JP6307792B2 - Decorative sheet and method for producing the same - Google Patents

Description

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

  Conventionally, in order to give design properties to the interior and exterior of buildings, furniture, fittings, interiors of vehicles, surface decorative materials for home appliances, etc., a design with a matte feeling was expressed by reducing the gloss of the surface protective layer A decorative sheet is used.

  As a method for reducing the gloss of the surface protective layer of the decorative sheet, a method of adding a large amount of a matting agent such as silica to the surface protective layer is used. According to this method, silica fine particles are removed from the surface of the surface protective layer. Since the surface of the decorative sheet is rubbed, the surface of the decorative sheet is rubbed off and the surface is smoothed, resulting in a glossy surface. There is a problem that the scratches are conspicuous and the scratch resistance is lowered.

  Further, since a fine uneven shape is formed on the surface of the decorative sheet, there is a problem that even if the dirt adheres, even if it is wiped off, the details cannot be wiped off, and the dirt is difficult to remove and the stain resistance is lowered. The above-mentioned problems become prominent when a decorative sheet is laminated on a medium density fiberboard (MDF) or the like and used as a flooring decorative material or the like.

  Further, when the decorative sheet is used as a flooring decorative material, the surface is required to have anti-slip properties. As a decorative sheet satisfying such performance, a decorative sheet has been proposed in which the ionizing radiation curable resin forming the surface protective layer includes a resin exhibiting a glass transition temperature in a specific range (for example, Patent Document 1). reference).

  Such a decorative sheet is a decorative sheet that is excellent in anti-slip properties and excellent in stain resistance because the ionizing radiation curable resin forming the surface protective layer contains the above-mentioned resin.

  Such a decorative sheet is also excellent, but when a large amount of a matting agent is added to the surface protective layer for the purpose of reducing the gloss and imparting design properties, the foot and resin during walking etc. due to the protrusion of fine particles There is a problem that the anti-slip property corresponding to the amount of the resin exhibiting the anti-slip property cannot be obtained, and the stain resistance is lowered. A cosmetic sheet excellent in design by expressing scratch resistance, stain resistance and low gloss while maintaining the slip resistance required for the decorative sheet has not yet been developed.

JP 2007-118596 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a decorative sheet having anti-slip properties required for a decorative sheet, excellent in design properties by expressing scratch resistance, stain resistance, and low gloss, and a method for producing the decorative sheet.

  As a result of intensive research, the inventors of the present invention have at least a solid printing gloss adjusting layer and a surface protective layer laminated in this order on the base sheet, and the solid printing gloss adjusting layer contains fine particles, The inventors have found that the above object can be achieved by setting the center line average roughness of the front surface of the solid printing gloss adjusting layer within a specific range, and have completed the present invention.

That is, this invention relates to the following decorative sheet and its manufacturing method.
1. A decorative sheet in which at least a solid printing gloss adjusting layer and a surface protective layer are laminated in this order on a base sheet,
(1) The solid printing gloss adjusting layer contains fine particles having an average particle size of 8 to 20 μm,
(2) the solid print gloss center line average roughness Ra of the front surface of the adjustment layer (JIS B0601: 1982) is Ri der than 0.5 [mu] m,
(3) The surface protective layer contains a matting agent, and the content of the matting agent is 8 to 14 parts by mass with respect to 100 parts by mass of the resin solid content of the resin forming the surface protective layer.
A decorative sheet characterized by that.
2. The decorative sheet according to Item 1, wherein the surface protective layer contains a matting agent, and the matting agent has an average particle size of 10 to 20 μm.
3 . Item 3. The decorative sheet according to Item 1 or 2 , wherein the content of the fine particles is 30 to 70% by mass with respect to 100% by mass of the resin solid content of the resin forming the solid printing gloss adjusting layer.
4 . Item 4. The decorative sheet according to any one of Items 1 to 3 , wherein the surface protective layer is an ionizing radiation curable resin layer and has a thickness of 6 µm or more.
5 . Item 5. The decorative sheet according to any one of Items 1 to 4 , wherein the surface protective layer contains an ionizing radiation curable resin having a glass transition point (Tg) of 0 ° C or lower.
6 . Item 6. The decorative sheet according to any one of Items 1 to 5 , wherein the solid print gloss adjusting layer has a thickness of 0.5 to 5.0 µm.
7 . Item 7. The decorative sheet according to any one of Items 1 to 6 , which is embossed from the front surface side of the layer immediately below the solid printing gloss adjusting layer.
8 . Item 8. The decorative sheet according to any one of Items 1 to 7 , which is embossed from the surface protective layer side.
9 . On the base sheet, at least a solid printing gloss adjusting layer and a surface protective layer are laminated in this order,
(1) The solid printing gloss adjusting layer contains fine particles having an average particle size of 8 to 20 μm,
(2) the solid print gloss center line average roughness Ra of the front surface of the adjustment layer (JIS B0601: 1982) is Ri der than 0.5 [mu] m,
(3) The decorative sheet in which the surface protective layer contains a matting agent, and the content of the matting agent is 8 to 14 parts by mass with respect to 100 parts by mass of the resin solid content of the resin forming the surface protective layer. A manufacturing method of
A method for producing a decorative sheet comprising the following steps (i) and (ii):
(I) Solid printing gloss containing fine particles having an average particle diameter of 8 to 20 μm on the base sheet and having a center line average roughness Ra (JIS B0601: 1982) of 0.5 μm or more. Step 1 of forming the adjustment layer,
(Ii) Step 2 of forming a surface protective layer having a matting agent content of 8 to 14 parts by mass with respect to 100 parts by mass of the resin solid content of the resin forming the surface protective layer on the solid printing gloss adjusting layer 2 .
10 . The decorative board formed by sticking the decorative sheet in any one of said claim | item 1-8 to a to-be-adhered material.

  In the decorative sheet of the present invention, at least a solid printing gloss adjusting layer and a surface protective layer are laminated in this order on a base sheet, (1) the solid printing gloss adjusting layer contains fine particles, and (2) the solid printing The centerline average roughness Ra (JIS B0601: 1982) of the front surface of the gloss adjusting layer is 0.5 μm or more.

  The decorative sheet of the present invention having the above characteristics has a solid printing gloss adjusting layer containing fine particles, and the center line average roughness Ra (JIS B0601: 1982) of the front surface of the solid printing gloss adjusting layer is 0. .5 μm or more. For this reason, when viewed from the front surface of the decorative sheet (surface on the surface protective layer side), the uneven shape of the front surface of the solid printing gloss adjustment layer is visually recognized through the surface protective layer, and the low gloss design And is excellent in design.

  In addition, the uneven shape of the front surface of the solid printing gloss adjustment layer is coated on the surface protective layer and is not exposed on the surface of the decorative sheet. Is excellent.

  In addition, since the surface protective layer is coated with the uneven shape on the front surface of the solid printing gloss adjustment layer, the protruding fine particles are hard to be scraped off even if the decorative sheet surface is rubbed, and the gloss of the rubbed area is increased and scratched. Is suppressed and is excellent in scratch resistance.

  Furthermore, since the centerline average roughness Ra of the front surface of the solid printing gloss adjusting layer is 0.5 μm or more, a low gloss feeling is expressed. There is no need to contain a large amount of fine particles. For this reason, when providing anti-slip property by adding resin which shows anti-slip property to a surface protective layer, anti-slipping property commensurate with the addition amount of resin showing anti-slip property can be exhibited.

  Since the decorative sheet of the present invention has the above-described configuration, it has anti-slip properties required for the decorative sheet, and is excellent in design properties due to the expression of scratch resistance, stain resistance, and low gloss, and particularly in the surface protective layer. When the anti-slip property is imparted by adding a resin exhibiting anti-slip property, the anti-slip property commensurate with the addition amount of the resin exhibiting anti-slip property can be exhibited.

  Hereinafter, the decorative sheet and the method for producing the decorative sheet of the present invention will be described in detail. In the decorative sheet of the present invention, the surface protective layer is a so-called “front surface” (surface visually recognized after construction). Therefore, in this specification, the direction in which the surface protective layer is present with respect to the base sheet is referred to as “front” or “upper”, and the opposite side is referred to as “back” or “lower”.

(Decorative sheet)
Each layer constituting the decorative sheet will be specifically described.

The base sheet has a solid printing gloss adjusting layer and the like sequentially laminated on the surface (front surface). 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 substrate sheet may be subjected to corona discharge treatment on the surface (front surface) in order to improve the adhesion of the ink forming the solid printing gloss adjusting 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 the back surface primer layer mentioned later as needed.

Solid printing gloss adjustment layer The solid printing gloss adjustment layer is a layer that imparts a low gloss feeling (design) to the surface of the decorative sheet. In the decorative sheet of the present invention, since the solid printing gloss adjusting layer contains fine particles, the surface of the solid printing gloss adjusting layer has an uneven shape, and the uneven shape is the front surface (surface protective layer side) of the decorative sheet. When viewed from the front surface), it is visually recognized through the surface protective layer and expresses a low gloss design.

  In the decorative sheet of the present invention, the ratio of the area occupied by the solid print gloss adjusting layer on the base sheet is not particularly limited as long as the decorative sheet surface can express a low gloss feeling, but the area of the entire surface of the base sheet surface is not limited. 100% is preferably 50% or more, more preferably 75% or more, and still more preferably 90% or more. Moreover, it is particularly preferable that a solid printing gloss adjusting layer is provided over the entire surface (100%) on the base sheet. By setting the ratio of the area in such a range, a low gloss feeling can be sufficiently expressed, and a decorative sheet excellent in design can be obtained.

  The fine particles are not particularly limited as long as an uneven shape can be formed on the surface of the solid printing gloss adjusting layer. For example, inorganic fine particles such as silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate, silicone resin, etc. And organic fine particles such as crosslinked alkyl, crosslinked styrene, inzoguanamine resin, urea-formaldehyde resin, phenol resin, polyethylene, and nylon. Among these, silica fine particles are preferable.

  The average particle diameter of the fine particles is preferably 5 μm or more. 5-20 micrometers is more preferable and 5-15 micrometers is still more preferable. By setting the average particle diameter in such a range, the uneven shape of the solid printing gloss adjusting layer can easily express a low gloss design. In addition, if the average particle size of the fine particles is smaller than 5 μm, a large amount of matting agent must be added to the surface protective layer in order to express a sufficiently low gloss feeling as a decorative sheet. Since a lot of fine particles as a matting agent protrude, the decorative sheet may be inferior in stain resistance and scratch resistance.

  The content of the fine particles in the solid printing gloss adjusting layer is preferably 30 to 70% by mass and more preferably 40 to 60% by mass with respect to 100% by mass of the resin solid content of the resin forming the solid printing gloss adjusting layer.

  The center line average roughness Ra of the front surface of the solid printing gloss adjusting layer is 0.5 μm or more. By setting the center line average roughness Ra in such a range, it is possible to express a low gloss design having an excellent uneven shape of the solid print gloss adjusting layer. Moreover, since the low gloss is expressed by setting the center line average roughness Ra in such a range, it is not necessary to contain a large amount of fine particles in the surface protective layer for expressing the low gloss, and the surface protection. In the case where anti-slip properties are imparted by adding a resin exhibiting anti-slip properties to the layer, it is possible to exhibit anti-slip properties commensurate with the amount of the resin exhibiting anti-slip properties in the surface protective layer.

  The center line average roughness Ra is preferably 0.7 μm or more, and more preferably 1.0 μm or more. The centerline average roughness Ra is preferably 5.0 μm or less, and more preferably 2.0 μm or less. If Ra is too large, the surface of the solid printing gloss adjusting layer is not uniform, and thus when the surface protective layer is formed, there is a possibility that a portion not covered with the surface protective layer is formed, so-called coating loss. In addition, the center line average roughness Ra of the front surface of the solid printing gloss adjusting layer in the present specification is a value measured according to JIS B0601: 1982.

  The method for forming the solid printing gloss adjusting layer is not particularly limited. For example, fine particles 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 by the printing method using the ink containing this. As the ink, an aqueous composition can be used 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 a neutralizing agent, a surfactant 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. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above natural rubber, etc. Resin can also be used. The said binder resin can be used individually or in combination of 2 or more types.

  The solid printing gloss adjusting layer has a property of causing an interaction with the curable resin composition (uncured curable resin) forming the surface protective layer, and the curable resin composition (uncured curable resin). It is appropriately selected in relation to the cured product. Specifically, the ink vehicle preferably contains 50% by mass or more of urethane resin or polyvinyl acetal resin. The urethane-based resin is a urethane resin obtained by reacting a polyol such as acrylic polyol, polyester polyol, or polyether polyol with an isocyanate component such as tolylene diisocyanate, xylene diisocyanate, or diphenylmethane diisocyanate (linear). And any of those crosslinked in a network form). Moreover, a polyvinyl acetal type resin is obtained by condensation (acetalization) of polyvinyl alcohol and aldehydes. Examples of the polyvinyl acetal resin include polyvinyl formal (formal resin), polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral (butyral resin), and polyvinyl hexyl. Polyvinyl butyral is particularly preferable because of the good appearance of visual unevenness (recognized visually as a recess).

  The thickness of the solid print gloss adjusting layer is not particularly limited and can be appropriately set according to product characteristics, but is about 0.5 to 5.0 μm.

  The decorative sheet of the present invention is preferably embossed from the front surface side (the surface side on which the solid printing gloss adjusting layer is formed) of the layer immediately below the solid printing gloss adjusting layer. With such a configuration, the concave-convex pattern on the front surface side of the layer immediately below and the low gloss feeling of the solid print gloss adjusting layer can be combined to provide a decorative sheet with further excellent design.

  The embossing method is not particularly limited, and for example, a preferable method is to heat and soften a layer immediately below the solid printing gloss adjusting layer, pressurize and shape with an embossing plate, and then cool. 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.

Surface Protective Layer The decorative sheet of the present invention has a surface protective layer formed on the solid printing gloss adjusting layer. The surface protective layer is not limited, but preferably contains an ionizing radiation curable resin or a two-component curable urethane resin as a resin component. Substantially those formed from these resins are preferred. When the surface protective layer is formed from an ionizing radiation curable resin or a two-component curable urethane resin, it is easy to improve the wear resistance, impact resistance, stain resistance, scratch resistance, weather resistance, etc. of the decorative sheet.

  The ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds capable of undergoing a crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent resin containing as a main component can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used. The details of the ultraviolet ray source and the electron beam source will be described in the item of the decorative sheet manufacturing method described later.

  The two-component curable urethane resin is not particularly limited. Among them, a polyol component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) having an OH group as a main component and an isocyanate component (tolylene diene) which is a curing agent component. Isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate and the like) can be used.

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

  The surface protective layer of the decorative sheet of the present invention preferably contains an ionizing radiation curable resin having a glass transition point (Tg) of 0 ° C. or lower. By containing such a resin, in addition to the anti-slip property required for the decorative sheet, it is possible to provide a further excellent anti-slip property. The glass transition point is more preferably −20 ° C. or lower. Moreover, although the minimum of the said glass transition point is not specifically limited, About -60 degreeC is preferable.

  Examples of the ionizing radiation curable resin having a glass transition point of 0 ° C. or lower include urethane (meth) acrylate oligomers. Among them, a bifunctional urethane (meth) acrylate oligomer is preferable, and a bifunctional urethane (meth) acrylate oligomer having a Tg of −55 ° C. and a molecular weight (Mn) of about 5000 is more preferable.

  The ionizing radiation curable resin having a glass transition point (Tg) of 0 ° C. or lower is preferably used in a mixed state with a urethane (meth) acrylate oligomer having a Tg exceeding 0 ° C. For example, 1) a urethane (meth) acrylate oligomer having a Tg of 0 ° C. or lower, 2) a urethane (meth) acrylate oligomer having a Tg of 20-30 ° C., and 3) a urethane (meth) acrylate oligomer having a Tg of 200 ° C. or higher. It is preferable to use in a state.

  The content of the ionizing radiation curable resin having a glass transition point of 0 ° C. or less is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, with the resin component forming the surface protective layer being 100% by mass. By setting the content in such a range, the surface protective layer exhibits a further excellent anti-slip property in addition to the anti-slip property required for the decorative sheet.

  The thickness of the surface protective layer of the decorative sheet of the present invention is not particularly limited, but is preferably 6 μm or more, and more preferably 10 μm or more. By setting the thickness of the surface protective layer in such a range, a decorative sheet having excellent scratch resistance can be obtained. Further, the thickness is preferably 50 μm or less, and more preferably 20 μm or less. If the thickness of the surface protective layer is too thick, when the decorative sheet is viewed from the surface, the low gloss feeling of the solid print gloss adjusting layer laminated on the lower layer may not be visible.

  Further, it is preferable to add an ultraviolet absorber such as benzotriazole, benzophenone, salicylate, or triazine to the surface protective layer in order to improve the weather resistance. In the case of curing the resin layer by irradiating with ultraviolet rays, as photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-aminoxime ester, tetramethylthiuram monosulfide, thioxanthones, aromatic diazonium salts N-butylamine, triethylamine, tri-n-butylphosphine and the like are used as photopolymerization accelerators (sensitizers) such as aromatic sulfonium salts and metallocenes.

  In addition, an antibacterial agent may be added to the surface protective layer in order to impart antibacterial properties. Antibacterial agents include inorganic antibacterial agents and organic antibacterial agents. In particular, inorganic antibacterial agents are desirable because they are generally safer than organic antibacterial agents and are excellent in durability and heat resistance. Inorganic antibacterial agents are those in which antibacterial metals such as silver, copper and zinc are supported on various inorganic carriers. The addition amount of the antibacterial agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin component.

  In addition, the surface protective layer may contain various additives such as colorants such as solvents, dyes and pigments, fillers such as matting agents and extenders, antifoaming agents, leveling agents, and thixotropic agents, as necessary. Can be added.

  The matting agent added to the surface protective layer is not particularly limited as long as it does not impair the design properties expressed by the decorative sheet of the present invention, and known or commercially available ones can be used. Examples thereof include inorganic particles such as silica and silicone resin; organic particles such as crosslinked alkyl, crosslinked styrene, inzoguanamine resin, urea-formaldehyde resin, phenol resin, polyethylene, and nylon.

  The amount of the matting agent added to the surface protective layer is preferably 4 to 14 parts by mass, and more preferably 8 to 12 parts by mass with respect to 100 parts by mass of the resin solid content of the resin forming the surface protective layer. If the addition amount of the matting agent is too large, a lot of fine particles as the matting agent protrude from the surface of the surface protective layer, and the decorative sheet may be inferior in stain resistance and scratch resistance.

  The average particle size of the matting agent is preferably 3 to 20 μm, more preferably 4 to 14 μm. By setting the average particle diameter of the matting agent in such a range, the surface protective layer can express a low gloss feeling and can be provided with stain resistance and scratch resistance required for a decorative sheet.

  The surface protective layer is formed by, for example, applying an ionizing radiation curable resin or a two-component curable urethane resin on a transparent resin layer by a known coating method such as gravure coating or roll coating, and then curing the resin. it can.

(Layer structure of decorative sheet)
In the decorative sheet of the present invention, the specific configuration (layer configuration) is not limited as long as at least the solid printing gloss adjusting layer and the surface protective layer are laminated in this order on the base sheet. For example, a decorative sheet formed by sequentially laminating a colored hiding layer, a pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer, a solid printing gloss adjusting layer, and a surface protective layer on a base sheet. .

  Hereinafter, the layer sheet other than the base sheet, the solid print gloss adjusting layer, and the surface protective layer described above will be specifically described with the decorative sheet having such a layer configuration as a representative example.

Colored concealment layer In the decorative sheet of the present invention, a color concealment layer may be 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.

For the formation of the colored concealing layer, a method that can be formed so as to cover the entire substrate sheet (entirely solid) is preferable. For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.
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.

Pattern pattern layer The pattern 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, an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin is used. What is necessary is just to form on the base-material sheet | seat surface by the printing method. As the ink, an aqueous composition can be used 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. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above natural rubber, etc. Resin can also be used. The said binder resin can be used individually or in combination of 2 or more types.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate 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.

Transparent adhesive layer A transparent adhesive layer may be formed on the pattern layer in order to enhance the adhesion between the transparent resin layer and the pattern layer. 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 adhesives can be used individually by 1 type or in combination of 2 or more types. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  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 may be formed on the transparent adhesive layer. When the above pattern layer is provided, a transparent resin layer is formed above the pattern layer, and a solid print gloss adjusting layer is further formed on the transparent resin layer. When there is a part that is visible through the adjustment layer or a part of the solid printing gloss adjustment layer is not formed, the part is visually recognized in a part without the solid printing gloss adjustment layer. In this case, since there is a transparent resin layer having a certain thickness between the pattern layer and the solid printing gloss adjusting layer, these layers are separated by a distance corresponding to the thickness of the transparent resin layer. It will be visually recognized, and a design with a three-dimensional feeling can be expressed. In addition, as will be described later, when embossing is performed from the transparent resin layer side or the surface protective layer side, the design with the above three-dimensional effect and the front surface side of the transparent resin layer or the surface protective layer In combination with the concavo-convex pattern, the decorative sheet can be further improved in design.

  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 can be 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 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.

A primer layer may be provided on the primer layer transparent resin layer. The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set according to the product characteristics.

  Although the thickness of a primer is not specifically limited, Usually, it is 0.01-10 micrometers, Preferably it is about 0.1-5 micrometers.

If necessary, a back primer layer may be provided on the back surface of the back primer layer substrate sheet (the surface opposite to the surface on which the solid print gloss adjusting layer is laminated). For example, it is effective when a base material sheet and an adherend are bonded to produce a decorative material.

  A back surface primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane-based resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set according to the product characteristics.

  Although the thickness of a back surface primer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-5 micrometers.

  The decorative sheet of the present invention may be embossed from the transparent resin layer side after forming the transparent resin layer. Further, when a surface protective layer is formed on the transparent resin layer, the surface protective layer may be laminated on the transparent resin layer and then embossed from the surface protective layer side. . With such a configuration, the decorative sheet on the front surface side of the transparent resin layer or the surface protective layer is combined with the low gloss feeling of the solid printing gloss adjustment layer, and a decorative sheet with further excellent design is obtained. be able to.

  The embossing method is not particularly limited. For example, a preferable method is to heat and soften the front surface of the transparent resin layer or the surface protective layer, pressurize and shape with an embossing plate, and then cool. 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.

(Decorative board)
A decorative sheet can be obtained by laminating the decorative sheet of the present invention on an adherend. The adherend is not limited, and the same adherend as that used for a known decorative board 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 includes, for example, interior materials for buildings such as walls, ceilings, and floors; exterior materials such as balconies and verandas; surface decorative boards and furniture for furniture such as window frames, doors, and handrails; Alternatively, it can be used for a surface decorative plate of a cabinet such as a light electric or OA device. In particular, the decorative board can be suitably used as a floor decorative material.

(Manufacturing method of decorative sheet)
In the method for producing a decorative sheet of the present invention, at least a solid printing gloss adjusting layer and a surface protective layer are laminated in this order on a base sheet, (1) the solid printing gloss adjusting layer contains fine particles, (2) A method for producing a decorative sheet, wherein the centerline average roughness Ra (JIS B0601: 1982) of the front surface of the solid printing gloss adjusting layer is 0.5 μm or more, comprising: (i) fine particles on a substrate sheet And (ii) on the solid printing gloss adjusting layer, forming a solid printing gloss adjusting layer having a center line average roughness Ra (JIS B0601: 1982) of 0.5 μm or more. And a manufacturing method including step 2 of forming a surface protective layer.

Hereinafter, each process in the manufacturing method of the decorative sheet of the present invention will be described taking the decorative sheet as an example.

(I) Step 1
Step 1 is a step of forming a solid printing gloss adjusting layer containing fine particles and having a center line average roughness Ra (JIS B0601: 1982) of 0.5 μm or more on the base sheet. is there.

  A base material sheet can be obtained by forming the resin composition containing the resin component for forming the base material sheet mentioned above, for example by the calendar method.

A solid printing gloss adjusting layer is formed on the obtained base material sheet. The solid printing gloss adjusting layer is formed by forming the ink for forming the solid printing gloss adjusting layer using a known method, and by appropriately setting the conditions at that time, the center line average in the above range is used. What is necessary is just to show roughness Ra. For example, the above-mentioned known colorant (dye or pigment) is dissolved (or dispersed) in a solvent (or dispersion medium) together with a binder resin and formed by a printing method using ink containing fine particles. That's fine. Although it does not specifically limit as a printing method, For example, well-known printing methods, such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, an inkjet printing method, are mentioned.
Although the thickness of the said ink is not specifically limited, Usually, it is about 0.5-5 micrometers.

  When providing a colored concealing layer, a pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer, and a solid printing gloss adjusting layer on the base sheet, first, the colored concealing layer is provided on the base sheet. It is formed by a known method.

  Next, a pattern layer is formed on the colored hiding layer by a known printing method similar to the above-described printing method.

  Next, a transparent adhesive layer is formed on the pattern layer by a known method, and a transparent resin composed of a sheet or film formed in advance is laminated on the surface to form a transparent resin layer. Moreover, you may form a transparent resin layer by melt-extruding the resin composition for forming the transparent resin layer mentioned above.

  Next, a primer layer can be formed on the transparent resin layer by a known printing method similar to the above-described printing method. A solid printing gloss adjusting layer may be provided on the obtained primer layer by the method described above.

(Ii) Step 2
Step 2 is a step of forming a surface protective layer on the solid printing gloss adjusting layer. About the formation method of a surface protective layer, what is necessary is just to follow a well-known method. For example, a composition (paint) containing the above-mentioned ionizing radiation curable resin or the like 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 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 coating, the formed coating film may be 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 insulated 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.

  In the present invention, a primer layer (particularly a primer layer made of a urethane resin) may be provided in advance as a base under the solid printing gloss adjusting layer. In this case, the adhesiveness between the solid printing gloss adjusting layer and the substrate sheet is high, which is preferable. The method for forming the primer layer is not limited, and any known method may be followed.

  The decorative sheet of the present invention has a solid printing gloss adjusting layer containing fine particles, and the center line average roughness Ra (JIS B0601: 1982) of the front surface of the solid printing gloss adjusting layer is 0.5 μm or more. Therefore, when viewed from the front surface of the decorative sheet (surface on the surface protective layer side), the uneven shape of the front surface of the solid printing gloss adjustment layer is visually recognized through the surface protective layer, resulting in a low gloss design. Because it can be expressed, it is excellent in design.

  In addition, the uneven shape of the front surface of the solid printing gloss adjustment layer is coated on the surface protective layer and is not exposed on the surface of the decorative sheet. Also excellent.

  In addition, since the surface protective layer is coated with the uneven shape on the front surface of the solid printing gloss adjustment layer, the protruding fine particles are hard to be scraped off even if the decorative sheet surface is rubbed, and the gloss of the rubbed area is increased and scratched. Is suppressed and is excellent in scratch resistance.

  Furthermore, since the centerline average roughness Ra of the front surface of the solid printing gloss adjusting layer is 0.5 μm or more, a low gloss feeling is expressed. It is not necessary to contain a large amount of fine particles, and when the anti-slip property is added to the surface protective layer by adding a non-slip property, the anti-slip property corresponding to the added amount of the anti-slip property should be exhibited. Can do.

  Since the decorative sheet of the present invention has the above-described configuration, it has anti-slip properties required for the decorative sheet, and is excellent in design properties due to the expression of scratch resistance, stain resistance, and low gloss, and particularly in the surface protective layer. When the anti-slip property is imparted by adding a resin exhibiting anti-slip property, the anti-slip property commensurate with the addition amount of the resin exhibiting anti-slip property can be exhibited.

It is sectional drawing which shows an example of the decorative sheet of this invention.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
(Production of decorative sheet)
A corona discharge treatment was applied to the front and back surfaces of a 60 μm thick polypropylene sheet (base material sheet), and then a primer layer (back surface primer layer) was formed on the back surface of the base material sheet by gravure printing.

  Subsequently, the pattern layer of the woodgrain pattern was formed on the front surface of the base material sheet by gravure printing. A transparent resin layer (thickness: 80 μm) is formed by forming a 2 μm-thick adhesive layer made of a two-component curable urethane resin on the pattern layer and extruding a polypropylene resin on the adhesive layer surface. Formed.

  Next, after a corona discharge treatment was applied to the surface, a primer layer was formed by applying a two-component curable urethane resin.

  On the primer layer, gravure printing was performed using a printing ink containing silica having an average particle size of 8 μm to provide a solid printing gloss adjusting layer. The content of silica in the solid print gloss adjusting layer was 50% by mass with respect to 100% by mass of the resin solid content of the resin forming the solid print gloss adjusting layer. Further, the center line average roughness Ra (JIS B0601: 1982) of the front surface of the solid printing gloss adjusting layer was 0.9 μm.

  Next, an ionizing radiation curable resin (EB resin) is applied with a thickness of 13 μm by a gravure coating method, and an electron beam is applied under an acceleration voltage of 175 keV and 5 Mrad using an electron beam irradiation apparatus in an environment having an oxygen concentration of 200 ppm or less. Was irradiated to form a surface protective layer. The average particle diameter of the matting agent (silica) in the surface protective layer was 10 μm, and the content was 10 parts by mass with respect to 100 parts by mass of the resin solid content.

The composition of the ionizing radiation curable resin used for the surface protective layer is as follows.
· Bifunctional urethane acrylate oligomer (Tg: 25 ° C, molecular weight (Mn): 1500) 80 parts by mass · Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher, molecular weight (Mn): 1500) 20 parts by mass Finally, surface protection The layer side was heated with an infrared non-contact type heater to soften the base sheet and the transparent resin layer, and then immediately embossed by hot pressure to form a textured pattern with a wood grain pattern to produce a decorative sheet .

(Production of decorative board)
Water-based emulsion adhesive (Rikabond BA-10L (main agent): BA-11B (curing agent) manufactured by Chuo Rika Kogyo Co., Ltd.) = 100: 2.5 (mass ratio) on 2.5 mm medium density wood fiberboard (MDF) )) Was uniformly applied at 80 g / m ² , the decorative sheets were bonded together, and cured at room temperature for 3 days to prepare a decorative board.

Examples 2 and 3, Comparative Examples 1 and 2
By changing the content of the resin forming the surface protective layer and the matting agent (silica) as shown in Table 1, and changing the average particle diameter of silica in the solid printing gloss adjusting layer, the solid printing gloss adjusting layer The decorative sheets and decorative plates of Examples 2 and 3 and Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the center line average roughness of the front surface was changed as shown in Table 1.

The composition of the anti-slip ionizing radiation curable resin (anti-slip EB resin) used for the surface protective layer of the decorative sheet of Example 3 and Comparative Example 2 is as follows.
· Bifunctional urethane acrylate oligomer (Tg: 25 ° C, molecular weight (Mn): 1500) 68 parts by mass · Bifunctional urethane acrylate oligomer (Tg: -55 ° C, molecular weight (Mn): 5000) 12 parts by mass · 6 functional urethane acrylate Oligomer (Tg: 200 ° C. or higher, molecular weight (Mn): 1500) 20 parts by mass In each decorative sheet, the center line average roughness of the front surface of the solid printing gloss adjustment layer is in accordance with JIS B0601: 1982. Measured.

(Evaluation method)
≪60 ° gloss measurement (evaluation of low gloss) ≫
The 60 ° gloss of the surface of the decorative sheet was measured by a method based on JIS Z-8741. Measurement of 60 gloss was performed using a glossiness measuring instrument (trade name: GMX-202, manufactured by Murakami Color Research Laboratory Co., Ltd.).

≪Coin scratch test (scratch resistance test) ≫
The surface of each decorative board produced as described above was rubbed once with a coin (10-yen coin) in contact with the decorative board surface at an angle of 45 °, and the surface condition was visually confirmed. Evaluation was performed according to the following evaluation criteria.
○: The gloss of the rubbed part is not clear ×: The gloss of the rubbed part is obvious

≪Stain resistance test≫
The test was conducted according to the JAS plywood contamination B test. Specifically, each decorative board produced as described above was cut into a 10 cm square and used as a test piece. After placing the test piece horizontally, a red crayon (JIS S 6026) was applied to the surface protective layer surface of the test piece. Then, a straight line having a width of 10 mm and a length of 10 cm was drawn, left for 2 hours, wiped with a dry cloth, and the surface condition was visually observed. Evaluation was performed according to the following evaluation criteria.
○: The straight line was wiped off ×: The straight line was not wiped off and contamination remained

≪Anti-slip test (OY ・ PSM) ≫
For each decorative board produced as described above, the slip resistance value (CSR value) by socks was measured using a Tokyo Institute of Technology slip tester (O-Y PSM). Evaluation was performed according to the following evaluation criteria.
A: The measured value is 0.40 or more. B: The measured value is 0.35 or more and less than 0.40. Δ: The measured value is 0.30 or more and less than 0.35. X: The measured value is less than 0.30. The range of the slip resistance value that indicates slipperiness and that humans feel comfortable is within the range of 0.30 to 0.50.

  The results are shown in Table 1 below.

  As is clear from the results in Table 1, the solid printing gloss adjusting layer and the surface protective layer are laminated, the solid printing gloss adjusting layer contains fine particles, and the center line average roughness of the front surface of the solid printing gloss adjusting layer In Examples 1 to 3 in which Ra (JIS B0601: 1982) is 0.5 μm or more, 60 ° gloss was low, low gloss was expressed, and the design was excellent. In addition, good results were obtained in the coin scratch test, stain resistance test and anti-slip test, and the scratch resistance, stain resistance and anti-slip property were excellent. Further, Example 3 using the anti-slip EB resin as the resin for forming the surface protective layer shows particularly excellent anti-slip properties, and the anti-slip property is imparted by adding a resin showing anti-slip properties to the surface protective layer. In some cases, it was found that the anti-slip property commensurate with the amount of the resin having anti-slip property can be exhibited.

  On the other hand, the decorative sheets of Comparative Examples 1 and 2 in which the center line surface roughness Ra of the front surface of the solid printing gloss adjusting layer is 0.4 μm are used as a matting agent in the surface protective layer in order to express a low gloss feeling. A large amount of the silica had to be added. For this reason, silica particles protrude from the surface of the surface protective layer, and a fine uneven shape is formed on the surface of the decorative sheet. Even if the dirt adheres to the surface, the fine details cannot be wiped off. It was inferior in pollution. Further, when the surface of the surface protective layer from which the silica particles protruded was rubbed, the protruding fine particles in the rubbed part were scraped to smooth the surface, the rubbed part was glossy, scratches were conspicuous, and the scratch resistance was poor. . In Comparative Example 2 using an anti-slip EB resin as the resin for forming the surface protective layer, the anti-slip test was evaluated as “good”, and the anti-slip property corresponding to the amount of the resin exhibiting anti-slip property was exhibited. There wasn't.

1. 1. Back primer layer 2. base material sheet Pattern layer 4. 4. Transparent adhesive layer 5. Transparent resin layer Primer layer 7. Solid printing gloss adjustment layer 8. Surface protective layer

Claims (10)

A decorative sheet in which at least a solid printing gloss adjusting layer and a surface protective layer are laminated in this order on a base sheet,
(1) The solid printing gloss adjusting layer contains fine particles having an average particle size of 8 to 20 μm,
(2) the solid print gloss center line average roughness Ra of the front surface of the adjustment layer (JIS B0601: 1982) is Ri der than 0.5 [mu] m,
(3) The surface protective layer contains a matting agent, and the content of the matting agent is 8 to 14 parts by mass with respect to 100 parts by mass of the resin solid content of the resin forming the surface protective layer.
A decorative sheet characterized by that.   The decorative sheet according to claim 1, wherein the surface protective layer contains a matting agent, and the matting agent has an average particle diameter of 10 to 20 μm. The decorative sheet according to claim 1 or 2 , wherein the content of the fine particles is 30 to 70% by mass with respect to 100% by mass of the resin solid content of the resin forming the solid printing gloss adjusting layer. The decorative sheet according to any one of claims 1 to 3 , wherein the surface protective layer is an ionizing radiation curable resin layer and has a thickness of 6 µm or more. The decorative sheet according to any one of claims 1 to 4 , wherein the surface protective layer contains an ionizing radiation curable resin having a glass transition point (Tg) of 0 ° C or lower. The solid print luster control layer has a thickness of 0.5 to 5.0 .mu.m, the decorative sheet according to any one of claims 1-5. The decorative sheet according to any one of claims 1 to 6 , wherein the decorative sheet is embossed from the front surface side of a layer immediately below the solid printing gloss adjusting layer. The decorative sheet according to any one of claims 1 to 7 , which is embossed from the surface protective layer side. On the base sheet, at least a solid printing gloss adjusting layer and a surface protective layer are laminated in this order,
(1) The solid printing gloss adjusting layer contains fine particles having an average particle size of 8 to 20 μm,
(2) the solid print gloss center line average roughness Ra of the front surface of the adjustment layer (JIS B0601: 1982) is Ri der than 0.5 [mu] m,
(3) The decorative sheet in which the surface protective layer contains a matting agent, and the content of the matting agent is 8 to 14 parts by mass with respect to 100 parts by mass of the resin solid content of the resin forming the surface protective layer. A manufacturing method of
A method for producing a decorative sheet comprising the following steps (i) and (ii):
(I) Solid printing gloss containing fine particles having an average particle diameter of 8 to 20 μm on the base sheet and having a center line average roughness Ra (JIS B0601: 1982) of 0.5 μm or more. Step 1 of forming the adjustment layer,
(Ii) Step 2 of forming a surface protective layer having a matting agent content of 8 to 14 parts by mass with respect to 100 parts by mass of the resin solid content of the resin forming the surface protective layer on the solid printing gloss adjusting layer 2 . A decorative board formed by sticking the decorative sheet according to any one of claims 1 to 8 to an adherend.

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