JP5428424B2 - Embossed plate and decorative sheet embossed using the same - Google Patents

Description

  The present invention relates to an embossed plate and a decorative sheet embossed using the embossed plate. More specifically, the present invention relates to an embossed plate having a specific surface roughness obtained through sandblasting and a low-gloss decorative sheet obtained by embossing using the embossed plate.

  The decorative sheet is often used by sticking to the surface of the wooden board for the purpose of protecting the surface of the wooden board, decorating and the like. And the decorative board obtained by this is used for various building materials, furniture, etc.

  As a decorative sheet, for example, a laminate in which a base sheet, a picture layer, a transparent resin layer, and a surface protective layer are sequentially laminated is known, and an adherend (for example, a wooden board) is laminated on the base sheet side. It is used as a decorative board.

The decorative sheet is required to have a low gloss front surface depending on the application. Therefore, it is known to reduce the gloss by including a matting agent in the surface protective layer. For example, Patent Document 1 discloses a layer made of 1 to 10 g / m ² of a thermosetting or electron beam curable anchor agent on a base sheet provided with an arbitrary pattern, and 3 to 10 g / m ² of matte. There is described a matte decorative sheet comprising a layer made of an electron beam curable resin containing an agent.

  However, when the matting agent such as an inorganic filler is used to reduce the matting, if the matting agent content increases, internal haze (white turbidity) is generated in the surface protective layer, and the pattern of the lower layer is clear. There is a problem of lowering. For this reason, there is a limit to the reduction in matting with a matting agent. In recent years, attempts have been made to reduce the glossiness of the front surface by embossing from the surface protective layer side. This embossing is performed mainly by an embossed plate subjected to glass bead blasting. That is, an embossed plate in which a blast pattern is formed by spraying a projection material onto the surface of the embossing cylinder by a glass bead blasting method is used. In the glass bead blasting process, spherical glass particles having a Mohs hardness of about 5 are generally used as the projection material.

  However, in the embossed plate, the front surface of the decorative sheet cannot be sufficiently glossed, and there is room for further improvement.

JP-A-8-281896

  Accordingly, an object of the present invention is to provide an embossing plate useful for reducing the front surface of a decorative sheet by embossing and a low-gloss decorative sheet obtained by embossing using the embossed plate. To do.

  As a result of intensive studies in view of the problems of the prior art, the present inventor is able to achieve the above object when embossing using an embossed plate having a specific surface roughness obtained through sandblasting. The headline and the present invention were completed.

That is, this invention relates to the manufacturing method of the following decorative sheet, a decorative board, and a decorative sheet.
1. A decorative sheet having a surface protective layer on the outermost surface,
The surface protective layer contains an ionizing radiation curable resin and an inorganic filler, and the content of the inorganic filler is 15 parts by weight or less with respect to 100 parts by weight of the resin component,
The decorative sheet is a chrome layer after sandblasting the surface of a copper substrate having a concavo-convex pattern using at least one of alumina particles and titania particles as a projection material and having a particle size of 100 or less. Or an embossed plate having a surface roughness Rz of 30 or more, which is obtained by laminating a chromium layer on the surface of a copper base material having a concavo-convex pattern and then sandblasting using the projection material. A decorative sheet in which the 60 ° gloss value of the outermost surface is 10 or less by embossing from the surface side.
2 . The said decorative sheet is a decorative sheet of said claim | item 1 which has a pattern layer, a transparent resin layer, and a surface protective layer in order on a base material sheet.
3 . A decorative board obtained by joining the decorative sheet according to Item 1 or 2 and an adherend.
4 . Item 4. The decorative board according to Item 3 , wherein the adherend is a wood material.
5 . A method for producing a decorative sheet having a surface protective layer on the surface according to item 1, wherein the 60 ° gloss value of the outermost surface is 10 or less,
Surface protection by coating a coating liquid containing an ionizing radiation curable resin and an inorganic filler on the outermost surface, and the content of the inorganic filler is 15 parts by weight or less with respect to 100 parts by weight of the resin component, followed by curing. After the step of forming a layer and the surface of the copper base material having a concavo-convex pattern, sandblasting is performed using at least one of alumina particles and titania particles as a projection material and having a particle size of 100 or less . An embossed plate having a surface roughness Rz of 30 or more obtained by laminating a chromium layer or laminating a chromium layer on the surface of a copper substrate having an uneven pattern and then sandblasting using the projection material The manufacturing method containing the process of embossing from the outermost surface side using.

  Hereinafter, the embossed plate and the decorative sheet of the present invention will be described.

1. Embossed plate The embossed plate of the present invention is obtained by 1) sandblasting the surface of a copper substrate having a concavo-convex pattern and then laminating a chromium layer, or 2) after laminating a chromium layer on a copper substrate having a concavo-convex pattern The surface roughness Rz is 30 or more, which is obtained by sandblasting.

  The uneven pattern imparted to the copper base material is a pattern to be imparted to the front surface of the decorative sheet by embossing. Examples of the concavo-convex pattern include directional patterns such as a wood grain conduit pattern, a float pattern (a concavo-convex pattern of raised annual rings), a hairline, and a satin texture, and a desired pattern can be appropriately selected from these patterns. . Among these, the wood grain conduit pattern is suitable as an uneven pattern imparted to the front surface of the woody decorative sheet.

  The method for imparting the concavo-convex pattern to the copper base material is not limited. For example, a concavo-convex pattern can be imparted to the copper base material by a known corrosion method or the like. An example of the uneven | corrugated pattern provision process is shown. First, after creating a pattern of a predetermined concavo-convex pattern (wood conduit pattern, float pattern, etc.) on a computer screen, an endless file is created so that the image of the pattern is endless with the circumference of the cylinder of the embossed plate. To create an endless file, software for generating an endless pattern may be designed, and the file joint portion may be corrected with commercially available retouching software. The concavo-convex pattern data of the endless file is directly output and baked on a copper base material (embossed cylinder) coated with a resist photosensitive solution using a laser stream plate making apparatus. In this case, the width feed function of the laser stream plate making apparatus can be used in the cylinder width direction. Subsequently, a desired embossed concavo-convex pattern can be imparted to the copper base material by performing development, corrosion, and resist peeling of the cylinder. The surface roughness of the concavo-convex pattern to be applied to the copper base material is not limited and may be the same as the conventional case of providing the concavo-convex pattern to the copper base material (embossed cylinder), but the concavo-convex pattern disappears by the subsequent sandblasting treatment. In order to avoid this, it is preferable to set the depth of the uneven pattern (plate depth) to 35 μm or more. In addition, it is preferable that the Mohs hardness of a copper base material is about 3 (about 2-4).

  When sandblasting a copper substrate having a concavo-convex pattern by the method of 1), the surface roughness Rz of the embossed plate obtained by laminating subsequent chromium layers should be 30 or more (preferably 30 to 60). If it does not specifically limit. The same applies to the case where the chrome layer is laminated on the copper base material having the concavo-convex pattern by the method 2) and then sandblasted.

  The laminated thickness of the chromium layer is preferably about 15 to 30 μm in the method 1), preferably 15 μm or more in the method 2), and the upper limit is not limited as long as the uneven pattern is not lost. For example, about 300 μm Can be set. A chromium layer is provided by plating etc., for example.

  As the projection material used for the sandblasting treatment, inorganic particles such as iron, silicon carbide, alumina, titania, chromium oxide, iron oxide and the like can be used. Among these projection materials, at least one of alumina particles and titanium oxide particles is preferable. The shape of the inorganic particles is not limited, but is generally indefinite. The Mohs hardness of the inorganic particles is preferably about 7 (about 6 to 9). The particle size of the inorganic particles is preferably 100 or less (# 100 or less). The sand blasting is performed by spraying inorganic particles as a projection material, for example, from the tip of the nozzle to the surface of the copper substrate by the force of compressed air. In the present invention, the sandblasting treatment can be performed once or a plurality of times so that a predetermined surface roughness can be obtained in combination with the lamination of chromium layers.

  When the chromium layer is laminated on the treated surface following the sandblasting process by the method 1), the laminated thickness of the chromium layer is about 15 to 30 μm. Thereby, an embossed plate having a surface roughness Rz of 30 or more (preferably 30 to 60) is obtained. Moreover, when laminating a chromium layer prior to sandblasting by the method 2), the thickness of the chromium layer is preferably 15 μm or more, and the upper limit is about 300 μm. After lamination of the chromium layer, an embossed plate having a surface roughness Rz of 30 or more (preferably 30 to 60) is obtained by sandblasting.

  In addition, Rz of this specification is a ten-point average roughness prescribed | regulated to JISB0601, and is a measured value on measurement length 4mm and cut-off value 0.8mm conditions (Rz is a sandblasting process + chromium layer) This is the surface roughness of the blasted surface obtained by laminating, and does not include the influence of uneven patterns such as the wood grain conduit pattern).

  The embossed plate obtained through the above process has a specific sandblast pattern resulting from the sandblasting process in addition to the uneven pattern to be applied to the decorative sheet (embossed uneven pattern such as a wood grain conduit pattern). When the outermost surface of the decorative sheet is embossed using such an embossed plate, a sandblast pattern is provided in addition to the embossed uneven pattern. And by providing such a sandblast pattern, the front surface of the decorative sheet has a low gloss (60 ° gloss value is 10 or less).

2. The decorative sheet of the present invention is a decorative sheet having a surface protective layer on the outermost surface, and the 60 ° gloss value of the outermost surface is 10 or less by being embossed from the outermost surface side by the embossed plate of the present invention. It is characterized by low gloss.

  The layer configuration of the decorative sheet is not particularly limited as long as it has a surface protective layer on the outermost surface, and the configurations of known decorative sheets can be widely adopted. Among them, a decorative sheet having a pattern layer, a transparent resin layer, and a surface protective layer in this order on a base sheet is a preferred example.

  Hereinafter, this layer configuration will be specifically described by taking an example.

The base material sheet and the transparent resin layer The base material sheet and the transparent resin layer can be made of a material (resin) used in a known decorative sheet, except that the latter is transparent.

  The resin used for forming these layers is preferably a thermoplastic resin. Specifically, soft, semi-rigid or rigid polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples include polymers, ionomers, acrylic esters, and methacrylic esters. In the present invention, a polyolefin resin such as polypropylene is particularly preferable as the transparent resin layer.

  These layers may be colored. In this case, it can color by mix | blending a coloring agent (a pigment or dye) with the said resin. Colorants include titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene. Examples thereof include organic pigments (including dyes) such as blue RS and aniline black, metal pigments such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate, and the like. These can be used alone or in combination of two or more. Further, the addition amount of the colorant may be appropriately set according to the desired color tone.

  In addition, these layers include various kinds of fillers, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, soft components (for example, rubber), and the like. Additives may be included.

  A flame retardant is added in order to provide flame resistance. For example, chlorinated paraffin, tricresyl phosphate, chlorinated oil, tetrabromophthalic anhydride, tetrabromobisphenol A, dibromopropyl phosphate, tri (2,3-dibromopropyl) phosphate, antimony oxide, hydrous alumina, barium borate, etc. It can be used suitably.

  Antioxidants are added to suppress or prevent oxidative degradation. For example, alkylphenols, amines, quinones and the like are suitable.

  The ultraviolet absorber absorbs ultraviolet rays in a wavelength range of 280 to 450 nm that causes deterioration of the resin (particularly polyolefin resin). Examples thereof include benzophenone-based, salicylate-based, benzotriazole-based, and acrylonitrile-based ultraviolet absorbers. For example, an organic compound having an OH group in the molecule can be used. Specifically, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'- 2′-hydroxyphenyl-5-5 such as isobutyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-isobutyl-5′-propylphenyl) -5-chlorobenzotriazole Chlorobenzotriazole ultraviolet absorbers, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazo Benzotriazole-based UV absorbers such as 2'-hydroxyphenylbenzotriazole-based UV absorbers such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxy-4,4′-tetrahydroxybenzophenone UV absorbers, 2,4-dihydroxy Examples include benzophenone ultraviolet absorbers such as 2-hydroxybenzophenone ultraviolet absorbers such as benzophenone, and salicylic acid ester ultraviolet absorbers such as phenyl salicylate and 4-tert-butylphenyl salicylate. In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into the benzotriazole skeleton can also be used. Of these, benzotriazole-based ultraviolet absorbers are particularly preferred in consideration of absorption wavelength and colorability problems.

  The radical scavenger is added to prevent discoloration due to sunlight, cracks, whitening, strength deterioration, and the like and improve weather resistance. As the radical scavenger, in addition to bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, for example, a hindered amine radical scavenger such as a compound disclosed in JP-B-4-82625, Piperidyl radical scavengers and the like are used.

  The method for forming these layers is not limited, for example, a method in which a preformed sheet or film is laminated on an adjacent layer, or a resin composition containing the resin is applied onto an adjacent layer by melt extrusion. Any of a method and a method of laminating together with adjacent layers can be employed. In the present invention, it is particularly preferable to form a layer by melt extrusion, and it is particularly desirable to form a polyolefin resin by melt extrusion. Specifically, it can be suitably formed by previously forming an adhesive layer on the pattern layer and applying a polypropylene thermoplastic elastomer on the adhesive layer by melt extrusion. What is necessary is just to implement the method of melt extrusion, for example according to the well-known method using a T die.

  The thickness of these layers can be appropriately set depending on the use of the final product, the method of use, and the like, but generally it is preferably in the range of 50 to 250 μm. In particular, the transparent resin layer is preferably about 20 to 200 μm.

  Corona discharge treatment can also be performed on the front surface (front surface) and / or the back surface of the base sheet, if necessary, in order to enhance the adhesion with the adjacent layers. The method and conditions for the corona discharge treatment may follow a known method.

  Moreover, a primer layer can also be formed on the front surface (front surface) and / or the back surface of the base sheet. As a material for forming the primer layer (primer agent), for example, polyester resins, polyurethane resins, acrylic resins, polycarbonate resins, vinyl chloride / vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, and other resins Further, compounds such as alkyl titanate and ethyleneimine can also be used. In particular, it is preferable to use a two-component curable urethane resin. It is preferable to use fatty acid isocyanate (aliphatic isocyanate) such as hexamethylene diisocyanate (HMDI) as the isocyanate and acrylic polyol as the polyol, because more excellent weather resistance and adhesion can be obtained.

  The primer layer can be formed according to a known printing method, coating method, or the like by dissolving or dispersing the primer agent as it is or in a solvent.

Picture layer The picture layer (printing layer) can represent characters, symbols, drawings, etc. in addition to the patterns of natural materials such as wood grain and joints.

  The pattern layer can be formed using an ink containing a colorant and a resin binder. As the binder, for example, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, polyester resin, urethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, cellulose resin, and the like can be used. Or 2 or more types can be used. As the colorant, known or commercially available products can be used. Specifically, the above colorants can be used.

  The pattern layer can be suitably formed by a known printing method such as gravure printing, offset printing, silk screen printing, or transfer printing from a transfer sheet. For example, printing may be performed using an ink colored by adding a pigment (or dye) so that the pattern layer has a wood grain base color.

An adhesive layer may be interposed between the adhesive layer picture layer and the transparent resin layer.

  The adhesive used in the adhesive layer can be appropriately selected from known or commercially available adhesives according to the components constituting the pattern layer or the transparent resin layer. Examples thereof include thermosetting resins such as polyester resins, polyurethane resins, and epoxy resins, in addition to polyolefin resins such as polyethylene and polypropylene.

  Among these, in this invention, a urethane type resin adhesive is preferable at the point that heat resistance etc. can be improved more. Examples of the urethane resin adhesive include a two-component curable urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent).

  The polyol has two or more hydroxyl groups in the molecule. For example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol and the like are used.

  Moreover, as said isocyanate, the polyvalent isocyanate which has a 2 or more isocyanate group in a molecule | numerator is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, aliphatics such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate (or Alicyclic) isocyanates are used. Further, adducts or multimers of the above various isocyanates can also be used. Examples thereof include adducts of tolylene diisocyanate and trimers of tolylene diisocyanate.

  If necessary, the adhesion surface can be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, and surface roughening treatment.

  What is necessary is just to implement as an adhesion | attachment method according to a well-known method according to the kind etc. of adhesive agent to be used. For example, a method of coating on a pattern layer by melt extrusion (extrusion coating method) using a polyolefin resin such as polyethylene or polypropylene, an isocyanate to a thermosetting resin such as a polyester resin, a polyurethane resin, or an epoxy resin, Apply an adhesive such as a crosslinking agent such as amine, a polymerization initiator such as methyl ethyl ketone peroxide, hydroperoxide, azabisisobutyronitrile, a polymerization accelerator such as cobalt naphthenate, dimethylaniline, etc. A dry laminating method can be employed. In the present invention, the picture layer and the transparent resin layer can be laminated by thermocompression bonding using an adhesive that can be thermocompression bonded.

  The thickness of the adhesive layer varies depending on the surface protective layer, the type of adhesive used, and the like, but is usually about 0.1 to 30 μm.

A surface protective layer is formed on the surface protective layer transparent resin 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 forming a transparent surface protective layer with ionizing radiation curable resin or two-component curable urethane resin, it is easy to improve the abrasion resistance, impact resistance, contamination 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.

  As the ultraviolet light source, for example, 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, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton 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. Among them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

  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.

  These surface protective layers may contain a weathering agent, a plasticizer, a stabilizer, an inorganic filler, a dispersant, a colorant such as a dye and a pigment, a solvent, and the like, if necessary. In addition, although the glossiness of a surface protective layer can also be aimed at by containing an inorganic filler, when content increases, there exists a problem that internal haze (white turbidity) generate | occur | produces and the clarity of the pattern of a lower layer falls. Therefore, the content of the inorganic filler is preferably set to 15 parts by weight or less (preferably 6 to 14 parts by weight) with respect to 100 parts by weight of the resin component.

  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.

  The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the characteristics of the final product, but is usually about 0.1 to 50 μm, preferably about 1 to 20 μm.

Embossing In the present invention, embossing is performed from the outermost surface (surface protective layer) side of the decorative sheet using the embossed plate of the present invention.

  For embossing, for example, after the decorative sheet is heated and softened on a heating drum, it is further heated to 160 to 180 ° C. with an infrared radiation heater, and pressed and shaped with an embossed plate provided with a concavo-convex pattern of a desired shape. , Cooled and fixed. In this invention, as long as the said embossing plate is used as an embossing plate, the embossing machine which installs an embossing plate is not limited. For example, in a known single wafer or rotary embossing machine, an embossing plate replaced with the embossing plate can be used.

  By embossing using the embossed plate of the present invention, a sandblast pattern having a surface roughness Rz of about 18 or more is given in addition to the desired uneven pattern. By applying this sandblast pattern, the 60 ° gloss value of the surface protective layer becomes 10 or less (preferably 5 to 9). In this invention, since the surface of a decorative sheet is made low gloss by embossing, content of the matting agent (inorganic filler) mix | blended with a surface protective layer can be restrained low. For example, it can be set to 15 parts by weight or less with respect to 100 parts by weight of the resin component of the surface protective layer. Therefore, since the problem of haze due to the blending of the matting agent is improved, the decorative sheet can be reduced in gloss without affecting the sharpness of the pattern.

3. Decorative plate The decorative sheet of the present invention becomes a decorative plate by joining adherends.

Adhering material The adhering material is not limited, and the same material as a known decorative board can be used. For example, wood materials, metals, ceramics, plastics, glass and the like can be mentioned. In particular, the decorative sheet of the present invention can be suitably used for wood materials. Specific examples of 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. Etc.

The method of laminating and laminating the adherend is not limited, and for example, a method of sticking a decorative sheet to the adherend with an adhesive 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 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.

  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.

  The embossed plate of the present invention is obtained by 1) sandblasting the surface of a copper substrate having a concavo-convex pattern and then laminating a chromium layer, or 2) laminating a chromium layer on a copper substrate having a concavo-convex pattern and then sandblasting. It is obtained by processing, and the surface roughness Rz is 30 or more. By embossing the outermost surface of the decorative sheet using this embossed plate, a sandblast pattern is imparted to the outermost surface of the decorative sheet, and the 60 ° gloss value of the outermost surface can be reduced to 10 or less. Such an effect cannot be obtained by the conventional blasting with glass beads, but can be obtained for the first time by the sandblasting.

It is a figure which shows the layer structure of the decorative sheet produced in the Example and the comparative example. It is a figure which shows (a) surface roughness of the embossing plate used in Example 1, and (b) surface roughness of the outermost surface of the decorative sheet produced in Example 1. In the figure, the horizontal scale (horizontal direction with respect to the surface of the embossed plate or decorative sheet) indicates 1000 μm / 10 scale, and the vertical scale (perpendicular direction with respect to the surface of the embossed plate or decorative sheet) indicates 20 μm / 10 scale. . The same applies to FIGS. (A) It is a figure which shows the surface roughness of the embossing plate used in the comparative example 1, and (b) the surface roughness of the outermost surface of the decorative sheet produced in the comparative example 1. (A) It is a figure which shows the surface roughness of the embossing plate used in Comparative Example 3, and (b) the surface roughness of the outermost surface of the decorative sheet produced in Comparative Example 3. (A) It is a figure which shows the surface roughness of the embossing plate used in Comparative Example 4, and (b) the surface roughness of the outermost surface of the decorative sheet produced in Comparative Example 4. (A) It is a figure which shows the surface roughness of the outermost surface of the decorative sheet produced in the comparative example 5. FIG.

  Examples and comparative examples are shown below to explain the present invention more clearly. However, the present invention is not limited to the examples.

Examples 1-4 and Comparative Examples 1-6
A decorative sheet having a layer structure shown in FIG. 1 was produced. A polypropylene resin film (thickness: 60 μm) was prepared as the base sheet 1 colored with the colorant. After performing corona discharge treatment on the front and back surfaces, a primer layer using a urethane resin as a binder was formed on the surface by gravure printing. Next, the pattern layer 2 (thickness 2 μm) was formed by gravure printing using an ink having a urethane-based resin as a binder. On the other hand, a primer layer (not shown) using urethane resin as a binder was formed on the back surface by gravure printing.

  Next, a coating solution made of a two-component curable urethane resin was applied on the pattern layer to form an adhesive layer (thickness 3 μm). On top of that, a transparent thermoplastic resin layer 3 (thickness 80 μm) was formed by melt extrusion coating a polypropylene thermoplastic elastomer with a T-die. A two-component curable urethane-based resin was applied on the transparent resin layer 3 to form a primer layer (thickness: 2 μm).

  Next, after forming a coating film by gravure coating using a coating liquid (EB coating liquid) containing an ionizing radiation curable resin, the coating film is crosslinked by irradiating an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy). The surface protective layer 4 (thickness 15 μm) was formed by curing.

  Finally, the surface protective layer side was heated with an infrared non-contact heater to soften the surface protective layer and the transparent resin layer, and then immediately embossed by heat pressure from the surface of the surface protective layer. Thereby, a decorative sheet having an embossed pattern (wood grain conduit pattern) and a blast pattern on the surface resin layer was obtained.

  Details of the embossed plate and the EB coating liquid are shown below.

<Example 1>
・ Embossed plate After sandblasting (projection material: alumina particles of # 60, Mohs hardness 9) on a copper substrate (Mohs hardness 3) having an uneven shape of wood grain conduit depth (conduit plate depth 60 μm), chromium plating (20 μm) is applied. Thus, an embossed plate having a surface roughness Rz of 43 was produced.

The surface roughness of the embossed plate is shown in FIG. Moreover, the surface roughness of the surface protective layer after embossing is shown in FIG. The measuring instrument is “Surfcom 120A” manufactured by Tokyo Seimitsu Co., Ltd.
・ EB coating liquid Urethane acrylate oligomer 100 parts by weight Silica (manufactured by Fuji Silysia: Cicilia 450) 14 parts by weight Antibacterial agent (silver ion-carrying zeolite: average particle size 6.4 μm) 0.5 parts by weight Ethyl acetate 100 parts by weight <Example 2>
・ Embossed plate After sandblasting (projection material: # 40 alumina particles, Mohs hardness 9) on a copper substrate (Mohs hardness 3) with a grained shape (grain depth 60 μm) in wood grain, chromium plating (20 μm) is applied. Thus, an embossed plate having a surface roughness Rz of 45 was produced.
-EB coating liquid The same thing as Example 1 was used.

<Example 3>
・ Embossed plate Sand-blasting (projection material: # 100 alumina particles, Mohs hardness 9) on a copper substrate (Mohs hardness 3) having an uneven shape of wood grain conduit depth (conduit plate depth 60 μm), followed by chromium plating (20 μm) Thus, an embossed plate having a surface roughness Rz of 30 was produced.
-EB coating liquid The same thing as Example 1 was used.

<Example 4>
Embossing plate A copper layer (Mohs hardness 3) having a grain shape of the grain (conduit depth 60 μm) is laminated by plating 20 μm of a chromium layer (Mohs hardness 9), and sandblasting (projection material: # 60 alumina particles, By applying Mohs hardness 9), an embossed plate having a surface roughness Rz of 33 was produced.
-EB coating liquid The same thing as Example 1 was used.

<Comparative Example 1>
・ Embossed plate A copper substrate (Mohs hardness 3) having a grain-concave shape (conduit depth 60 μm) is subjected to glass bead blasting (projection material: glass beads having an average particle size of 200 μm, Mohs hardness 5), and then chrome plating (20 μm). ) To produce an embossed plate having a surface roughness Rz of 7.5.

The surface roughness of the embossed plate is shown in FIG. Moreover, the surface roughness of the surface protective layer after embossing is shown in FIG.
-EB coating liquid The same thing as Example 1 was used.

<Comparative example 2>
・ Embossed plate After sandblasting (projection material: # 200 alumina particles, Mohs hardness 9) on a copper substrate (Mohs hardness 3) having an uneven shape of wood grain conduit (conduit depth 60 μm), chromium plating (20 μm) is applied. Thus, an embossed plate having a surface roughness Rz of 13 was produced.
-EB coating liquid The same thing as Example 1 was used.

<Comparative Example 3>
・ Embossed plate A copper substrate (Mohs hardness 3) having an uneven shape (grain depth 60 μm) in a wood grain is sandblasted (projection material: alumina particles of # 150, Mohs hardness 9) and then chromium plated (20 μm). Thus, an embossed plate having a surface roughness Rz of 15 was produced.

The surface roughness of the embossed plate is shown in FIG. Moreover, the surface roughness of the surface protective layer after embossing is shown in FIG.
-EB coating liquid The same thing as Example 1 was used.

<Comparative Example 4>
-Embossed plate Wood grain conduit uneven shape (conduit plate depth 60μm) and satin textured copper substrate (Mohs hardness 3) glass bead blasting (projection material: glass beads with an average particle size of 200μm, Mohs hardness 5), then chromium By applying plating (20 μm), an embossed plate having a surface roughness Rz of 38 was produced.

The surface roughness of the embossed plate is shown in FIG. Moreover, the surface roughness of the surface protective layer after embossing is shown in FIG.5 (b).
-EB coating liquid The same thing as Example 1 was used.

<Comparative Example 5>
・ Embossed plate A copper substrate (Mohs hardness 3) having a grain-concave shape (conduit depth 60 μm) is subjected to glass bead blasting (projection material: glass beads having an average particle size of 200 μm, Mohs hardness 5), and then chrome plating (20 μm). ) To produce an embossed plate having a surface roughness Rz of 7.5.

FIG. 6B shows the surface roughness of the surface protective layer after embossing.
-EB coating liquid Urethane acrylate oligomer 100 parts by weight Silica (manufactured by Fuji Silysia: Cicilia 450) 18 parts by weight Antibacterial agent (silver ion-carrying zeolite: average particle size 6.4 μm) 0.5 parts by weight Ethyl acetate 100 parts by weight <Comparative Example 6>
-Embossed plate A copper layer (Mohs hardness 3) having a grain shape of a wood grain conduit (conduit depth 60 μm) is laminated by plating with a chromium layer (Mohs hardness 9) 20 μm, and sandblasting (projection material: # 180 alumina particles, An embossed plate having a surface roughness Rz of 6 was produced by applying a Mohs hardness of 9).
-EB coating liquid The same thing as Example 1 was used.

Test example 1
The physical properties of the embossed plates prepared in Examples and Comparative Examples and the physical properties of the decorative sheet after embossing were examined. The results are shown in Table 1. The measurement method was as follows.
(1) Embossed plate surface roughness: Rz
The surface roughness (Rz: 10-point average roughness) of the embossed plate was measured according to JIS B 0601 with a measurement length of 4 mm and a cut-off value of 0.8 mm. In addition, Rz is Rz of the surface in which the blast pattern is formed, and is not the surface roughness which considered the unevenness | corrugation of the wood grain conduit pattern.
(2) Pattern clarity The pattern was observed from the front surface of the decorative sheet. The case where the pattern was clear was evaluated as ◯, and the case where the pattern was unclear due to whitening of the surface protective layer was evaluated as X.
(3) 60 ° gloss value of the front surface of the decorative sheet The 60 ° gloss value of the front surface of the decorative sheet was measured based on the 60 ° specular gloss measurement method defined in JIS Z 8761.

  From Table 1, it can be seen that the gloss value of the front surface of the decorative sheet can be effectively reduced without causing whitening or the like in the surface protective layer by using the embossed plate of the present invention.

1. 1. Base sheet 2. 2. Pattern printing layer 3. Transparent resin layer Surface protective layer

Claims (5)

A decorative sheet having a surface protective layer on the outermost surface,
The surface protective layer contains an ionizing radiation curable resin and an inorganic filler, and the content of the inorganic filler is 15 parts by weight or less with respect to 100 parts by weight of the resin component,
The decorative sheet is a chrome layer after sandblasting the surface of a copper substrate having a concavo-convex pattern using at least one of alumina particles and titania particles as a projection material and having a particle size of 100 or less. Or an embossed plate having a surface roughness Rz of 30 or more, which is obtained by laminating a chromium layer on the surface of a copper base material having a concavo-convex pattern and then sandblasting using the projection material. A decorative sheet in which the 60 ° gloss value of the outermost surface is 10 or less by embossing from the surface side. The decorative sheet has a pattern layer, a transparent resin layer and a surface protective layer in this order on a substrate sheet, the decorative sheet according to claim 1. Claim 1 or 2 decorative sheet and made by joining a adherend veneer according to. The decorative board according to claim 3 , wherein the adherend is a wooden material. A method for producing a decorative sheet comprising the surface protective layer according to claim 1, wherein the outermost surface has a 60 ° gloss value of 10 or less,
Surface protection by coating a coating liquid containing an ionizing radiation curable resin and an inorganic filler on the outermost surface, and the content of the inorganic filler is 15 parts by weight or less with respect to 100 parts by weight of the resin component, followed by curing. After the step of forming a layer and the surface of the copper base material having a concavo-convex pattern, sandblasting is performed using at least one of alumina particles and titania particles as a projection material and having a particle size of 100 or less . An embossed plate having a surface roughness Rz of 30 or more obtained by laminating a chromium layer or laminating a chromium layer on the surface of a copper substrate having an uneven pattern and then sandblasting using the projection material The manufacturing method containing the process of embossing from the outermost surface side using.

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