JP5076588B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet.

  The decorative sheet is used by sticking it on the surface of a wooden board, a plastic board or the like for the purpose of surface protection, decoration, and the like. And the decorative board obtained by this is used for various building materials, furniture, etc.

  A desired pattern can be applied to the decorative sheet in order to impart design properties. Examples of the pattern include a wood grain pattern, a leather pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  Conventionally, there is a need for a decorative sheet with a texture and high design. For example, a woodgrain decorative sheet has a three-dimensional effect (depth) and requires a woodgrain pattern close to real natural wood. In addition, the decorative sheet is required to have a smooth tactile sensation in order to provide a more realistic picture (for example, wood grain pattern).

  The decorative sheet usually has a surface protective layer on the outermost surface. By providing a surface protective layer on the outermost surface, scratch resistance and the like can be imparted to the decorative sheet.

  Even a decorative sheet having such a surface protective layer has a textured texture (three-dimensional effect, close to real (natural wood, etc.)), and the surface protective layer has a smooth feel. Is required.

  For example, in order to improve the tactile sensation of a decorative sheet having a surface protective layer, a decorative sheet containing synthetic resin beads in the surface protective layer is disclosed (Patent Document 1).

However, the decorative sheet of Patent Document 1 is limited to a peach skin decorative sheet and has a limited range of application depending on the type of pattern.
JP 2004-262105 A

  The main object of the present invention is to provide a decorative sheet having a texture (three-dimensional effect, close to natural wood, natural leather, etc.) and a smooth tactile feel.

  As a result of intensive studies, the present inventor has found that a specific decorative sheet can achieve the above object, and has completed the present invention.

That is, the present invention relates to the following decorative sheet.
1. A decorative sheet having a leather pattern layer and a surface protective layer on the outermost surface,
(1) The surface protective layer includes resin beads having an average particle diameter of 6 to 30 μm, and a ratio of the average particle diameter of the resin beads to the thickness of the surface protective layer is 1: 0.17 to 0.83. ,
(2) The decorative sheet is a decorative sheet that is embossed from the surface protective layer side.
2. Item 2. The decorative sheet according to Item 1, wherein the surface protective layer is a layer formed by crosslinking a resin.
3. Item 3. The decorative sheet according to Item 2, wherein the resin is an ionizing radiation curable resin.
4). Item 4. The decorative sheet according to Item 3, wherein the surface protective layer is a layer formed by irradiating an electron beam onto a coating film containing the ionizing radiation curable resin.
5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the surface protective layer has a thickness of 15 μm or less.
6). Item 6. The decorative sheet according to any one of Items 2 to 5, wherein the content of the resin beads in the surface protective layer is 10 to 50 parts by weight with respect to 100 parts by weight of the resin.
7). Item 7. The decorative sheet according to any one of Items 1 to 6, comprising the pattern layer, the transparent adhesive layer, the transparent resin layer, the primer layer, and the surface protective layer in this order on the substrate sheet.
8). Item 8. The decorative sheet according to Item 7, wherein the primer layer is a layer formed by crosslinking a resin.
9. Item 9. The decorative sheet according to Item 7 or 8, wherein at least one of the surface protective layer and the primer layer contains silica as a matting agent.
10. Item 10. A decorative board in which the decorative sheet is laminated on an adherend so that the surface protective layer of the decorative sheet according to any one of Items 1 to 9 is an outermost surface layer.

The decorative sheet of the present invention has a three-dimensional effect as compared with conventional decorative sheets, has a pattern close to the real thing (for example, natural wood, natural leather, etc.), and has a smooth surface tactile sensation. That is, the decorative sheet of the present invention is closer to natural wood, natural leather, etc., and has a high-class feeling as compared with the conventional decorative sheet.

The decorative sheet of the present invention is a decorative sheet having a surface protective layer on the outermost surface,
(1) The surface protective layer includes resin beads having an average particle diameter of 1 to 30 μm,
(2) The decorative sheet is embossed from the surface protective layer side.

  The decorative sheet of the present invention is obtained by embossing a decorative sheet having a surface protective layer containing resin beads.

  The decorative sheet of the present invention has a dramatic improvement in the texture of the pattern as compared with a conventional decorative sheet obtained by embossing a surface protective layer that does not contain resin beads. For example, if the decorative sheet of the present invention is a woodgrain decorative sheet, the woodgrain pattern has a three-dimensional effect and the appearance is close to that of natural wood, compared to conventional decorative sheets. In addition, when the decorative sheet of the present invention is a leather pattern, the leather pattern has a three-dimensional effect and the appearance is close to natural leather compared to a conventional decorative sheet. Moreover, the decorative sheet of the present invention has a smooth tactile sensation, and such a tactile sensation further enhances the authenticity (for example, natural wood, natural leather, etc.).

Decorative sheet The decorative sheet of the present invention has a surface protective layer on the outermost surface.

(Surface protective layer)
By forming the surface protective layer, the surface of the decorative sheet is easily damaged and the scratch resistance is improved. The surface protective layer may be colored as long as it is transparent. Moreover, it may be translucent within the range in which the postscript pattern layer is visible.

  The surface protective layer includes resin beads having an average particle diameter of 1 to 30 μm, preferably 5 to 30 μm. By including the resin beads, a smooth feel can be imparted to the decorative sheet. The resin beads in the surface protective layer only have to protrude from the surface of the surface protective layer. The average particle diameter of the resin beads can be measured by a known method such as a laser diffraction method, a Coulter counter method, or a precipitation method.

  Examples of the resin beads include known or commercially available resin beads such as acrylic resin beads, urethane resin beads, styrene resin beads, and polyester resin beads. These resin beads may be used alone or in combination of two or more. In particular, in the present invention, it is preferable to use at least one kind of beads selected from the group consisting of urethane resin beads and acrylic resin beads as the resin beads.

  The shape of the resin beads is usually spherical, but is not particularly limited to a spherical shape as long as the effects of the present invention are not hindered. The resin beads may be colored. By appropriately coloring, depending on the type of the pattern, a stereoscopic effect close to the real thing may be suitably imparted.

  The thickness of the surface protective layer is usually 15 μm or less, particularly preferably 1 to 15 μm, and more preferably 3 to 10 μm. When the thickness of the surface protective layer is 15 μm or less, a smooth tactile sensation can be suitably imparted to the decorative sheet while effectively preventing the lack of the beads.

  As long as the effect of the present invention is not hindered, some resin beads may be buried in the surface protective layer.

  The ratio between the average particle diameter of the resin beads and the thickness of the surface protective layer is preferably 1: 0.1 to 2, and more preferably 1: 0.3 to 1.5. When the ratio between the average particle diameter of the resin beads and the thickness of the surface protective layer is 1: 0.1 to 2, it is possible to suitably impart a smooth feel to the decorative sheet while effectively preventing the loss of the beads.

  The surface protective layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent.

  The surface protective layer is preferably a layer formed by crosslinking a resin from the viewpoint of scratch resistance and the like. Examples of the resin include at least one of a thermosetting resin and an ionizing radiation curable resin, and an ionizing radiation curable resin is particularly preferable.

Hereinafter, the case where the resin component as a matrix constituting the surface protective layer (hereinafter sometimes abbreviated as “matrix resin”) is an ionizing radiation curable resin will be specifically described.
An ionizing radiation curable resin refers to a resin that crosslinks and cures when irradiated with ultraviolet rays, electron beams, and the like.

  As the ionizing radiation curable resin, known products or commercially available products can be used. Specifically, a composition containing at least one of a prepolymer, an oligomer and a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is used.

  Examples of the prepolymer or oligomer include methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate; polyester acrylate, polyether acrylate, urethane acrylate, polyol acrylate, melamine acrylate, and the like. Examples include acrylates.

  Monomers include styrene monomers such as styrene and α-methylstyrene; acrylic acid such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, and phenyl acrylate. Esters; methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate; acrylic acid-2- (N, N -Diethylamino) ethyl, methacrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N-dibenzylamino) methyl, acrylic acid-2- (N, N-diethylamino) propyl, etc. Substituted amino alcohol esters of unsaturated acids.

  In addition, unsaturated carboxylic acid amides such as acrylamide and methacrylamide; ethylene glycol diacrylate, propylene glycol diacrylate, neobenzyl glycol diacrylate, 1,6-hexanediol diacrylate, ethyl carbitol acrylate, diethylene glycol diacrylate, Multifunctional materials such as triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate; Trimethylolpropane trithioglycolate, Trime Trimethylolpropane tri thio propiolate, there is a polythiol compound having two or more thiol groups in the molecule, such as dipentaerythritol tetra thioglycolic.

  About the resin of the said illustration, 1 type (s) or 2 or more types can be used together.

  The content of the resin beads in the surface protective layer is preferably 10 to 50 parts by weight and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the matrix resin. When the content of the resin beads is 10 to 50 parts by weight with respect to 100 parts by weight of the matrix resin, a smooth tactile sensation can be suitably imparted to the decorative sheet.

  The surface protective layer may contain silica as a matting agent. The content of the matting agent is preferably 0.1 to 50 parts by weight, and more preferably 5 to 35 parts by weight with respect to 100 parts by weight of the resin component other than the resin beads. The average particle diameter of silica is preferably 1 to 30 μm, and more preferably 1 to 15 μm. The silica may be exposed from the surface protective layer. When the silica is exposed from the surface protective layer, the feel of the decorative sheet of the present invention becomes smoother.

  About the formation method of the surface protection layer by ionizing radiation curable resin, what is necessary is just to follow a well-known method. For example, a composition (coating material) containing an ionizing radiation curable resin may be prepared and applied by a known coating method such as a gravure coating method or a roll coating method. The coating amount of the composition in this case is not particularly limited, and may be set as appropriate so that the thickness of the surface protective layer falls within the above range.

  After application, the formed coating film is irradiated with ionizing radiation. Ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion beam, etc. There is. In particular, ultraviolet rays, electron beams, and the like can be used as ionizing radiation. In particular, the surface protective layer is preferably a layer formed by irradiating the coating film containing the ionizing radiation curable resin with an electron beam. By irradiating the electron beam, a surface protective layer uniformly crosslinked with resin can be obtained with certainty. Moreover, when the resin is crosslinked by electron beam irradiation, the resin can be stably crosslinked and cured without using a photopolymerization initiator, and unlike the resin crosslinking by UV irradiation, the curing reaction rate is influenced by temperature. This is advantageous in that it does not receive much.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of about 190 to 380 nm can be used. As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The acceleration voltage of the electron beam is generally about 100 to 1000 keV, preferably about 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  The decorative sheet of the present invention only needs to have a surface protective layer on the outermost surface, and the specific configuration may be appropriately set according to the use of the decorative sheet. For example, the decorative sheet which has a pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer, and the said surface protective layer in order on a base material sheet is mentioned.

  Hereinafter, the decorative sheet of the present invention will be specifically described with a decorative sheet having a pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer and the surface protective layer in this order as a representative example on a base sheet. To do.

(Substrate sheet)
A pattern layer etc. are laminated | stacked one by one on the surface (front surface) of a base material sheet.

  As the base sheet, for example, a sheet (film) formed of a thermoplastic resin is suitable. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer Examples include polymers, ionomers, acrylic esters, and methacrylic esters. The said base material sheet is formed by using these resin individually or in combination of 2 or more types.

  The base material sheet may be colored. In this case, a coloring material (pigment or dye) can be added to the above thermoplastic resin for coloring. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. These can be selected from one or more known or commercially available ones. Further, the addition amount of the colorant may be appropriately set according to the desired color tone.

  The base sheet contains various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers as necessary. It may be.

  Although the thickness of a base material sheet can be suitably set with the use of a final product, a usage method, etc., generally 20-300 micrometers is preferable.

  If necessary, the base sheet may be subjected to corona discharge treatment on the surface (front surface) in order to enhance the adhesion of the ink forming the pattern layer. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method. Moreover, you may give a corona discharge process to the back surface of a base material sheet, and may form a back surface primer layer as needed.

(Picture layer)
The pattern layer provides a desired pattern (design) to the decorative sheet, and the type of the pattern is not limited. For example, a wood grain pattern, a leather pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a geometric figure, a character, a symbol, an abstract pattern, and the like can be given.

  The method for forming the pattern layer is not particularly limited. For example, printing using ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form in the base-material sheet | seat surface by a method. As the ink, it is desirable to use an aqueous composition from the viewpoint of reducing the VOC of the decorative sheet.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  As binder resin, in addition to polyester urethane resin treated with hydrophilicity, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative Alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, and the like can also be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Resin, water-soluble phenolic resin, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides and the like can also be used. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, modified polyurethane-polyacrylic resin or mixture of natural rubber, other resins, etc. Can also be used. The binder resin can be used alone or in combination of two or more.

  The pattern layer may be formed by a known printing method such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, or an ink jet printing method.

  The thickness of the pattern layer is not particularly limited and can be appropriately set according to product characteristics. The layer thickness at the time of coating is about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.

(Colored hiding layer)
In the decorative sheet of the present invention, a colored concealing layer may be further formed between the base sheet and the pattern layer.

  The colored concealment layer only needs to conceal the ground color of the adherend when the decorative sheet and the adherend are joined, and is usually formed so as to cover the base sheet.

  The known printing method can be used for forming the colored concealing layer. Moreover, the ink used for formation of the said picture layer can be used as it is.

  The known printing method can be used for forming the colored concealing layer.

The coating amount is desirably in the range of ^{2 to} 30 g / m2.

  The thickness of the colored masking layer is usually about 0.1 to 20 μm, preferably about 1 to 10 μm.

(Transparent adhesive layer)
A transparent adhesive layer is formed in order to improve the adhesion between the transparent resin layer and the pattern layer described later. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

  Examples of known adhesives in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins, and thermosetting resins such as urethane resins. These colorants are used alone or in combination of two or more. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  The known printing method can be used for forming the transparent adhesive layer.

  Although the thickness of a transparent adhesive bond layer is not specifically limited, The thickness after drying is about 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

(Transparent resin layer)
A transparent resin layer is formed on the transparent adhesive layer.

  The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. Examples of the resin constituting the transparent resin layer include polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, and ethylene / acrylic acid ester copolymer. Examples thereof include coalescence, ionomer, polymethylpentene, acrylic acid ester, methacrylic acid ester, polycarbonate, and cellulose triacetate. These resins are used alone or in combination of two or more.

  Preferably, a polyolefin resin typified by polypropylene resin is used. Therefore, when using polyolefin-type resin as a transparent resin layer, the various polyolefin-type resin quoted as what comprises a base material sheet can be used.

  The transparent resin layer may be colored as long as it has transparency, but it is particularly desirable not to add a colorant.

  The method for forming the transparent resin layer is not limited, for example, a method of laminating a preformed sheet or film on an adjacent layer, an adjacent layer by melt-extruding a resin composition capable of forming a transparent resin layer Any of a method of coating on top and a method of laminating together with an adjacent layer can be employed. Examples of the laminating method include a laminating method by a dry laminating method.

  The thickness of the transparent resin layer is usually about 20 to 200 μm, but may exceed the above range depending on the use of the decorative sheet.

(Primer layer)
By providing the primer layer, the formation of the surface protective layer can be facilitated. The primer layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and translucent.

  The primer layer can be formed by applying a known or commercially available primer agent on the transparent resin layer. In particular, the primer layer is preferably a layer formed by crosslinking a resin. Examples of the primer agent for forming such a layer include a urethane resin primer agent made of an acrylic-modified urethane resin and the like, a resin primer agent made of a block copolymer of acrylic and urethane, and the like. These primer agents are used alone or in combination of two or more.

  The primer layer may contain silica as a matting agent. 0.1-50 weight part is preferable with respect to 100 weight part of resin components, and, as for content of the silica in a primer agent, 10-40 weight part is more preferable.

  Furthermore, you may make a primer agent contain a well-known additive as needed. For example, the adhesiveness of the said transparent resin layer and the said surface protective layer can be improved more by making a primer agent contain a hexamethylene diisocyanate type hardening | curing agent.

  For the formation of the primer layer, the above known methods can be used. For example, a method similar to the method for forming the surface protective layer using the ionizing radiation curable resin can be employed.

  The thickness of the primer layer is not particularly limited, but is usually about 0.1 to 100 μm, preferably about 0.5 to 15 μm.

(Embossing)
The decorative sheet of the present invention is embossed from the surface protective layer side.

  For example, after embossing, the surface protective layer is heated and softened on a heating drum, further heated to 140 to 170 ° C. with an infrared radiation heater, and pressed and shaped with an embossed plate having a desired uneven pattern. Then, it is performed by cooling and fixing. Embossing can be performed with a known single wafer or rotary embossing machine.

  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.

  The depth of the concave portion of the concavo-convex pattern may be appropriately set according to the thickness of the decorative sheet, but is preferably 1 to 200 μm, more preferably 10 to 150 μm. By setting the depth of the recess to 10 to 150 μm, it is possible to give a more stereoscopic effect.

Decorative plate The decorative plate of the present invention is formed by laminating the decorative sheet on the adherend so that the surface protective layer of the decorative sheet becomes the outermost surface layer.

  The adherend is not limited, and the same materials as known decorative sheets can be used. For example, a wood material, a metal, ceramics, plastics, glass, etc. are mentioned. In particular, the decorative sheet of the present invention can be suitably used for a wood material. Specifically, wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. ) And the like.

  The lamination method is not limited. For example, a method of sticking a decorative sheet to an adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like. These adhesives are used alone or in combination of two or more.

  The decorative board manufactured in this way is, for example, interior decoration materials for buildings such as walls, ceilings and floors, surface decorative boards for furniture such as window frames, doors and handrails, furniture or light electrical appliances, cabinets such as OA equipment. It can be preferably used for a surface decorative board or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
A decorative sheet having the structure shown in FIG. 1 was produced by the following method.

  Corona discharge treatment was performed on both the front and back surfaces of the base sheet 1 made of a colored polypropylene film having a thickness of 60 μm. Thereafter, a colored masking layer 2 having a thickness of 2 μm and a leather-like pattern layer 3 having a thickness of 4 μm were formed on the base sheet 1 by a gravure printing method using a colored ink having an acrylic resin as a binder resin.

  Next, a urethane resin is applied on the pattern layer 3 so that the thickness of the solid content is 3 μm, and a polypropylene resin sheet is laminated by a dry laminating method, and the transparent adhesive layer 4 having a thickness of 3 μm. And the transparent resin layer 5 of thickness 80micrometer was formed.

  On the surface of the transparent resin layer 5, acrylic urethane resin, silica (30 parts by weight with respect to 100 parts by weight of acrylic urethane resin), and hexamethylene diisocyanate curing agent (20 parts with respect to 100 parts by weight of acrylic urethane resin). A primer layer 6 having a thickness of 1 μm was formed by a gravure printing method using a resin composition comprising (part by weight).

Furthermore, on the primer layer 6, a resin composition comprising a urethane acrylate oligomer which is an ionizing radiation curable resin and urethane resin beads having an average particle diameter of 20 μm (20 parts by weight with respect to 100 parts by weight of the ionizing radiation curable urethane acrylate oligomer). The product was coated and dried by gravure printing so that the solid content was 5 g / m ² to form an uncured coating film.

  Thereafter, in an environment with an oxygen concentration of 200 ppm, the uncured resin layer is irradiated with an electron beam under the conditions of an acceleration voltage of 125 KeV and 5 Mrad to cure the resin, and the surface protective layer 7 (layer thickness is exposed). : 5 μm).

  Next, a leather pattern uneven pattern (not shown) having a recess depth of 50 μm was formed from above the surface protective layer 7 by embossing.

  For embossing, after the surface protective layer 7 is heated and softened on a heating drum, it is further heated to 140 ° C. with an infrared radiation heater, pressed and shaped with an embossed plate having a leather pattern, and cooled and fixed. It was done by doing.

Example 2
A decorative sheet was prepared in the same manner as in Example 1 except that acrylic resin beads having an average particle diameter of 20 μm were used instead of urethane resin beads having an average particle diameter of 20 μm.

Example 3
A decorative sheet was prepared in the same manner as in Example 1 except that urethane resin beads having an average particle diameter of 30 μm were used instead of urethane resin beads having an average particle diameter of 20 μm.

Example 4
A decorative sheet was prepared in the same manner as in Example 1 except that urethane resin beads having an average particle diameter of 14 μm were used instead of urethane resin beads having an average particle diameter of 20 μm.

Example 5
A decorative sheet was prepared in the same manner as in Example 1 except that urethane resin beads having an average particle diameter of 6 μm were used instead of urethane resin beads having an average particle diameter of 20 μm.

Comparative Example 1
A decorative sheet was prepared in the same manner as in Example 1 except that urethane resin beads having an average particle diameter of 20 μm were not used.

Comparative Example 2
A decorative sheet was prepared from the surface protective layer 7 by the same method as in Example 1 except that the embossing was not performed (the embossed pattern was not formed).

Test example 1 (feel)
The tactile sensations of the decorative sheets prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were confirmed. Specifically, it was confirmed by stroking the surface protective layer side of the decorative sheet by hand.

  It was smooth and smooth and had a touch of suede. The evaluation was ○, and it was rough and the resistance to the hand was high.

  The results are shown in Table 1.

Test example 2 (texture)
The texture of the leather pattern of the decorative sheets produced in Examples 1 to 5 and Comparative Examples 1 and 2 was confirmed. Specifically, the surface protective layer side of the decorative sheet was confirmed by visual observation.

  The leather pattern had a three-dimensional effect, and the leather pattern was evaluated as ○ when the leather pattern was close to the real (natural leather), and the leather pattern was flat, and the leather pattern was not natural (natural leather).

  The results are shown in Table 1.

FIG. 1 is a conceptual diagram (cross-sectional view) of a decorative sheet produced in Examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material sheet 2 ... Colored concealment layer 3 ... Picture layer 4 ... Transparent adhesive layer 5 ... Transparent resin layer 6 ... Primer layer 7 ... Surface protective layer 8 ... Resin beads

Claims (10)

A decorative sheet having a leather pattern layer and a surface protective layer on the outermost surface,
(1) The surface protective layer includes resin beads having an average particle diameter of 6 to 30 μm, and a ratio of the average particle diameter of the resin beads to the thickness of the surface protective layer is 1: 0.17 to 0.83. ,
(2) The decorative sheet is a decorative sheet that is embossed from the surface protective layer side. The decorative sheet according to claim 1, wherein the surface protective layer is a layer formed by crosslinking a resin. The decorative sheet according to claim 2, wherein the resin is an ionizing radiation curable resin. The decorative sheet according to claim 3, wherein the surface protective layer is a layer formed by irradiating an electron beam to a coating film containing the ionizing radiation curable resin. The decorative sheet according to any one of claims 1 to 4, wherein the surface protective layer has a thickness of 15 µm or less. The decorative sheet according to any one of claims 2 to 5, wherein the content of the resin beads in the surface protective layer is 10 to 50 parts by weight with respect to 100 parts by weight of the resin. The decorative sheet according to any one of claims 1 to 6, further comprising the pattern layer, the transparent adhesive layer, the transparent resin layer, the primer layer, and the surface protective layer in this order on the base sheet. The decorative sheet according to claim 7, wherein the primer layer is a layer formed by crosslinking a resin. The decorative sheet according to claim 7 or 8, wherein at least one of the surface protective layer and the primer layer contains silica as a matting agent. A decorative board in which the decorative sheet is laminated on an adherend so that the surface protective layer of the decorative sheet according to any one of claims 1 to 9 becomes an outermost surface layer.

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