing method in addition to the gravure printing method. Etc. can be formed. About the bonding method of the raw fabric resin sheet 6 and the transparent resin sheet 3, in addition to the dry laminating method, a method using hot pressure or an extrusion laminating method can be used.

Moreover, the resin composition which forms the transparent resin layer 3 in the decorative sheet 1 of each embodiment is prepared by the following method.
First, a method for preparing a nucleating agent vesicle by the supercritical reverse phase evaporation method is as follows: methanol 100 parts by weight, phosphate metal salt nucleating agent (Adeka Stub NA-11, manufactured by ADEKA) as a nucleating agent 82 parts by weight After placing 5 parts by weight of phosphatidylcholine as a substance constituting the outer membrane of the vesicle in a high-pressure stainless steel container kept at 60 ° C. and injecting carbon dioxide so that the pressure becomes 20 MPa, a supercritical state is obtained. Then, 100 parts by weight of ion-exchanged water is injected with vigorous stirring and mixing. After stirring for 15 minutes while maintaining the temperature and pressure in the supercritical state, the nucleating agent is encapsulated in a vesicle having a single-layer outer membrane by discharging carbon dioxide and returning to atmospheric pressure. To obtain a nucleating agent vesicle. When actually forming the transparent resin sheet 3 as the transparent resin layer 3, the pentad fraction is 97.8%, the MFR (melt flow rate) is 15 g / 10 min (230 ° C.), the molecular weight distribution MWD (Mw / Mn ) Is 2.3 in a highly crystalline homopolypropylene resin, hindered phenol antioxidant (Irganox 1010: manufactured by BASF) 500 ppm, benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) 2000 ppm, A high crystal having a thickness of 80 μm is used as a transparent resin layer 3 by extruding a resin added with 2000 ppm of a hindered amine light stabilizer (Kimasorb 944: manufactured by BASF) and 1000 ppm of the nucleating agent vesicle using a melt extruder. A transparent resin sheet 3 made of conductive polypropylene is obtained.

<Effect of 2nd Embodiment and 3rd Embodiment>
(1) The decorative sheet 1 has one or more intermediate layers on one surface of the base material layer B, and has one or more surface protective layers 2 on the intermediate layer. At least one of the surface protective layers 2 contains a dispersant having a hydroxyl group, an amino group or an unsaturated double bond, and inorganic nanoparticles having a particle size in the range of 10 nm to 50 nm, and is inorganic. The nanoparticles are encapsulated in a vesicle having a single layer outer membrane containing a dispersant.

According to this configuration, the inorganic nanoparticles are uniformly dispersed in the resin composition that is the main component of the surface protective layer 2 by suppressing secondary aggregation of extremely small inorganic nanoparticles having a particle size of 10 nm to 50 nm. Therefore, excellent transparency, scratch resistance and post-processability can be imparted. Further, since the dispersant has a hydroxyl group, amino group or unsaturated double bond, the hydroxyl group, amino group or unsaturated double bond and the resin composition which is the main component of the surface protective layer 2 are strong. And the inorganic nanoparticles can be immobilized on the surface of the surface protective layer 2. For this reason, it is possible to provide a decorative sheet 1 that is excellent in scratch resistance by preventing the inorganic nanoparticles from falling off.

(2) The decorative sheet 1 has one or more intermediate layers on one surface of the base material layer, and has one or two or more surface protective layers on the intermediate layer. At least one of the protective layers contains a dispersant having a hydroxyl group, an amino group, or an unsaturated double bond, and inorganic nanoparticles having a particle diameter in the range of 10 nm to 50 nm. It is encapsulated in a vesicle having a monolayer outer membrane made of lipid.
According to this configuration, because of the high dispersibility of the dispersant vesicle, it is possible to uniformly disperse inorganic nanoparticles having a particle size of 10 nm or more and 50 nm or less, so that excellent transparency, scratch resistance, and resistance to scratches can be obtained. Post workability can be imparted. Further, since the dispersant has a hydroxyl group, amino group or unsaturated double bond, the hydroxyl group, amino group or unsaturated double bond and the resin composition which is the main component of the surface protective layer 2 are strong. And the inorganic nanoparticles can be immobilized on the surface of the surface protective layer 2. For this reason, it is possible to provide a decorative sheet 1 that is excellent in scratch resistance by preventing the inorganic nanoparticles from falling off.

(3) In the decorative sheet 1, the main component of the surface protective layer is a curable resin.
According to this configuration, the scratch resistance of the surface protective layer 2 can be improved by curing by crosslinking of the curable resin, and the makeup also has flexibility with excellent post-processing resistance such as V-cut bending. Sheet 1 can be provided.

(4) The decorative sheet 1 has a transparent resin layer mainly composed of crystalline polypropylene resin as a layer constituting the intermediate layer, and the transparent resin layer is included in a vesicle having an outer film of a single layer film. Containing a nucleating agent.
According to this structure, the decorative sheet 1 provided with the transparent resin layer 3 having excellent transparency, scratch resistance, and post-processing resistance can be provided.

[Second Embodiment]
Examples of the second embodiment and the third embodiment will be described below.

<Preparation of inorganic nanoparticle vesicles>
First, a method for preparing inorganic nanoparticle vesicles used in the following examples will be described. Inorganic nanoparticle vesicles are prepared by supercritical reverse phase evaporation. First, 100 parts by weight of methanol, 64 parts by weight of silica nanoparticles having a particle diameter of 40 nm as inorganic nanoparticles (AEROSIL OX50, manufactured by Evonik), and a dispersant having a hydroxyl group. 6 parts by weight of alcohol-modified silicone oil (XF42-B0970, manufactured by Momentive Performance Materials) and 5 parts by weight of phosphatidylcholine as a phospholipid constituting the outer membrane of the vesicle are placed in a high-pressure stainless steel container kept at 60 ° C. The container is sealed, and carbon dioxide is injected into the container so that the pressure becomes 20 MPa to obtain a supercritical state. Thereafter, the inside of the container is vigorously stirred and 100 parts by weight of ion exchange water is injected. After stirring and mixing for another 15 minutes while maintaining the temperature and pressure in a supercritical state, carbon dioxide is discharged from the container and returned to atmospheric pressure to provide a monolayer outer membrane (including a dispersant) made of phospholipid. Inorganic nanoparticle vesicles containing inorganic nanoparticles in vesicles were obtained. In addition, the above dispersant is 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group, or 3-aminopropyl as a dispersant having an unsaturated double bond. By changing to methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), an inorganic nanoparticle vesicle encapsulated in a vesicle having an outer membrane containing a dispersant having each reactive group is obtained. Can do.

<Preparation of dispersant vesicle>
Moreover, the preparation method of the dispersing agent vesicle used in the following Examples and Comparative Examples will be described. Dispersant vesicles were prepared by supercritical reverse phase evaporation. First, 100 parts by weight of methanol, 70 parts by weight of alcohol-modified silicone oil (XF42-B0970, manufactured by Momentive Performance Materials) as a dispersant having a hydroxyl group, 5 parts by weight of phosphatidylcholine as a phospholipid constituting the outer membrane is put in a high-pressure stainless steel container kept at 60 ° C. and sealed, and carbon dioxide is injected into the container so that the pressure becomes 20 MPa. To do. Thereafter, the inside of the container is vigorously stirred and 100 parts by weight of ion exchange water is injected. Dispersion having a hydroxyl group in a vesicle having a monolayer outer membrane made of phospholipid by discharging the carbon dioxide from the container and returning to atmospheric pressure after stirring and mixing for 15 minutes while maintaining the temperature and pressure in a supercritical state. Dispersant vesicles containing the agent were obtained. In addition, the above dispersant is 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group, or 3-aminopropyl as a dispersant having an unsaturated double bond. By changing to methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), a dispersant vesicle containing a dispersant having each reactive group can be obtained.

<Preparation of nucleating agent vesicle>
Furthermore, the preparation method of the nucleating agent vesicle added to the transparent resin layer 3 in the following Examples and Comparative Examples will be described. The nucleating agent vesicle is prepared by supercritical reverse phase evaporation, first 100 parts by weight of methanol, 82 parts by weight of a phosphate ester metal salt nucleating agent (Adeka Stub NA-11, manufactured by ADEKA) as a nucleating agent, After placing 5 parts by weight of phosphatidylcholine as a substance constituting the outer membrane in a high-pressure stainless steel container kept at 60 ° C. and sealing it, and injecting carbon dioxide so that the pressure becomes 20 MPa, While stirring and mixing, 100 parts by weight of ion exchange water is injected. A nucleating agent for a vesicle having a monolayer outer membrane made of phospholipid by stirring for 15 minutes while maintaining the temperature and pressure in a supercritical state and then discharging carbon dioxide to return to atmospheric pressure. A nucleating agent vesicle encapsulating is obtained.

<Preparation of transparent resin layer 3 added with nucleating agent vesicle and method for film formation>
Hereinafter, the detailed preparation method of the resin composition which forms the transparent resin layer 3 which added said nucleating agent vesicle and the film forming method of the transparent resin sheet 3 are demonstrated.
The resin composition forming the transparent resin layer 3 has a high pentad fraction of 97.8%, MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and molecular weight distribution MWD (Mw / Mn) of 2.3. Hindered phenolic antioxidant (Irganox 1010: manufactured by BASF) 500 ppm, benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) 2000 ppm, and hindered amine light stabilization for crystalline homopolypropylene resin An agent (Kimasorb 944: manufactured by BASF) 2000 ppm and the nucleating agent vesicle 1000 ppm are used. The resin composition was melted and extruded using a melt extruder to form a transparent resin sheet 3 having a thickness of 100 μm to be used as the transparent resin layer 3.

<Example 2-1>
In Example 2-1, the particle size of the vesicle having a monolayer film containing a dispersant having an amino group with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle was added. The decorative sheet 1 was provided with a surface protective layer 2 formed of a resin composition in which 0.05 part by weight of inorganic nanoparticle vesicles containing 40 nm inorganic nanoparticles was added to 100 parts by weight of a thermosetting resin.

Specifically, both surfaces of the transparent resin sheet 3 as the transparent resin layer 3 to which the above-described nucleating agent vesicle is added are subjected to corona treatment so that the wetting tension becomes 40 dyn / cm or more. In addition, on one side of a base material layer (raw fabric resin sheet) 6 as a concealing 70 μm original fabric layer, the binder resin content of a two-component urethane ink (V180, manufactured by Toyo Ink Manufacturing Co., Ltd.) On the other hand, the pattern layer 5 was formed by a gravure printing method using an ink added with 0.5 part by weight of a hindered amine light stabilizer (Kimasorb 944, manufactured by BASF). In addition, a primer layer 8 was formed on the other surface of the raw fabric resin sheet 6. Thereafter, an adhesive for dry lamination (Takelac A540, manufactured by Mitsui Chemicals, Inc .; application amount 2 g / m ² ) as an adhesive layer 4 is laminated so as to overlap the pattern layer 5, and the adhesive layer 4 is interposed therebetween. The raw fabric resin sheet 6 and the transparent resin sheet 3 were bonded together by a dry laminating method. Moreover, after embossing pattern 3a is given to the surface of the transparent resin sheet 3, it is an inorganic nanoparticle with respect to 100 weight part of 2 liquid-curing-type urethane topcoats (W184, the product made by DIC graphics) which is a thermosetting resin. The embossed pattern 3a is covered at a coating amount of 15 g / m ² with a resin composition containing 0.05 parts by weight of the inorganic nanoparticle vesicle prepared using silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik). Thus, the surface protective layer 2 was formed. In this way, a decorative sheet 1 of this example shown in FIG. 1 having a total thickness of 200 μm was obtained.

<Example 2-2>
In Example 2-2, a vesicle comprising a single layer film containing a dispersant having an unsaturated double bond on the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added. Formed by adding a resin composition in which 0.05 part by weight of an inorganic nanoparticle vesicle encapsulating inorganic nanoparticles having a particle diameter of 40 nm is added to a mixed resin of 60 parts by weight of a thermosetting resin and 40 parts by weight of a photocurable resin. A decorative sheet 1 having a surface protective layer 2 was obtained.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. DIC graphics) 60 parts by weight and photocurable urethane acrylate (Unidic 17-824-9, manufactured by DIC Graphics) 40 parts by weight, which is a photocurable resin. The resin composition containing 0.05 part by weight of the inorganic nanoparticle vesicle prepared using silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik Co., Ltd.) as nanoparticles is shown in FIG. A decorative sheet 1 was obtained.

<Example 2-3>
In Example 2-3, a vesicle having a monolayer film containing a dispersant having an amino group on the surface of the transparent resin layer 3 (transparent resin sheet 3) to which no nucleating agent is added has a particle diameter of 40 nm. The decorative sheet 1 was provided with a surface protective layer 2 formed of a resin composition in which 0.05 part by weight of inorganic nanoparticle vesicles containing inorganic nanoparticles was added to 100 parts by weight of a thermosetting resin.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the transparent resin sheet 3 has a pentad fraction of 97.8%, MFR (melt flow rate). Is a hindered phenolic antioxidant (Irganox 1010, manufactured by BASF) 500 ppm for a highly crystalline polypropylene resin having a molecular weight distribution MWD (Mw / Mn) of 2.3, 15 g / 10 min (230 ° C.), While using a resin composition to which 2000 ppm of a benzotriazole-based ultraviolet absorber (Tinuvin 328, manufactured by BASF) and 2000 ppm of a hindered amine light stabilizer (Kimasorb 944, manufactured by BASF) was used, as the surface protective layer 2, Two-part curable urethane topcoat (W184, manufactured by DIC Graphics), which is a curable resin 10 Using a resin composition in which 0.05 part by weight of the inorganic nanoparticle vesicle prepared using silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik Co., Ltd.) as inorganic nanoparticles is used with respect to parts by weight. A decorative sheet 1 of this example shown in FIG.

<Example 2-4>
In Example 2-4, a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added. A surface protective layer 2 formed of a resin composition in which 0.005 part by weight of a dispersant vesicle encapsulating and 0.05 part by weight of inorganic nanoparticles having a particle diameter of 40 nm are added to 100 parts by weight of a thermosetting resin. A decorative sheet 1 was obtained.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. The above-mentioned dispersant vesicle prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of DIC Graphics) A decorative sheet 1 of this example shown in FIG. 1 was obtained using a resin composition to which 0.005 parts by weight and 0.05 parts by weight of silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik) were added.

<Example 2-5>
In Example 2-5, an unsaturated double bond was formed on the vesicle having a monolayer film made of phospholipid on the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle was added. Addition of 0.005 part by weight of a dispersant vesicle encapsulating a dispersing agent and 0.05 part by weight of inorganic nanoparticles having a particle diameter of 40 nm to a mixed resin of 60 parts by weight of a thermosetting resin and 40 parts by weight of a photocurable resin It was set as the decorative sheet 1 provided with the surface protection layer 2 formed with the made resin composition.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. DIC Graphics Co., Ltd.) and 60 parts by weight of photocurable urethane acrylate (Unidic 17-824-9, manufactured by DIC Graphics Co., Ltd.), which is a photocurable resin, are mixed. Silica nanoparticle having 0.005 parts by weight of the above-mentioned dispersant vesicle and 40 nm particle diameter prepared using 3-methacryloxypropyltrimethoxysilane (KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having a saturated double bond A decorative sheet of the present embodiment shown in FIG. 1 using a resin composition to which 0.05 parts by weight of particles (AEROSIL OX50, manufactured by Evonik) was added. It was obtained.

<Example 2-6>
In Example 2-6, a dispersant having an amino group is included in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which no nucleating agent is added. A decorative sheet comprising a surface protective layer 2 formed of a resin composition obtained by adding 0.005 part by weight of the dispersant vesicle and 0.05 part by weight of inorganic nanoparticles having a particle diameter of 40 nm to 100 parts by weight of a thermosetting resin It was set to 1.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. The above-mentioned dispersant vesicle prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of DIC Graphics) A decorative sheet 1 of this example shown in FIG. 1 was obtained using a resin composition to which 0.005 parts by weight and 0.05 parts by weight of silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik) were added.

<Comparative Example 2-1>
In Comparative Example 2-1, the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle was added, 0.005 parts by weight of a dispersant having an amino group and an inorganic nanoparticle having a particle diameter of 40 nm. A decorative sheet 1 including a surface protective layer 2 formed of a resin composition in which 0.05 part by weight of the particles was added to 100 parts by weight of a thermosetting resin was obtained.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. (Manufactured by DIC Graphics) 100 parts by weight of 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group and particle size A decorative sheet 1 of this comparative example shown in FIG. 1 was obtained using a resin composition to which 0.05 parts by weight of 40 nm silica nanoparticles (AEROSIL OX50, manufactured by Evonik) was added.

<Comparative Example 2-2>
In Comparative Example 2-2, a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added. A surface protective layer 2 formed of a resin composition in which 0.005 part by weight of a dispersant vesicle encapsulating and 0.05 part by weight of inorganic fine particles having a particle diameter of 4.5 μm are added to 100 parts by weight of a thermosetting resin. It was set as the decorative sheet 1 provided.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. The above-mentioned dispersant prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of 100 parts by weight of DIC Graphics) A decorative sheet 1 of this comparative example shown in FIG. 1 is prepared using a resin composition to which 0.005 part by weight of vesicle and 0.05 part by weight of silica fine particles (AEROSIL OX50, manufactured by Evonik) having a particle diameter of 4.5 μm are added. Obtained.

<Comparative Example 2-3>
In Comparative Example 2-3, a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added. The surface protective layer 2 is formed of a resin composition in which 0.0001 part by weight of a dispersant vesicle encapsulating and 0.001 part by weight of inorganic nanoparticles having a particle diameter of 40 nm are added to 100 parts by weight of a thermosetting resin. A decorative sheet 1 was obtained.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. The above-mentioned dispersant prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of 100 parts by weight of DIC Graphics) A decorative sheet 1 of this comparative example shown in FIG. 1 was obtained using a resin composition to which 0.0001 part by weight of vesicle and 0.001 part by weight of silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik) were added. .

<Comparative Example 2-4>
In Comparative Example 2-4, a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added. A decorative sheet provided with a surface protective layer 2 formed of a resin composition in which 2.5 parts by weight of a dispersant vesicle encapsulating and 25 parts by weight of inorganic nanoparticles having a particle diameter of 40 nm are added to 100 parts by weight of a thermosetting resin It was set to 1.

Specifically, the basic structure of each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin. The above-mentioned dispersant prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of 100 parts by weight of DIC Graphics) A decorative sheet 1 of this comparative example shown in FIG. 1 was obtained using a resin composition to which 2.5 parts by weight of vesicles and 25 parts by weight of silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik) were added.

<Evaluation>
Each decorative sheet 1 obtained in Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4 was bonded to the wooden base material B using a urethane-based adhesive, and then visually. The surface transparency, the Hoffman scratch test and the steel wool rubbing test were used to determine the surface hardness and the V-groove bending workability test was evaluated. The obtained evaluation results are shown in Table 2.

<Hoffman scratch test>
The Hoffman scratch test of the present example is the same as the Hoffman scratch test described in the example of the first embodiment. Therefore, the description of this test is omitted here.
<Steel wool rubbing test>
The steel wool rubbing test of this example is the same as the steel wool rubbing test described in the example of the first embodiment. Therefore, the description of this test is omitted here.
<V-groove bending test>
The V-groove bending test of the present example is the same as the V-groove bending test described in the example of the first embodiment. Therefore, the description of this test is omitted here.

Explanation of symbols in the evaluation results of Table 2 is as follows.
◎: Very good transparency, scratch resistance or post-processing resistance ○: Good transparency, scratch resistance or post-processing resistance ×: Transparency, scratch resistance or post-processing resistance Inferior

In the decorative sheets 1 of Examples 2-1 to 2-6, as shown in Table 2, the transparency was good, and good results were also obtained in the Hoffman scratch test, the steel wool test, and the V-groove bending test. Obtained.
This is because, in the decorative sheets 1 of Examples 2-1 to 2-6, the inorganic nanoparticles can be uniformly dispersed by adding inorganic nanoparticle vesicles or dispersant vesicles to the surface protective layer 2. This is probably because the surface hardness was improved due to the inorganic nanoparticles while maintaining good transparency and post-processing suitability required for the decorative sheet.

On the other hand, the decorative sheet 1 of Comparative Example 2-1 has a post-processing suitability required for the decorative sheet 1, but uses a non-vesicle dispersant for the surface protective layer 2. Further, it is considered that the dispersibility of the inorganic nanoparticles was not sufficiently obtained, and the transparency and scratch resistance required for the decorative sheet could not be obtained. Further, in the decorative sheet 1 of Comparative Example 2-2, since the particle diameter of the inorganic fine particles is too large, irregularities are formed on the surface of the surface protective layer 2 and the transparency is impaired. It is considered that the fine particles were not sufficiently bonded, resulting in poor scratch resistance and post-working resistance. Further, the decorative sheet 1 of Comparative Example 2-3 has the transparency and post-processing suitability required for the decorative sheet 1, but the amount of dispersant vesicle added and the amount of inorganic nanoparticles added are extremely small. Therefore, it is considered that the result was inferior in scratch resistance. Further, the decorative sheet 1 of Comparative Example 2-4 has post-processing suitability required for the decorative sheet 1, but the addition amount of the dispersant vesicle and inorganic nanoparticles was extremely large. The result is inferior in transparency, and the scratch resistance is considered to be inferior because the abrasive wear occurs due to the inorganic nanoparticles falling off during friction.

From the above evaluation results, the decorative sheet 1 of the present invention shown in Examples 2-1 to 2-6 has the transparency required for the decorative sheet, and is extremely excellent in scratch resistance and post-processing resistance. It became clear that it was a sheet.

[Reference example]
Hereinafter, decorative sheets other than the decorative sheets described in the second embodiment and the third embodiment will be briefly described as reference examples of the present invention.
In recent years, for example, in JP-A-2-128843, JP-A-4-083664, JP-A-6-001881, JP-A-6-198831, JP-A-9-328562, JP-A-3722634. As shown, many decorative sheets using olefin-based resins have been proposed as decorative sheets that replace polyvinyl chloride decorative sheets.
However, these decorative sheets do not use vinyl chloride resin, so that the generation of toxic gases at the time of incineration is suppressed. However, since general polypropylene sheets or soft polypropylene sheets are used, the surface is resistant to scratches. The conventional polyvinyl chloride decorative sheet was much inferior in scratch resistance.

Accordingly, the present inventors have proposed a decorative sheet having excellent surface scratch resistance and post-processing resistance described in Japanese Patent No. 3772634 in order to eliminate these drawbacks. Thereafter, the use of the decorative sheet using the decorative sheet having the structure as shown in the above-mentioned Japanese Patent No. 3772634 has been increasingly expanded, and further improvement in post-process resistance such as surface scratch resistance and V-groove bending. It has been demanded.
Moreover, since consumers' consciousness about quality has also advanced, not only the above-mentioned functionality but high designability is also required.
The decorative sheet of the present invention is not limited to the above embodiments and examples, and various modifications can be made without departing from the characteristics of the invention.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Surface protective layer 3 Transparent resin layer 4 Adhesive layer 5 Picture pattern layer 6 Base material layer 7 Concealing layer 8 Primer layer B Base material

Claims (12)

1. A decorative sheet having one or two or more intermediate layers on one surface of a base material layer, and having one or more surface protective layers on the intermediate layer,
   The main component of the surface protective layer of each of the above layers is a curable resin,
   At least one of the one or two or more surface protective layers contains a dispersant and inorganic nanoparticles,
   A decorative sheet, wherein both the dispersant and the inorganic nanoparticles are encapsulated in a vesicle.
2. 2. The decorative sheet according to claim 1, wherein the dispersant and the inorganic nanoparticles are vesicled in a form of being encapsulated in a liposome having an outer membrane made of phospholipid.
3. 3. The decorative sheet according to claim 1, wherein the dispersant has a hydroxyl group or an amino group.
4. The decorative sheet according to claim 1 or 2, wherein the dispersant has an unsaturated double bond.
5. A decorative sheet having one or two or more intermediate layers on one surface of a base material layer, and having one or more surface protective layers on the intermediate layer,
   At least one of the one or two or more surface protective layers is composed of a dispersant having a hydroxyl group, an amino group or an unsaturated double bond, and inorganic nanoparticles having a particle diameter of 10 nm to 50 nm. Containing
   A decorative sheet, wherein the inorganic nanoparticles are encapsulated in a vesicle having a single-layer outer membrane containing the dispersant.
6. A decorative sheet having one or two or more intermediate layers on one surface of a base material layer, and having one or more surface protective layers on the intermediate layer,
   At least one of the one or two or more surface protective layers comprises a dispersant having a hydroxyl group, an amino group, or an unsaturated double bond, and inorganic nanoparticles having a particle size in the range of 10 nm to 50 nm. Contains,
   A decorative sheet, wherein the dispersant is encapsulated in a vesicle having a monolayer outer membrane made of phospholipid.
7. The decorative sheet according to claim 5 or 6, wherein the main component of the surface protective layer of each layer is a curable resin.
8. As a layer constituting the intermediate layer, it has a transparent resin layer mainly composed of crystalline polypropylene resin,
   The decorative sheet according to any one of claims 1 to 7, wherein the transparent resin layer contains a nucleating agent contained in a vesicle.
9. A method for producing a decorative sheet according to any one of claims 1 to 4,
   A method for producing a decorative sheet, wherein the vesicle encapsulates the dispersant and the inorganic nanoparticles by a supercritical reverse phase evaporation method.
10. A method for producing a decorative sheet according to claim 5,
    A method for producing a decorative sheet, comprising encapsulating the inorganic nanoparticles in the vesicle by a supercritical reverse phase evaporation method.
11. It is a manufacturing method of the decorative sheet according to claim 6,
    A method for producing a decorative sheet, wherein the dispersant is encapsulated in the vesicle by a supercritical reverse phase evaporation method.
12. The layer constituting the intermediate layer is a transparent resin layer mainly composed of crystalline polypropylene resin,
    The method for producing a decorative sheet according to any one of claims 9 to 11, wherein the transparent resin layer contains a nucleating agent encapsulated in the vesicle.

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