JP2017177807A - Decorative sheet and manufacturing method of decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having excellent scratch resistance, abrasion resistance and post-processing resistance while ensuring high transparency in a surface protective layer, and a method for producing the same. A decorative sheet 1 has one layer or two or more intermediate layers on one surface of a base material layer 6, and has one or two or more surface protective layers 2 on the intermediate layers. In the decorative sheet 1, the main component of the surface protective layer 2 of each of the above layers is a curable resin, and at least one of the one layer or two or more layers of the surface protective layer 2 is a dispersant and inorganic nanoparticles. And its dispersant and inorganic nanoparticles are both encapsulated in the vesicle. [Selection diagram] Fig. 1

Description

  The present invention relates to a building material used for exterior and interior of a building, a surface of a fitting, a surface sheet of a household appliance, and a method for manufacturing the decorative sheet.

Conventionally, for the purpose of imparting physical properties such as scratch resistance, stain resistance and impact resistance to the surface protective layer forming the surface layer of the decorative sheet, a thermosetting resin (for example, a two-component curable resin) A curable resin represented 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, a matting agent such as silica particles is included in the surface protective layer for the purpose of imparting a matte appearance to the decorative sheet.

  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 decorative sheets is increasing more and more, and improvement in scratch resistance, wear resistance and post-processing resistance is required.

Japanese Patent No. 5573986 JP 2012-187922 A

  The present invention pays attention to the above points, and provides a decorative sheet excellent in scratch resistance, abrasion resistance and post-processing resistance while ensuring transparency in the surface protective layer, and a method for producing the decorative sheet The purpose is to provide.

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.

  In order to solve the problem, the decorative sheet according to another aspect of the present invention has one or two or more intermediate layers on one surface of the base material layer, and one layer on the intermediate layer. Or a decorative sheet having two or more surface protective layers, 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 provided. The curable resin is formed by adding a dispersant and inorganic nanoparticles, and both the dispersant and the inorganic nanoparticles are encapsulated in a vesicle.

  In order to solve the problem, the method for producing a decorative sheet which is one embodiment of the present invention has one or more intermediate layers on one surface of the base material layer, and the intermediate layer is formed on the intermediate layer. It has one or two or more surface protective layers, 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 A method for producing a decorative sheet comprising a dispersant and inorganic nanoparticles, wherein both the dispersant and the inorganic nanoparticles are encapsulated in a vesicle, wherein the dispersant and the inorganic nanoparticles are obtained by a supercritical reverse phase evaporation method. It is characterized by being included in a vesicle.

  In order to solve the problem, a method for producing a decorative sheet according to another aspect of the present invention has one or more intermediate layers on one surface of a base material layer, 1 layer or two or more surface protective layers, 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, A method for producing a decorative sheet, which is formed by adding a dispersant and inorganic nanoparticles to the curable resin, and in which both the dispersant and the inorganic nanoparticles are encapsulated in a vesicle, comprising a supercritical reverse phase evaporation method The dispersion agent and the inorganic nanoparticles are included in a vesicle.

According to the aspect 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-processing resistance. Become.
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 embodiment based on this invention.

Next, embodiments 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. Further, the embodiment described 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 the component parts 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.

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.

In addition, the layer thickness of the decorative sheet 1 having the above-described configuration is, for example, 3 to 20 μm for the surface protective layer 2, 20 to 200 μm for the transparent resin layer 3, 20 μm, the pattern layer 5 is 3 to 20 μm, the base material 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. Examples of paper include thin paper, titanium paper, resin-impregnated paper, organic or inorganic nonwoven fabric, and synthetic paper. Examples of the resin for 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, and ethylene-propylene copolymer. Examples of the rubber include polymer 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, and there are lamination methods such as thermal lamination, extrusion lamination, and dry lamination. Adhesives are appropriately selected from acrylic, polyester, polyurethane, and epoxy. You can choose. 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.
Examples of transparent polyolefin resins include polypropylene, polyethylene, polybutene and the like, as well as α-olefins (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-tetrade Or the like, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene, etc.・ 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. In the present embodiment, the nucleating agent in the resin constituting the transparent resin layer 3 may be encapsulated in a vesicle with a part of the nucleating agent exposed.

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.
In addition, it is preferable that the said nucleating agent is contained within the range of 0.01-1.0 mass part with respect to 100 mass parts of crystalline polypropylene resin which forms the transparent resin layer 3. FIG. If content of a nucleating agent is in the said range, the transparency of the transparent resin layer 3 will increase more.

Various additions such as an existing heat stabilizer, ultraviolet absorber, light stabilizer, anti-blocking agent, catalyst scavenger, colorant, light scattering agent and gloss adjusting agent are added to the transparent resin layer 3 as necessary. An agent can also be added.
Although there is no restriction | limiting in particular also in the lamination | stacking method of the transparent resin layer 3, The method which applied the hot pressure, the extrusion lamination method, the dry lamination method, etc. 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 in which the transparent resin layer 3 embossed simultaneously with the extrusion and the raw fabric layer 6 are bonded together by heat or dry lamination. The position where the pattern layer 5 and the adhesive layer 4 are applied may be on the raw fabric layer 6 side as usual, or on the transparent resin layer 3 side.

  The decorative sheet according to the present embodiment based on the present invention is a decorative sheet including a raw fabric layer made of a resin composition containing an olefin resin as a main component, and the raw fabric layer contains an ultraviolet absorber. In particular, the ultraviolet absorber is added to the resin composition constituting the raw fabric layer in the state of the ultraviolet absorber vesicle included in the outer membrane (vesicle).

  As described above, one of the features (invention specific matter) of the decorative sheet of the present embodiment is that “the transparent resin layer contains a nucleating agent contained in a vesicle”. Then, by adding the nucleating agent to the resin composition in a state where the nucleating agent is encapsulated in the vesicle, there is an effect that the dispersibility of the nucleating agent in the resin material, that is, in the transparent resin layer is drastically improved. It can be said that it is impractical to specify the characteristics directly by the structure and characteristics of the object in the state of the finished decorative sheet, because it may be difficult depending on the situation. The reason is as follows. The nucleating agent added in the state of vesicle is in a dispersed state having high dispersibility, and the nucleating agent is highly dispersed in the transparent resin layer even in the state of the produced decorative sheet. . However, after the nucleating agent is added to the resin composition constituting the transparent resin layer in the form of a vesicle to produce the transparent resin layer, the decorative sheet is usually produced by a compression treatment or curing to the laminate. Various treatments such as treatment are performed, but by such treatment, the outer membrane of the vesicle encapsulating the nucleating agent is crushed or chemically reacted, and the nucleating agent is not included (encapsulated) in the outer membrane. This is because the possibility that the outer membrane is crushed or chemically reacted varies depending on the process of the decorative sheet. In situations where this nucleating agent is not included in the outer membrane, it is difficult to specify the physical properties themselves in the numerical range, and whether the crushed outer membrane constituent material is the outer membrane of the vesicle. It may be difficult to determine whether the material is added separately from the nucleating agent. Thus, although the present invention is different from the conventional one in that the nucleating agent is blended in a highly dispersed state, whether or not it is because it is added in the state of a vesicle encapsulating the nucleating agent is a cosmetic. In the state of the sheet, it may be impractical to specify the structure and characteristics within the numerical range analyzed based on the measurement.

<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, and cleanability. 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 an anti-mold agent, a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye or a pigment, a solvent, or the like, if 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 for 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, the main component of the surface protective layer 2 is preferably a urethane-based one using isocyanate from the viewpoints of workability, cost, cohesion of the resin itself, and the like. Isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), methylhexane diisocyanate (HTDI), Although it can be appropriately selected from methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc., in view of 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 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 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.

The amount of the 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. When the added amount of the inorganic nanoparticles is within the above range, the transparency, scratch resistance, wear resistance and post-working resistance of the surface protective layer 2 are further enhanced.
Moreover, the compounding quantity of the vesicle in that case will be a ratio of 0.00535-21.4 mass parts with respect to 100 mass parts of resin compositions.
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 produced nanoparticles 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 polycarboxylic acids, polycarboxylic acid alkylamines, polyoxyethylene alkyl ethers, polymer surfactants such as sorbitan fatty acid esters, oleic acid, Fatty acid metal salts in which fatty acids such as linoleic acid, γ-linolenic acid, linolenic acid and the like 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-acrylo Silane coupling agents such as cyclopropyltrimethoxysilane, hydrogen tetrakis [2,2-bis [(allyloxy) methyl] butan-1-olato-O1] bis (ditridecyl phosphito-O '') titanate (2-), Titanium and titanate coupling agents such as bis (isooctadecanoato-kO) bis (2-propanolato)-(9CI), waxes obtained by thermally decomposing polyolefins and further oxidizing them.

  In addition, there exists a preferable combination in nature between the curable resin and the dispersant. 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.

  As described above, one of the features (invention specific matter) of the decorative sheet of the present embodiment is that “at least one of the surface protective layers of one layer or two or more layers includes a dispersant and inorganic nanoparticles. And the dispersant and the inorganic nanoparticles are both encapsulated in the vesicle. The effect of dramatically improving the dispersibility of the inorganic nanoparticles in the resin material, that is, in the surface protective layer, is added to the resin composition in a state where the dispersant and the inorganic nanoparticles are encapsulated in the vesicle. However, it can be said that it is impractical to specify the characteristics directly with the structure and characteristics of the object in the state of the finished decorative sheet, which may be difficult depending on the situation. The reason is as follows. The dispersant and inorganic nanoparticles added in the state of vesicles are dispersed with high dispersibility, and even in the state of the prepared decorative sheet, the inorganic nanoparticles are highly dispersed in the surface protective layer. Has been. However, after the preparation of the surface protective layer after adding the dispersant and inorganic nanoparticles in the state of vesicles to the resin composition constituting the surface protective layer, the decorative sheet is usually compressed into a laminate. Various treatments such as treatment and curing treatment are performed. By such treatment, the outer membrane of the vesicle encapsulating the dispersant and the inorganic nanoparticles is crushed or chemically reacted, so that the dispersant and the inorganic nanoparticles are removed. This is because there is a high possibility that the outer membrane is not embraced (foreskin) by the membrane, and the state in which the outer membrane is crushed or chemically reacted varies depending on the process of the decorative sheet. And, in the situation where the dispersant and inorganic nanoparticles are not included in the outer membrane, it is difficult to specify the physical properties themselves in the numerical range, and the constituent material of the crushed outer membrane is outside the vesicle. It may be difficult to determine whether the material is a film or a material added separately from the dispersant and the inorganic nanoparticles. As described above, the present invention has a difference in that the inorganic nanoparticles are blended with high dispersion as compared with the conventional one, but whether or not it is added in the state of a vesicle enclosing the dispersant and the inorganic nanoparticles. However, in the state of the decorative sheet, it may be impractical to specify the structure and characteristics in the numerical range analyzed based on the measurement.

<Vesicle formation of dispersant and inorganic nanoparticles>
The vesicle formation of the dispersant and the inorganic nanoparticles 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, or the supercritical reverse phase evaporation method. 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. More specifically, in the present embodiment, the dispersant and the inorganic nanoparticles in the resin constituting the surface protective layer 2 are encapsulated in the vesicle with a part of at least one of the dispersant and the inorganic nanoparticles exposed. May be. In addition, the dispersant and the inorganic nanoparticles in the resin constituting the surface protective layer 2 have an outer membrane made of phospholipid, which will be described later, with a part of at least one of the dispersant and the inorganic nanoparticles exposed. It may be encapsulated in liposomes.
Hereinafter, the vesicle treatment will be briefly described. In the Bangham method, chloroform or a chloroform / methanol mixed solvent is placed in a container such as a flask, and phospholipid is further dissolved therein. Thereafter, the solvent is removed using an evaporator to form a thin film 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.

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

  Examples of phospholipids constituting vesicles include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated yolk lecithin, soybean lecithin, hydrogenated soybean lecithin and the like. Examples include sphingophospholipids such as glycerophospholipid, sphingomyelin, 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 the 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, or a polyvinyl butyral resin. A nitrocellulose-based resin can be used, and these resins can be used alone or mixed to form an adhesive composition, which can be formed using an appropriate coating 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, particularly preferably formed of a resin composed of a copolymer of an acrylic resin and a urethane resin and an isocyanate.

<Effect of this embodiment>
(1) The decorative sheet 1 is a decorative sheet 1 composed of a single layer or a plurality of layers, and has at least one surface protective layer 2 to which a vesicle-formed dispersant and inorganic nanoparticles are added. In the treatment), both the dispersant and the inorganic nanoparticles are vesicled such as encapsulated in liposomes. Note that the dispersant and the inorganic nanoparticles may be vesicles such as being encapsulated in liposomes with at least a part of at least one of the dispersant and the inorganic nanoparticles exposed.
According to this configuration, the scratch resistance can be improved by adding inorganic 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 As a result, the secondary aggregation of the inorganic nanoparticles can be suppressed and uniformly dispersed in the resin constituting the surface protective layer 2, so that higher transparency can be ensured.

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 becomes possible to improve the deterioration of the scratch resistance due to 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 becomes possible to improve the deterioration of 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. Note that the nucleating agent added to the transparent resin layer 3 may be vesicled with a part of the nucleating agent exposed.
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. Since the dispersibility is significantly improved, the scratch resistance can be improved while maintaining the transparency.

Next, examples of the present invention will be described.
In addition, the layer structure of the decorative sheet 1 described below is the same as that of the above-described embodiment.
<Example 1>
In Example 1, the surface of the transparent resin layer 3 to which the nucleating agent liposome was not added, both the dispersant having no reactive group and the inorganic nanoparticles were nano-treated by the Bangham method, 0.05 part by mass of the liposome encapsulated in the capsule composed of 100 parts by mass of the thermosetting resin constituting the surface protective layer 2 to form the surface protective layer 2, and the decorative sheet of Example 1 did.

  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, 500 ppm of hindered phenolic antioxidant (Irganox 1010: manufactured by BASF), 2000 ppm of benzotriazole-based ultraviolet absorber (manufactured by BASF), hindered amine light stabilizer (Kimasorb 944: BASF) The resin added with 2000 ppm was extruded using a melt extruder to form a transparent resin sheet made of a high crystalline polypropylene having a thickness of 100 μm to be used as the transparent resin layer 3. The both sides of the 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 A pattern printing layer 5 is provided by carrying out a 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) is added. A primer layer 8 was provided on the other surface of the substrate.
Thereafter, on one surface side of the base material layer 6, a transparent resin sheet is passed through an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc .; application amount 2 g / m ² ) as the adhesive layer 4. Were bonded together 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 ink obtained by blending 0.05 parts by mass to form a surface protective layer 2 was coated with coating thickness 15 g / m ^2, and the decorative sheet 1 of example 1. The total thickness of the decorative sheet 1 is 200 μm.

<Example 2>
In Example 2, the surface of the transparent resin layer 3 not added with the nucleating agent liposome is composed of a phospholipid in which both the dispersant having an amino group and the inorganic nanoparticles are nano-treated by the Bangham method. 0.05 parts by mass of the liposome encapsulated in 100 parts by mass of the thermosetting resin constituting the surface resin layer was added to form the surface protective layer 2 to obtain a decorative sheet 1 of Example 2.
Others were produced in the same manner as in Example 1 to obtain a decorative sheet 1 of Example 2.

<Example 3>
In Example 3, the surface of the transparent resin layer 3 to which the nucleating agent liposome was not added, both the dispersant having an unsaturated double bond and the inorganic nanoparticles were nano-treated by the Bangham method. 0.05 parts by mass of liposomes encapsulated in lipid capsules are added to 100 parts by mass of the curable resin constituting the surface resin layer to form the surface protective layer 2, and the decorative sheet 1 of Example 3 did. 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 in Example 1 to obtain a decorative sheet 1 of Example 3.

<Example 4>
In Example 4, the surface of the transparent resin layer 3 to which the nucleating agent liposome was added was dispersed in a phospholipid capsule in which both the dispersant and inorganic nanoparticles having an amino group were nanonized by the Bangham method. The encapsulated liposome was added to 0.05 parts 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, thereby obtaining a decorative sheet 1 of Example 4.
Specifically, a resin composition for forming the transparent resin layer 3 described below is 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 4 was obtained in the same manner as Example 2.

Here, nucleation of the nucleating agent was performed as follows.
"Preparation of nucleating agent liposomes"
Moreover, the vesicle formation of the nucleating agent added to the transparent resin layer 3 in the examples will be described. The nucleation of the nucleating agent is carried out 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 the 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>
Below, 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) 500PPM, benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) 2000PPM, and hindered amine light stabilization for crystalline homopolypropylene resin Agent (Kimasorb 944: manufactured by BASF) 2000PPM and the nucleating agent liposome 1000PPM 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 5>
In Example 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, 0.05 part by mass of the liposome encapsulated in the capsule consisting of 100 parts by mass of the thermosetting resin constituting the surface resin layer to form the surface protective layer 2, and the decorative sheet 1 of Example 5 did. Otherwise, the decorative sheet 1 of Example 5 was obtained in the same manner as Example 4.
Here, the vesicle formation of the inorganic nanoparticles and the dispersant was performed as follows.

That is, the preparation of a vesicle encapsulating both inorganic nanoparticles and a dispersant was performed with respect to 100 parts by mass of hexane, 70 parts by mass of inorganic nanoparticles, and 0.07 parts by mass of a dispersant with respect to a high-pressure stainless steel container maintained at 60 ° C. And 5 parts by mass of phosphatidylcholine as phospholipid are sealed, and carbon dioxide is injected so that the pressure in the container becomes 20 MPa to make a supercritical state, and 100 parts by mass of ethyl acetate is injected while stirring vigorously. Then, after stirring and mixing for 15 minutes while maintaining the temperature and pressure, it is carried out by supercritical reverse phase evaporation method that discharges carbon dioxide and returns to atmospheric pressure, and encloses inorganic nanoparticles and a dispersing agent having a phospholipid outer membrane. I got a vesicle.
Here, when 0.01 part by mass is added as a filler, 0.0107 part by mass of vesicle is added.

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

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

After pasting each decorative sheet 1 obtained in Examples 1 to 5 and Comparative Examples 1 to 5 to a wooden base material B using a urethane-based adhesive, the surface transparency and Hoffman are visually observed. The surface hardness was determined by a scratch test and a steel wool rubbing test, and the aptitude for V-groove bending was determined by a V-groove bending test, and evaluations were made respectively. The obtained evaluation results are shown in Table 1.
The test method of each evaluation test will be briefly described.

<Hoffman scratch test>
The Hoffman scratch test uses a Hoffman scratch hard tester (BYK-Gardner) to scratch the surface of each decorative sheet 1 bonded to the wooden substrate B at a constant speed under a load of 1200 g. 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 to 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. On the other hand, in the decorative sheet 1 of Comparative Examples 1-5, it was inferior to transparency, scratch resistance, and post-processability.
This is because, for the decorative sheets 1 of Examples 1 to 5, the inorganic nanoparticles can be uniformly dispersed by adding the vesicle encapsulating both the inorganic nanoparticles and the dispersant to the surface protective layer 2. This is considered to be because the surface hardness was improved due to the inorganic nanoparticles while maintaining good transparency and suitability for post-processing required for the decorative sheet 1.

  Moreover, about the decorative sheet 1 of the comparative example 1, since the dispersing agent and inorganic nanoparticle which do not have vesicle formation with respect to the surface protective layer 2 and do not have a reactive group were used, the dispersibility of an inorganic nanoparticle is enough It is considered that the transparency and scratch resistance required for the decorative sheet could not be obtained. About the decorative sheet 1 of the comparative example 2, since the dispersing agent which has not performed the vesicle formation with respect to the surface protective layer 2 was used, the dispersibility of an inorganic nanoparticle was not fully obtained but is required for a decorative sheet. It is considered that transparency and scratch resistance could not be obtained. For the decorative sheet 1 of Comparative Example 3, since the particle diameter of the inorganic particles is too large, irregularities are formed on the surface of the surface protective layer 2 and the transparency is impaired, and the thermosetting resin and the inorganic fine particles are sufficient. It is considered that the result was inferior in scratch resistance and post-working resistance without being bonded to. With regard to the decorative sheet 1 of Comparative Example 4, the amount of vesicles encapsulating the dispersant and inorganic nanoparticles in the capsule made of phospholipid was very small, so it is considered that the result was inferior in scratch resistance. With respect to the decorative sheet 1 of Comparative Example 5, the amount of vesicles encapsulating the dispersant and the inorganic nanoparticles in the capsule made of phospholipid was very large, resulting in inferior transparency. It is thought that the result was inferior because the abrasive wear occurred due to the dropping of the inorganic nanoparticles.

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

1 decorative sheet 2 surface protective layer 3 transparent resin layer 4 adhesive layer 5 pattern layer 6 base material layer 7 concealing layer 8 primer layer B base material

Claims (11)

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 layer 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 the dispersant and the inorganic nanoparticles are both encapsulated in a vesicle. 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 layer is a curable resin,
Forming at least one of the one or two or more surface protective layers by adding a dispersant and inorganic nanoparticles to the curable resin;
A decorative sheet, wherein the dispersant and the inorganic nanoparticles are both encapsulated in a vesicle.   The decorative sheet according to claim 1 or 2, wherein the dispersant and the inorganic nanoparticles are vesicled in a form of being encapsulated in a liposome having an outer membrane made of a phospholipid.   The cosmetic sheet according to claim 1 or 2, wherein both the dispersant and the inorganic nanoparticles are vesicled in a form of being encapsulated in a liposome having an outer membrane made of phospholipid.   The decorative sheet according to any one of claims 1 to 4, wherein the dispersant has a hydroxyl group or an amino group.   The decorative sheet according to any one of claims 1 to 4, wherein the dispersant has an unsaturated double bond. As a layer constituting the intermediate layer, having a transparent resin layer mainly composed of crystalline polypropylene resin,
The said transparent resin layer contains the nucleating agent included in the vesicle, The decorative sheet of any one of Claims 1-6 characterized by the above-mentioned. As a layer constituting the intermediate layer, having 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 is formed by adding a nucleating agent encapsulated in a vesicle to the crystalline polypropylene resin.   The said nucleating agent is contained in 0.01-1.0 mass part with respect to 100 mass parts of crystalline polypropylene resin which forms the said transparent resin layer, The Claim 7 or Claim characterized by the above-mentioned. Item 9. A decorative sheet according to Item 8.   The decorative sheet according to any one of claims 1 to 9, wherein the inorganic nanoparticles have a particle diameter in a range of 10 to 50 nm. It is a manufacturing method of a decorative sheet given in any 1 paragraph of Claims 1-10,
A method for producing a decorative sheet, wherein the dispersant and the inorganic nanoparticles are encapsulated in a vesicle by a supercritical reverse phase evaporation method.

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