JP2016064629A - Decorative sheet and method for producing the same, and decorative plate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which has excellent embossed shape-imparting characteristics, suppresses collapse of embossing when bonded to an adherend, has excellent curling resistance and can be wound so as to be in a rolled state.SOLUTION: There is provided a decorative sheet 1 in which at least a transparent resin layer 4 and a surface protective layer 5 are laminated in this order on a substrate sheet 2 and at least a backer layer 6 is laminated on the rear surface of the substrate sheet 2, wherein the surface of the decorative sheet 1 has a ten-point average roughness Rzof 40 μm or more, the surface protective layer 5 contains an ionizing radiation curable resin, all of the substrate sheet 2, the transparent resin layer 4 and the backer layer 6 contains a nonhalogen-based thermoplastic resin, the backer layer 6 has a Martens hardness of 50 to 80 N/mmand the backer layer 6 is laminated by extruding and molding a resin composition for forming a backer layer 6 in a molten state to the rear surface of the substrate sheet 2.SELECTED DRAWING: Figure 1

Description

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

  Conventionally, an interior material used for the interior of a building is required to have a design property, and a decorative board is used as such an interior material. In particular, the surface of the decorative board used for the floor surface is required to have scratch resistance as well as design properties.

  Further, in Western cultures, it is normal to walk on the ground even indoors such as houses, so low pressure melamine floors are mainly used for Western floors in consideration of scratch resistance. However, the low-pressure melamine floor has a problem that it is easy to resonate during walking, is hard to touch, and is cold.

  In recent years, instead of low-pressure melamine floors, floors (so-called hybrid floors) in which vinyl chloride resin decorative sheets (vinyl chloride decorative sheets) are bonded to chipboards typically represented by cork as adherends have been used. ing. Chipboards are mechanically pulverized wood chips, bark, small-diameter logs and construction waste materials discarded at the site of demolition work, which are discarded at a lumber mill, and then compression-molded with a synthetic resin adhesive. It is a base material obtained by molding into a plate material.

  The above-mentioned hybrid floor is excellent in that it is environmentally friendly, has sound insulation and heat insulation effects, and is soft to the touch by using a chip board as an adherend. The variation of is suppressed. However, when a vinyl chloride decorative sheet is bonded to the adherend, the sticking is worsened, so it is necessary to use a backer layer made of a hard vinyl chloride resin. In a sheet, bonding to an adherend is limited to sheet bonding (that is, in the vinyl chloride decorative sheet, it is difficult to employ roll lamination as bonding to the adherend). Therefore, the vinyl chloride decorative sheet has a problem that productivity is poor. Moreover, regulations on vinyl chloride resins are in progress in Europe in consideration of environmental issues. As a countermeasure to these problems, a decorative board that does not use a vinyl chloride resin is required.

  On the other hand, in Japan, as a decorative board not using a vinyl chloride resin, for example, a decorative board in which a decorative sheet using an olefin resin is bonded to an adherend is used. However, when such a decorative sheet is bonded to an adherend such as a chipboard to form a decorative plate, there is a problem that the uneven surface shape of the chipboard appears on the surface of the decorative sheet, and the surface of the decorative plate does not become smooth. (Note that the uneven shape that appears on the surface of the decorative sheet due to the uneven surface shape of the chipboard is also referred to as “duck”). In addition, when the smoothness of the surface of the decorative board is improved by a method of increasing the thickness of the decorative sheet, the decorative sheet is thick, so that the embossing property is inferior, and when the embossed shape is shallow, it is bonded to the adherend. There is a problem in that emboss crushing occurs and the designability is lowered. Further, when the thickness of the decorative sheet is increased, there is a problem that roll lamination becomes difficult due to winding when the decorative sheet is stored in a roll state.

JP 2003-013587 A

  The present invention can also be used in Europe and other countries where regulations on vinyl chloride resins are advancing, and when a decorative board is obtained by bonding to an adherend such as a chipboard, the uneven shape of the adherend is a cosmetic. It is suppressed from appearing on the surface of the plate, has excellent embossing shapeability, suppresses embossing when bonded to an adherend, has excellent curl resistance, and is in a roll state. An object of the present invention is to provide a decorative sheet that can be rolled up.

  As a result of intensive research, the inventors have laminated at least a transparent resin layer and a surface protective layer in order on the base sheet, and at least a backer layer is laminated on the back surface of the base sheet. The decorative sheet has a specific surface roughness, and the base sheet, the transparent resin layer and the surface protective layer contain a specific resin, and include a specific resin by extrusion molding. In the case of laminating a backer layer having a thickness and hardness as described above, the inventors have found that the above object can be achieved and have completed the present invention.

That is, this invention relates to the following decorative sheet and its manufacturing method, and a decorative board and its manufacturing method.
1. A decorative sheet in which at least a transparent resin layer and a surface protective layer are sequentially laminated on the base sheet, and at least a backer layer is laminated on the back surface of the base sheet,
(1) Ten-point average roughness Rz _jis of the surface of the decorative sheet is 40 μm or more,
(2) The surface protective layer contains an ionizing radiation curable resin,
(3) The base sheet, the transparent resin layer, and the backer layer each include a non-halogen thermoplastic resin,
(4) The backer layer has a thickness of 120 to 250 μm,
(5) Martens hardness of the backer layer is 50~80N / mm ^2,
(6) The backer layer is laminated by extruding the backer layer forming resin composition in a molten state with respect to the back surface of the base sheet.
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein a gloss adjusting layer is formed on the transparent resin layer, and the gloss adjusting layer is formed adjacent to the surface protective layer.
3. A roll-like product obtained by winding the decorative sheet according to Item 1 or 2 into a roll.
4). A decorative board in which the decorative sheet according to Item 1 or 2 or the decorative sheet obtained by unwinding the roll-shaped material according to Claim 3 is laminated on an adherend.
5. A method for producing a decorative sheet in which at least a transparent resin layer and a surface protective layer are sequentially laminated on a base material sheet, and at least a backer layer is laminated on the back surface of the base material sheet, the following steps: 1-3:
(i) A laminated sheet having at least a transparent resin layer and a surface protective layer in this order on a base sheet,
The surface protective layer contains an ionizing radiation curable resin,
Step 1 of obtaining a laminated sheet, wherein the base sheet and the transparent resin layer both contain a non-halogen thermoplastic resin,
(ii) Step 2 of _setting the ten-point average roughness Rz _jis of the surface of the laminated sheet to 40 μm or more by embossing from above the surface protective layer of the laminated sheet; and
(iii) by extruding the resin composition for forming a backer layer in a molten state with respect to the back surface of the base sheet,
The backer layer comprises a non-halogen thermoplastic resin;
The backer layer has a thickness of 120 to 250 μm,
The Martens hardness of the backer layer is 50 to 80 N / mm ² .
Step 3 of laminating the backer layer,
In order. The manufacturing method of the decorative sheet characterized by the above-mentioned.
6). A method for producing a decorative sheet in which at least a transparent resin layer and a surface protective layer are sequentially laminated on a base material sheet, and at least a backer layer is laminated on the back surface of the base material sheet, the following steps: 1-4:
(i) A laminate having at least a transparent resin layer on a substrate sheet,
Step 1 for obtaining a laminate in which the base sheet and the transparent resin layer each include a non-halogen thermoplastic resin;
(ii) Step 2 of embossing from above the transparent resin layer of the laminate;
(iii) By coating a resin composition for forming a surface protective layer containing an ionizing radiation curable resin on the transparent resin layer,
A laminated sheet having at least a transparent resin layer and a surface protective layer on a substrate sheet,
Step 3 of obtaining a laminated sheet having a ten-point average roughness Rz _jis of 40 μm or more on the surface of the laminated sheet, and
(iv) by extruding the resin composition for forming a backer layer in a molten state with respect to the back surface of the base sheet,
The backer layer comprises a non-halogen thermoplastic resin;
The backer layer has a thickness of 120 to 250 μm,
The Martens hardness of the backer layer is 50 to 80 N / mm ² .
Step 4 of laminating the backer layer,
In order. The manufacturing method of the decorative sheet characterized by the above-mentioned.
7). The manufacturing method of the decorative board which laminates | stacks the said decorative sheet on a to-be-adhered material so that the surface protection layer of the decorative sheet obtained by the manufacturing method of the decorative sheet of said claim | item 5 or 6 may become an outermost surface layer.

  The decorative sheet of the present invention has a specific surface roughness of the decorative sheet, and the base sheet, the transparent resin layer and the surface protective layer contain a specific resin, and include a specific resin by extrusion molding. When laminating a backer layer having a thickness and hardness of, it can also be used in Europe where regulation of vinyl chloride resin is advancing, and when a decorative board is obtained by pasting it on an adherend such as chipboard In addition, the uneven shape of the adherend is suppressed from appearing on the surface of the decorative plate, has excellent embossing shapeability, and the embossed crushing when the decorative plate is bonded to the adherend is suppressed. Therefore, it is excellent in curling resistance and can be wound up in a roll state without distortion without causing cracks on the surface of the decorative sheet.

It is sectional drawing which showed typically an example of the decorative sheet of this invention. It is a figure which shows the measuring method of Martens hardness. Specifically, it is a diagram showing a diamond indenter (a) used for measurement of Martens hardness in this specification, a schematic diagram (b) of an indentation operation, and an example (c) of an indentation load and displacement. It is sectional drawing which showed typically an example of the decorative sheet of this invention. It is sectional drawing which showed typically an example of the decorative sheet of this invention. It is sectional drawing which showed typically an example of the decorative sheet of this invention.

  Hereinafter, the decorative sheet, the manufacturing method of the decorative sheet, the decorative board, and the manufacturing method of the decorative board of the present invention will be described.

≪ １． The decorative sheet of the present invention >>
The decorative sheet of the present invention is a decorative sheet in which at least a transparent resin layer and a surface protective layer are sequentially laminated on a base sheet, and at least a backer layer is laminated on the back surface of the base sheet. ,
(1) Ten-point average roughness Rz _jis of the surface of the decorative sheet is 40 μm or more,
(2) The surface protective layer contains an ionizing radiation curable resin,
(3) The base sheet, the transparent resin layer, and the backer layer each include a non-halogen thermoplastic resin,
(4) The backer layer has a thickness of 120 to 250 μm,
(5) Martens hardness of the backer layer is 50~80N / mm ^2,
(6) The backer layer is laminated by extruding the backer layer forming resin composition in a molten state with respect to the back surface of the base sheet.
It is characterized by that.

The decorative sheet of the present invention has a specific surface roughness of the decorative sheet, and the base sheet, the transparent resin layer and the surface protective layer each contain a specific resin, and are specified by extrusion molding. When the backer layer is laminated (that is, when all the requirements (1) to (6) are satisfied), the following (a) to (f):
(a) Can be used in Europe and other countries where regulations on vinyl chloride resins are advancing.
(b) When a decorative board is obtained by bonding to an adherend such as chipboard, the uneven shape of the adherend is suppressed from appearing on the surface of the decorative board (the uneven shape of the adherend). ) Is suppressed, and
(c) Excellent emboss shapeability,
(d) The emboss crushing when the decorative board is obtained by bonding to the adherend is suppressed,
(e) Excellent curl resistance,
(f) It is possible to wind up so as to be in a roll state without distortion without causing a crack on the decorative sheet surface,
The effect is obtained.

  Hereinafter, the details of each layer constituting the decorative sheet of the present invention and the entire decorative sheet will be specifically described.

In the decorative sheet of the present invention, at least a transparent resin layer and a surface protective layer are sequentially laminated on the base material sheet, and at least a backer layer is laminated on the back surface of the base material sheet. As long as the requirements of () to (6) are satisfied, the layer structure and the resin component constituting each layer are not particularly limited. As the layer configuration, for example, a colored hiding layer, a pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer are sequentially laminated on the base sheet, and the base sheet A decorative sheet in which a backer layer and a back primer layer are laminated in order on the back surface of the sheet (note that the decorative sheet includes a backer layer, a base sheet, a colored hiding layer, a pattern layer, and transparency on the back primer layer. It can also be said that the adhesive layer, the transparent resin layer, the primer layer, and the surface protective layer are laminated in this order).
Here, in this specification, the direction in which the surface protective layer is laminated as viewed from the base sheet is referred to as “upper” or “front surface”, and the backer layer is laminated as viewed from the base sheet. The direction is referred to as “down” or “back”. The “front surface (side)” or “surface of the surface protective layer (side)” of the decorative sheet or decorative plate means a surface that is visually recognized after the decorative sheet or decorative plate is applied.

Base sheet The decorative sheet of the present invention has a base sheet. The base sheet contains a non-halogen thermoplastic resin. In addition, it is preferable that the resin component which comprises a base material sheet is a non-halogen-type thermoplastic resin.

  Examples of the non-halogen thermoplastic resin include low density polyethylene (the low density polyethylene includes linear low density polyethylene), medium density polyethylene, high density polyethylene, ethylene-α olefin copolymer, polypropylene (the polypropylene is (Including homopolypropylene), polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, or a mixture thereof Olefin thermoplastic resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, etc., polymeta Acrylic thermoplastic resins such as methyl acrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate, polyamide thermoplastic resins such as nylon-6 and nylon-66, or polyimide, polyurethane, polystyrene, Examples include acrylonitrile-butadiene-styrene resin. Further, these non-halogen thermoplastic resins may be used alone or in combination of two or more. Of these, olefin-based thermoplastic resins are preferred because they are excellent in printability and embossing suitability for the pattern layer and are inexpensive.

  The base material sheet may be colored. In this case, a coloring material (pigment or dye) can be added to the non-halogen thermoplastic resin as described above 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 is not specifically limited, 50-100 micrometers is preferable. When the thickness of the base sheet is within the above range, the unevenness appearing on the surface of the decorative board due to the uneven shape of the adherend can be further suppressed, and further curling is prevented when the decorative sheet is stored in a roll state. Thus, roll lamination can be performed more appropriately.

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

Backer layer The decorative sheet of the present invention has a backer layer on the back side of the base sheet. Here, the backer layer means a buffer layer for the purpose of shock absorption or the like in the decorative sheet (and the decorative board). The backer layer contains a non-halogen thermoplastic resin. In addition, it is preferable that the resin component which comprises a backer layer is a non-halogen-type thermoplastic resin.

  As said non-halogen-type thermoplastic resin, resin similar to each resin illustrated by the base material sheet is mentioned. In addition, you may use a non-halogen-type thermoplastic resin individually or in mixture of 2 or more types. Among the non-halogen thermoplastic resins, olefin thermoplastic resins are preferable.

  The backer layer may be colored similarly to the base sheet. As a coloring method, the same method as the coloring method by a base material sheet is mentioned. In addition, the backer layer has various additives (fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, etc.) as with the base sheet. It may be included.

  A backer layer is laminated | stacked on the back surface of a base material sheet by extruding and molding the resin composition for backer layer formation in a molten state. Specifically, (1) a resin component (eg, non-halogen thermoplastic resin) constituting the backer layer, and (2) a backer layer containing a colorant or the above-mentioned various additives as necessary. By extruding the forming resin composition in a molten state, the composition is laminated on the back surface of the base sheet while forming the film. Thereby, a backer layer is formed on the back surface of the base sheet. The backer layer adheres to the base sheet by the heat of the resin melted during extrusion molding. In the present invention, since the backer layer is laminated by the above extrusion molding, even if a recess is formed on the back surface of the base sheet by embossing or the like, air does not enter the concave portion, and the back surface is laminated with good adhesion. The In the present specification, the “molten state” means a state that can be molded by “extrusion molding” described later.

  As the extrusion molding, a known extrusion molding method can be employed. For example, extrusion molding using a T-die extruder, a cylindrical extruder, or the like can be given. Examples of the T die include a multi-manifold type and a feed block type.

  The backer layer has a thickness of 120 to 250 μm. When the thickness of the backer layer is less than 120 μm, the unevenness of the adherend cannot be sufficiently prevented from appearing on the surface of the decorative board. Moreover, when the thickness of a backer layer exceeds 250 micrometers, when a decorative sheet is preserve | saved in a roll state, a roll lamination will become difficult by being wound. If the thickness of a backer layer is in the above-mentioned range, it can be appropriately set depending on the use of the final product, the method of use, etc., but 120 to 180 μm is preferable.

The Martens hardness of the backer layer is 50 to 80 N / mm ² . If the Martens hardness of the backer layer is less than 50 N / mm ² , the unevenness of the adherend cannot be suppressed to the surface of the decorative board. Moreover, when the Martens hardness of a backer layer exceeds 80 N / mm < ² >, when a decorative sheet is preserve | saved in a roll state, a crack will arise in the decorative sheet surface. If the Martens hardness of a backer layer is in the above-mentioned range, it can be appropriately set depending on the use of the final product, the usage method, etc., but 50-60 N / mm ² is preferable.

In this specification, Martens hardness is a value measured using a surface film physical property tester (PICODERTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows. . In this measurement method, using the diamond indenter (Vickers indenter) shown in FIG. 2 (a), the diamond indenter is pushed into the measurement sample as shown in FIG. 2 (b), and the diagonal line of the pyramidal depression formed on the surface is obtained. The surface area A (mm ² ) is calculated from the length of and the hardness is obtained by dividing the test load F (N). As shown in FIG. 2 (c), the indentation conditions were as follows. First, a load of 0 to 5 mN was applied for 10 seconds, and then a 5 mN load was maintained for 5 seconds. Unloading to ~ 0mN is performed in 10 seconds. And the hardness calculated | required by F / A (= F / A) based on the surface area A and the test load F is the said Martens hardness. In addition, in this specification, in order to avoid the influence of the hardness of layers other than a backer layer, the Martens hardness of the cross section of a backer layer was measured. In this case, the decorative sheet is embedded with a resin (cold-curing type epoxy two-component curable resin), left to cure at room temperature for 24 hours or more, and then the cured embedded sample is mechanically polished to form a backer layer. The cross section was exposed, and the Martens hardness of the cross section was measured by pushing a diamond indenter into the cross section.

  The Martens hardness of the backer layer can be appropriately set by 1) selecting a resin component as appropriate, 2) mixing a plurality of resin components, 3) adding an elastomer to the resin, or the like.

  If necessary, the backer layer may be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, and surface roughening treatment on the adhesion surface. In consideration of adhesiveness to the adherend, a primer layer (back surface primer layer) may be further provided on the back surface of the backer layer.

  The back primer layer can be formed by applying a known primer to the backer layer. 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 application amount of the primer agent is not particularly limited, it is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a back surface primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

Pattern Pattern Layer The decorative sheet of the present invention may have a pattern pattern layer on the base sheet.

  A design pattern layer is a layer which gives a desired design (design) to a decorative sheet, and the kind of design etc. are 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.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Containing organic solvent; inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, 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 Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

  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.

A colored concealment layer may be further formed between the colored concealment layer base sheet and the pattern layer, if necessary. The colored concealment layer is provided when it is desired to conceal the ground color of an adherend such as a wooden base material from the front surface of the decorative sheet. Of course, when the base sheet is transparent, even when the base sheet is concealed, it may be formed to stabilize the concealment.

  As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used.

  The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). 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 thickness of the colored concealing layer is not particularly limited and can be appropriately set according to product characteristics. The thickness at the time of coating is about 0.2 to 10 μm, and the thickness after drying is about 0.1 to 5 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 The decorative sheet of the present invention has a transparent resin layer on a substrate sheet.

  The transparent resin layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent. The transparent resin layer contains a non-halogen thermoplastic resin. In addition, it is preferable that the resin component which comprises a transparent resin layer is a non-halogen-type thermoplastic resin.

  As said non-halogen-type thermoplastic resin, resin similar to each resin illustrated by the base material sheet is mentioned. In addition, you may use a non-halogen-type thermoplastic resin individually or in mixture of 2 or more types. Among the non-halogen thermoplastic resins, olefin thermoplastic resins are preferable.

  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 preferably about 20 to 200 μm, and more preferably 80 to 120 μm. The above range may be exceeded depending on the use of the decorative sheet.

A primer layer may be provided on the primer layer transparent resin layer.

  A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a transparent resin layer similarly to the above-mentioned back surface primer layer. As a primer agent, the thing similar to the primer agent mentioned by the above-mentioned back surface primer layer can be used. Moreover, an additive may be mix | blended with a primer layer as needed. The type and amount of additive are the same as the type and amount of additive in the back primer layer.

Although the application amount of the primer agent is not particularly limited, it is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

Gloss Control Layer A gloss control layer may be formed on the decorative sheet of the present invention. Examples of the form of the decorative sheet on which the gloss adjusting layer is formed include the forms shown in FIGS.

  When the gloss adjusting layer is formed on the decorative sheet of the present invention, the gloss adjusting layer is formed on the transparent resin layer so as to be adjacent to a surface protective layer described later. More specifically, the back surface of the gloss adjusting layer is adjacent to the front surface of the transparent resin layer (or the primer layer when the decorative sheet of the present invention has the primer layer), and The front surface and / or the side surface of the gloss adjusting layer is adjacent to the surface protective layer.

  The gloss adjustment layer may be formed on a part of the surface on the front surface side (the surface side visually recognized after the decorative sheet or decorative plate is applied) from the viewpoint of design, and (2 ) It may be formed on the entire front surface (entire surface). That is, the gloss adjustment layer may be (1) partially formed with respect to the front surface, and (2) formed over the entire surface with respect to the front surface. May be.

When the (1) gloss adjustment layer is formed on a part of the front surface, (a) the surface protective layer may be formed on a part of the front surface, (B) The surface protective layer may be formed on the entire front surface side. When both the gloss adjusting layer and the surface protective layer are formed on a part of the front side surface (in the case of (1) (a) above), the surface protective layer is formed by the gloss adjusting layer. It is formed so as to fill a region that has not been formed (region that does not exist).
In the form of FIG. 3, the gloss adjusting layer is formed on a part of the front side surface, and the surface protective layer is formed on the entire front side ((1) ( b)). In the form of FIG. 4, the gloss adjusting layer is formed on a part of the front side surface, and the surface protective layer is formed on a part of the front side surface ((1) above). (Form of (a)).

  On the other hand, when the (2) gloss adjusting layer is formed on the entire front surface, the surface protective layer is formed on a part of the front surface. In the form of FIG. 5, the gloss adjusting layer is formed on the entire front surface side, and the surface protective layer is formed on a part of the front surface side (form (2) above. ).

Here, the gloss value of the gloss adjusting layer is G _A , and the gloss value of the surface protective layer is _GP . If the decorative sheet of the present invention have a luster control layer, the relationship between the gloss value G _P of the surface protective layer described below with gloss values G _A luster control layer is a G _P ≠ G _A. Here, the G _P and the G _A in the present specification is a value measured according to Japanese Industrial Standard JIS Z8741. Specifically, in the present invention, the gloss value is measured under the condition of an incident angle = 60 ° using PG-3D manufactured by Nippon Denshoku Industries Co., Ltd. as a gross meter. In the present specification, the gloss value is also referred to as a gloss value or a gloss value.

Either (1) the gloss adjustment layer is formed on a part of the front surface side, or (2) the gloss adjustment layer is formed on the entire front surface side, Even so, both the gloss adjusting layer and the surface protective layer are visually recognized on the surface visually recognized after the decorative sheet or decorative plate is applied, and the gloss values of the gloss adjusting layer and the surface protective layer are the same. relationship is _{G P} ≠ _{G a.} Therefore, when the decorative sheet of the present invention is attached to the adherend, the influence of the uneven shape (duck) generated on the decorative sheet surface is further suppressed, and the design of the decorative sheet or decorative plate is improved. Therefore, the decorative sheet of the present invention in which the gloss adjusting layer is formed is a preferred embodiment as the present invention.

Next, the case (1) where the gloss adjusting layer is formed on a part of the surface on the front side (simply referred to as the case (1)) will be described. In the case of (1), the area ratio of the area where the gloss adjusting layer occupies per 1 cm ² of the front surface area of the decorative sheet or decorative plate is preferably 20 to 80%. In this case, it is preferable that the gloss adjusting layer is formed so that the front surface (surface to be visually recognized) side of the gloss adjusting layer has a pattern shape. When the gloss adjustment layer is in a pattern and the ratio of the area is 20 to 80%, the gloss difference between the gloss adjustment layer and the surface protective layer becomes clearer, and as a result, the design is further improved, and The influence of the uneven shape can be further suppressed. In addition, when the gloss adjustment layer is formed so as to have the pattern shape, the type of the pattern is not particularly limited. Specific examples of the pattern include those similar to the various patterns exemplified in the pattern pattern layer described above.

In this specification, the ratio of the area of the gloss adjusting layer (area where the gloss adjusting layer is present) occupying per 1 cm ² of the front surface area of the decorative sheet or decorative plate is defined as the ratio of the gloss adjusting layer. It may be called an occupied area ratio. The occupation area ratio of the gloss adjusting layer is calculated from plate-making data at the stage of producing a plate for forming the gloss adjusting layer. The occupied area ratio of the gloss adjusting layer can be calculated from the shape of the plate.

For the (1), in order to the uneven shape of the impact to further suppress (the further inconspicuous irregularities), the relationship between G _A and the G _P is G _{A <G P} is preferred. More preferably, G _A < _GP and G _A ≦ 5.

  Next, the case (2) where the gloss adjusting layer is formed on the entire front surface side (simply referred to as the case (2)) will be described. In the case of (2), the surface protective layer is formed on a part of the surface on the front surface side. In this case, it is preferable that the surface protective layer is formed so that the front surface (surface to be visually recognized) side of the surface protective layer has a pattern shape. Thereby, the gloss difference between the gloss adjusting layer and the surface protective layer becomes clearer, and as a result, the design property can be further improved and the influence of the uneven shape can be further suppressed. In addition, when the surface protective layer is formed to have the pattern shape, the type of the pattern is not particularly limited. Specific examples of the pattern include those similar to the various patterns exemplified in the pattern pattern layer described above.

For the (2), in order to the uneven shape of the impact of further suppressing (inconspicuous further the uneven shape), the relationship of G _A and the G _P | is preferably ≧ 2 _| G _P -G A , | _GP− G _A | ≧ 10 is more preferable (in other words, the difference between the gloss value of the gloss adjusting layer and the gloss value of the surface protective layer is preferably 2 or more, and the difference is 10 or more. preferable). The relationship between the _{G A} and the _{G P may} be a G A _{<G P,} or _may be a G P _{<G A.} That may be a low gloss than it is the surface protective layer of the luster control layer, also towards the surface protective layer may be a low glossy than luster control layer (Incidentally, are G A _{<G P} If a layer of the luster control layer is low luster, if a G P _{<G a} surface protective layer is a layer of low gloss). In the case of (2), it is preferable that the ratio of the area of the region where the low-gloss layer occupies per 1 cm ² of the front surface area of the decorative sheet or the decorative plate exceeds 50%.

In the present specification, the ratio of the area of the surface protective layer (area where the surface protective layer is present) occupying per 1 cm ² of the front surface area of the decorative sheet or decorative plate is defined as the surface protective layer It may be called an occupied area ratio. The occupation area ratio of the surface protective layer is calculated from plate-making data at the stage of producing a plate for forming the surface protective layer. The occupation area ratio of the surface protective layer can also be calculated from the shape of the plate. On the other hand, the ratio of the area where the low-gloss layer is exposed per 1 cm ² of the front surface area of the decorative sheet or plate (exposed area ratio of the low-gloss layer) is (i) low When the gloss layer is a surface protective layer, the occupied area ratio of the surface protective layer is directly the occupied area ratio of the low gloss layer, and (ii) when the low gloss layer is a gloss adjustment layer, After calculating the occupation area ratio of the surface protective layer, it is obtained by subtracting (minus) the occupation area ratio of the surface protection layer from 100 (%).

  The method for forming the gloss adjusting layer is not particularly limited. For example, as in the case of the above-described pattern layer, it is dissolved (or dispersed) in a solvent (or dispersion medium) together with known colorants (dyes, pigments, etc.) and vehicles. It can form with the ink obtained. About a coloring agent and a solvent, the thing similar to the coloring agent and solvent which were illustrated by the coloring agent and solvent in the above-mentioned pattern pattern layer, respectively can be used.

  The ink vehicle for forming the gloss adjusting layer preferably contains 50% by mass or more of urethane resin and / or polyvinyl acetal resin. The urethane resin is a polyol component such as an acrylic polyol, a polyester polyol, or a polyether polyol, and an isocyanate component such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, or the like, isophorone diisocyanate, hexamethylene diisocyanate, Examples include urethane resins obtained by reacting with aliphatic or cycloaliphatic isocyanates such as hydrogenated tolylene diisocyanate (linearly cross-linked or network cross-linked). be able to. 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. Among these, polyvinyl butyral is particularly preferable because it is soluble in a solvent, easily converted into an ink, and has a good appearance of visual unevenness (recognized visually as a recess).

  Moreover, in order to adjust a gloss value as needed, you may mix and use gloss adjustment resins, such as unsaturated polyester-type resin, acrylic resin, and a vinyl chloride-vinyl acetate copolymer. When the gloss adjusting resin is used, the mixing ratio is preferably in the range of 10 to 50% by mass with respect to the total amount of the vehicle. The ink for forming the gloss adjusting layer may be uncolored or may be colored by adding a colorant such as a pigment.

  Further, an extender pigment may be blended in the ink for forming the gloss adjusting layer. When the extender pigment is blended, it is possible to promote light scattering and further enhance the effect of eliminating the uneven shape (duck). The extender pigment is not particularly limited, and is suitably selected from, for example, silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. Among these, silica, which is a material having a high degree of freedom in material design such as oil absorption, particle size, pore volume, etc., and excellent in designability, whiteness, and coating stability as an ink, is preferable. Silica is preferred. In addition, as for the content, when using an extender, 5-15 mass parts is preferable with respect to 100 mass parts of inks (ink composition) other than an extender.

Gloss values G _A luster control layer, vehicle described above, luster control resin, a method for selecting a type of each substance and coloring agent (including extender pigments); and the like; how to set the contents of the above materials properly Can be adjusted.

  As the printing method used for forming the gloss adjusting layer, for example, the gravure printing method, the offset printing method, the screen printing method, the flexographic printing method, the electrostatic printing method, the inkjet method, and the like, as in the printing method used for forming the above-mentioned pattern pattern layer. The printing method etc. are mentioned. Moreover, when forming the whole surface solid-like gloss adjustment layer, the method similar to the various coating methods in formation of a pattern layer is mentioned.

  When the gloss adjusting layer is formed on a part of the surface on the front side (in the case of (1) above), the gloss adjusting layer is preferably formed so as to have a pattern shape. In particular, the gloss adjusting layer is more preferably formed in a pattern such as a dot shape, a lattice shape, or a wood grain conduit pattern (shape). Since the gloss adjustment layer is formed in the above pattern, the gloss of the area with the gloss adjustment layer is further different from the gloss of the area other than the gloss adjustment layer (area without the gloss adjustment layer). An optical illusion appears as if there is a recess, and it is visually recognized as a unique stereoscopic effect. For this reason, the uneven shape (duck) becomes less noticeable.

  When the above-mentioned pattern pattern layer is formed on the decorative sheet of the present invention, it is preferable to form the gloss adjusting layer so as to be interlocked (tuned) with the pattern of the pattern pattern layer. For example, when the pattern layer is formed in a wood grain pattern, a decorative sheet having a more excellent design can be obtained by printing the pattern in a wood conduit pattern to form a gloss adjusting layer.

  The thickness (film thickness) of the gloss adjusting layer is preferably 0.5 μm to 5 μm in consideration of printability and interaction with the resin composition for forming the surface protective layer.

Surface protective layer The decorative sheet of the present invention has a surface protective layer on the transparent resin layer.

  When the decorative sheet of the present invention has the gloss adjusting layer, the surface protective layer is formed adjacent to the gloss adjusting layer. Specifically, the back surface and / or the side surface of the surface protective layer is adjacent to the gloss adjusting layer. When the decorative sheet of the present invention has the gloss adjusting layer, the surface protective layer is preferably transparent.

  The surface protective layer contains an ionizing radiation curable resin (that is, the resin component constituting the surface protective layer contains an ionizing radiation curable resin). The resin component constituting the surface protective layer is preferably an ionizing radiation curable resin.

  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 ionizing radiation curable resin can be used alone or in combination of two or more.

  Among the ionizing radiation curable resins, an electron beam curable resin (EB resin) is preferable. Examples of the electron beam curable resin include urethane acrylate type electron beam curable resins.

  The surface protective layer may contain other resins in addition to the ionizing radiation curable resin. Examples of the resin other than the ionizing radiation curable resin include a two-component curable urethane resin.

  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.

  In order to improve the weather resistance, it is preferable to add a UV absorber such as benzotriazole, benzophenone, salicylate, or triazine to the surface protective layer. 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 can be 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. As for the addition amount of an antibacterial agent, 0.1-10 mass parts is preferable with respect to 100 mass parts of resin components which comprise a surface protective layer.

  In addition, various additives such as solvents, dyes and pigments, fillers such as extenders, antifoaming agents, leveling agents, and thixotropic agents can be added to the surface protective layer as necessary. .

  The surface protective layer is, for example, (1) ionizing radiation curable resin on the transparent resin layer or gloss adjusting layer, and (2) other resins, ultraviolet absorbers, antibacterial agents, and various other additives as necessary. It can be formed by curing a resin composition for forming a surface protective layer containing an agent, etc. by a known coating method such as gravure coating or roll coating, and then curing the ionizing radiation curable resin. Here, when the surface protective layer is formed on a part of the front side surface of the decorative sheet, the surface protective layer-forming resin composition is partially applied (for example, in a pattern), and then the surface protective layer is formed. The surface protective layer can be formed by curing the ionizing radiation curable resin in the resin composition. When the surface protective layer is formed on the entire front surface side of the decorative sheet, the surface protective layer-forming resin composition is applied over the entire surface, and then ionizing radiation in the resin composition. The surface protective layer can be formed by curing the curable resin.

The gloss value _GP of the surface protective layer is adjusted by a method of selecting the type of each material such as a resin component and an additive contained in the surface protective layer; a method of appropriately setting the content of each of the above materials; Can do.

  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 preferably 0.1 to 50 μm, and more preferably 1 to 30 μm.

Ten-point average roughness Rz _cis
The ten-point average roughness Rz _jis of the surface (surface protective layer surface) of the decorative sheet of the present invention is 40 μm or more. Therefore, it is excellent in the design property of a decorative sheet. The ten-point average roughness Rz _jis is preferably 40 to 120 μm.

In the present invention, a decorative sheet surface having a 10-point average roughness Rz _jis of 40 μm or more can be obtained by performing (applying) embossing, which will be described later. As will be described later, embossing may be performed on (1) the transparent resin layer or the gloss adjusting layer, or (2) on the surface protective layer.

In this specification, the ten-point average roughness Rz _jis (μm) is a value measured according to JIS B 0601: 2001. Specifically, the ten-point average roughness Rz _jis is _extracted from the cross-sectional curve by the reference length L in the direction of the average line, and the peak height from the highest peak to the fifth peak is extracted from the average line of the extracted part. It is the sum of the average value of the absolute values of (Yp) and the average value of the absolute values of the altitude (Yv) of the bottom valley from the lowest valley bottom to the fifth.

In the present specification, the ten-point average roughness Rz _jis of the decorative sheet is determined as shown in the following (A) to (C).
(A) First, a decorative sheet is cut into 15 cm × 15 cm.
(B) The surface roughness of the cut-out decorative sheet is measured with a surface roughness shape measuring instrument: Surfcom FLEX50A (Tokyo Seimitsu Co., Ltd.). The surface roughness of the decorative sheet can be measured by measuring the surface roughness for a distance of 2 cm in a direction perpendicular to the wood grain pattern when the embossed pattern is a wood grain pattern, etc. Measure in direction.
(C) The process of (B) is performed at three arbitrary points to obtain three Rz _jis values, and the lowest value (lower limit value) of the three Rz _jis is determined. If the minimum value of Rz _jis is 40 (μm) or more, the requirement (1) in the present invention is satisfied.

Ten-point average roughness Rz _jis is when selecting the depth and shape of the embossed plate, selecting the outermost surface layer (surface protective layer or transparent resin layer) to be embossed, and heating temperature and pressure when embossing The pressure can be adjusted by selecting the resin component constituting the transparent resin layer or the surface protective layer, setting the thickness, and the like.

Embossing In the present invention, a decorative sheet having a surface 10-point average roughness Rz _jis of 40 μm or more is preferably obtained by embossing. In this specification, the shape given by embossing is also called an embossed shape (pattern).

  An emboss shape may be formed by embossing from the transparent resin layer side after forming the said transparent resin layer (the manufacturing method 2 of the decorative sheet mentioned later). The embossed shape may be formed by laminating the surface protective layer on the transparent resin layer and then embossing from the surface protective layer side (a method for producing a decorative sheet described later) 1).

  The embossing method is not particularly limited, and 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 emboss plate, and then cool. For embossing, a known single-wafer or rotary embossing machine is used. Embossed shapes include, for example, floating patterns (uneven patterns of raised annual rings), wood grain conduit grooves, stone plate surface unevenness (such as granite cleaved surfaces), cloth surface textures, satin texture, sand texture, hairlines, all-line grooves Etc.

Rolled product of the present invention The decorative sheet of the present invention may be wound into a roll. That is, in this invention, a roll-shaped thing is obtained by winding the said decorative sheet of this invention in roll shape. The roll-shaped product of the present invention is a circular roll-shaped decorative sheet having no distortion, and the decorative sheet surface in the roll-shaped product is not cracked. Furthermore, curling of the roll-like product of the present invention is suppressed even when unrolling (feeding out). Thus, since the decorative sheet of the present invention can be suitably wound into a roll, it can be easily stored as a roll.

  The method for winding the decorative sheet of the present invention into a roll is not particularly limited, and examples thereof include use of a winder and winding by a person. The winding method when using the winder is not particularly limited. For example, center winding, surface winding, center-surface winding can be used. Either can be adopted.

  The roll diameter of the roll-like product of the present invention is not particularly limited, but is preferably 300 mm to 1000 mm. Moreover, although the width | variety (width | variety of a decorative sheet) of the said roll-shaped material is not specifically limited, 400 mm-1240 mm are preferable.

  The roll-like product of the present invention includes both (1) a roll-like product containing a core material in the center of a circular roll, and (2) a roll-like product not containing the core material in the center of the circular roll shape. To do. That is, the roll-like product of the present invention may have the core material or may not have the core material. The material of the core material is not particularly limited, and paper, wood, metal, resin (for example, acrylonitrile-butadiene-styrene (ABS), polypropylene (PP), polyethylene (PE), fiber reinforced plastic (FRP), etc.), etc. Can be mentioned. The shape of the cross section of the core material is not particularly limited, and may be any of a circle, a quadrangle, a pentagon, a hexagon, and the like. The length of the core material is preferably longer than the width of the roll.

≪ 2. Production method 1 of decorative sheet of the present invention >>
In the decorative sheet manufacturing method of the present invention (manufacturing method 1), at least a transparent resin layer and a surface protective layer are sequentially stacked on a base sheet, and at least a backer layer is stacked on the back surface of the base sheet. It is the manufacturing method of the decorative sheet currently performed, Comprising: The following processes 1-3:
(i) A laminated sheet having at least a transparent resin layer and a surface protective layer in this order on a base sheet,
The surface protective layer contains an ionizing radiation curable resin,
Step 1 of obtaining a laminated sheet, wherein the base sheet and the transparent resin layer both contain a non-halogen thermoplastic resin,
(ii) Step 2 of _setting the ten-point average roughness Rz _jis of the surface of the laminated sheet to 40 μm or more by embossing from above the surface protective layer of the laminated sheet; and
(iii) by extruding the resin composition for forming a backer layer in a molten state with respect to the back surface of the base sheet,
The backer layer comprises a non-halogen thermoplastic resin;
The backer layer has a thickness of 120 to 250 μm,
The Martens hardness of the backer layer is 50 to 80 N / mm ² .
Step 3 of laminating the backer layer,
In order. According to the production method, the decorative sheet of the present invention can be suitably obtained.

  In step 1, a laminated sheet having at least a transparent resin layer and a surface protective layer in order on the base sheet is obtained. The laminated sheet is an intermediate of the decorative sheet of the present invention and does not have a backer layer. For details of the substrate sheet, the transparent resin layer, and the surface protective layer in the laminated sheet, the above-mentioned items 1. This is the same as described for the base sheet, the transparent resin layer, and the surface protective layer in the decorative sheet of the present invention.

  When the laminated sheet is obtained in step 1, each layer such as a colored concealing layer, a pattern layer, a transparent adhesive layer, a primer layer, and a gloss adjusting layer may be formed as necessary. The details of each of the layers are as described above in item 1. This is the same as described for the colored hiding layer, the pattern layer, the transparent adhesive layer, the primer layer, and the gloss adjusting layer in the decorative sheet of the present invention.

In step 2, embossing is performed on the surface protective layer of the laminated sheet, so that the ten-point average roughness Rz _jis of the surface of the laminated sheet is _set to 40 μm or more (by this, the ten-point average roughness Rz _jis of the surface is _increased). Is a laminated sheet having a thickness of 40 μm or more). The details of the embossing and the ten-point average roughness Rz _jis of the surface of the laminated sheet are as described above in item 1. This is the same as the embossing and ten-point average roughness Rz _jis in the decorative sheet of the present invention.

  In step 3, the backer layer is laminated on the back surface of the base material sheet by extruding the backer layer forming resin composition in a molten state to the back surface of the base material sheet. The details of the step of extruding the backer layer and the resin composition for forming the backer layer are described in the above item 1. This is the same as described for the backer layer in the decorative sheet of the present invention. After forming the backer layer, the above-described back primer layer may be formed as necessary. For details of the back primer layer, refer to the above item 1. This is the same as described for the back primer layer in the decorative sheet of the present invention.

≪ 3. Production method 2 of decorative sheet of the present invention >>
In the method for producing a decorative sheet according to the present invention (manufacturing method 2), at least a transparent resin layer and a surface protective layer are sequentially laminated on a substrate sheet, and at least a backer layer is laminated on the back surface of the substrate sheet. It is the manufacturing method of the decorative sheet currently performed, Comprising: The following processes 1-4:
(i) A laminate having at least a transparent resin layer on a substrate sheet,
Step 1 for obtaining a laminate in which the base sheet and the transparent resin layer each include a non-halogen thermoplastic resin;
(ii) Step 2 of embossing from above the transparent resin layer of the laminate;
(iii) By coating a resin composition for forming a surface protective layer containing an ionizing radiation curable resin on the transparent resin layer,
A laminated sheet having at least a transparent resin layer and a surface protective layer on a substrate sheet,
Step 3 of obtaining a laminated sheet having a ten-point average roughness Rz _jis of 40 μm or more on the surface of the laminated sheet, and
(iv) by extruding the resin composition for forming a backer layer in a molten state with respect to the back surface of the base sheet,
The backer layer comprises a non-halogen thermoplastic resin;
The backer layer has a thickness of 120 to 250 μm,
The Martens hardness of the backer layer is 50 to 80 N / mm ² .
Step 4 of laminating the backer layer,
In order. According to the production method, the decorative sheet of the present invention can be suitably obtained.

  In step 1, a laminate having at least a transparent resin layer is obtained on the substrate sheet. The laminate is an intermediate of the decorative sheet of the present invention, and is also an intermediate of the laminated sheet described later. The laminate does not have a backer layer and a surface protective layer. About the detail of the said base material sheet and transparent resin layer in the said laminated body, respectively, the above-mentioned item 1. This is the same as described for the base sheet and the transparent resin layer in the decorative sheet of the present invention.

  When obtaining the said laminated body at the process 1, you may form each layers, such as a coloring concealment layer, a pattern pattern layer, a transparent adhesive layer, a primer layer, a glossiness adjustment layer, as needed. The details of each of the layers are as described above in item 1. This is the same as described for the colored hiding layer, the pattern layer, the transparent adhesive layer, the primer layer, and the gloss adjusting layer in the decorative sheet of the present invention.

In step 2, embossing is performed from above the transparent resin layer of the laminate. The 10-point average roughness Rz _jis of the surface of the laminate (by the embossed shape) obtained in step 2 is not particularly limited, and the 10-point average roughness of the surface of the laminated sheet or decorative sheet after step 3 and 4 described later. _What is _necessary is _just to emboss from a transparent resin layer so that Rz _jis may be 40 micrometers or more.

In step 3, a laminated sheet having a surface ten-point average roughness Rz _jis of 40 μm or more is applied on the transparent resin layer by applying a resin composition for forming a surface protective layer containing an ionizing radiation curable resin. obtain. The details of the step of applying the surface protective layer and the resin composition for forming the surface protective layer are described in the above item 1. This is the same as described for the surface protective layer in the decorative sheet of the present invention. In addition, the said laminated sheet is an intermediate body of the decorative sheet of this invention, Comprising: It does not have a backer layer.

  Before applying the resin composition for forming a surface protective layer in Step 3, each layer such as a primer layer and a gloss adjusting layer may be formed as necessary. The details of each of the layers are as described above in item 1. This is the same as described for the primer layer and gloss adjusting layer in the decorative sheet of the present invention.

  In step 4, the backer layer is laminated on the back surface of the base material sheet by extruding the backer layer forming resin composition in a molten state to the back surface of the base material sheet. The details of the process of extruding the backer layer and the resin composition for forming the backer layer are described in the above item 1. This is the same as described for the backer layer in the decorative sheet of the present invention. After forming the backer layer, the above-described back primer layer may be formed as necessary. For details of the back primer layer, refer to the above item 1. This is the same as described for the back primer layer in the decorative sheet of the present invention.

<< 4. Decorative plate of the present invention and manufacturing method thereof >>
A decorative sheet can be obtained by laminating the decorative sheet of the present invention on an adherend. Moreover, it can also be set as a decorative board by laminating | stacking the decorative sheet obtained by unwinding the roll-shaped thing of this invention on an adherend. The decorative board of the present invention is obtained by laminating the decorative sheet of the present invention on an adherend so that the surface protective layer of the decorative sheet of the present invention becomes the outermost surface layer.

  The adherend is not limited, and the same materials as those used for known decorative panels can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet of the present invention can be suitably used for a wood material. 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. , Chip boards, or composite substrates on which chip boards are laminated. As the wood material, it is preferable to use a chip board or a composite base material on which chip boards are laminated.

  The lamination method of laminating the decorative sheet and the adherend is not limited, and for example, a method of sticking the 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 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.

  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
A pattern layer having a thickness of 2 μm was formed on the front surface of a base sheet (Art Ply, manufactured by Mitsubishi Plastics Co., Ltd.) made of a colored polypropylene (PP) film having a thickness of 60 μm by printing. A 2 μm thick transparent adhesive layer made of urethane resin (Seika Bond E-263 / C-75N, manufactured by Dainichi Seika Kogyo Co., Ltd.) was formed on the pattern layer. On the adhesive layer, a transparent polypropylene (PP) resin sheet (Novatech PP, manufactured by Nippon Polypro Co., Ltd.) having a thickness of 100 μm was laminated by extrusion lamination to form a transparent resin layer.

  Next, after performing corona discharge treatment on the surface of the transparent resin layer, a primer layer (primer layer for forming a surface protective layer, by applying a two-component curable urethane resin on the transparent resin layer, 2 μm thick) was formed.

Gravure coating method on the front surface of the primer layer with a surface protective layer forming resin composition made of urethane acrylate electron beam curable resin (EB resin) so that the thickness (layer thickness) after curing is 15 μm. Then, in an environment having an oxygen concentration of 200 ppm or less, the electron beam curable resin was cured by irradiating an electron beam under the conditions of an acceleration voltage of 175 KeV and 5 Mrad using an electron beam irradiation apparatus. Thereby, a surface protective layer was formed. The composition of the electron beam curable resin is as follows.
· Bifunctional urethane acrylate (Tg = 25 (° C), molecular weight 1500) 80 parts by mass · Hexafunctional urethane acrylate (Tg = 200 (° C) or higher, molecular weight 1500) 20 parts by mass The substrate sheet and the transparent resin layer are softened by heating with a heater, and then immediately embossed (specifically, heat-pressed with an embossed plate with a grain pattern to be described later) (Grain pattern (grain 1)) was formed.

  Next, a backer layer was formed by laminating a homopolypropylene resin layer on the back surface of the base material sheet by melt extrusion laminating method (specifically, melting a backer layer forming resin composition made of homopolypropylene). A backer layer was formed and laminated on the back surface of the base material sheet by extrusion molding in a state).

  Furthermore, after the corona discharge treatment was performed on the back surface of the backer layer, a back surface primer layer (thickness 2 μm) was formed.

Thus, the decorative sheet of Example 1 was obtained.
<Each physical property of the decorative sheet of Example 1>
Ten point average roughness of the decorative sheet surface (ten point average roughness of the embossed shape by the embossed pattern) Rz _jis is 71 μm, the backer layer thickness is 120 μm, and the Martens hardness of the backer layer is 50-60 N / It was mm ^2. In addition, the measurement distance at the time of measuring said Rz _cis was 2 cm. The Martens hardness was measured in the cross-sectional direction of the backer layer. Further, when the gloss value (incident angle 60 °) of the surface protective layer was measured using PG-3D manufactured by Nippon Denshoku Industries Co., Ltd., the gloss value ( _GP ) was 13.

Example 2
First, a base sheet, a pattern layer, an adhesive layer, a transparent resin layer, and a primer layer were formed. Each of the layers was formed by the same method as in Example 1.
Next, the ratio of the area of the gloss adjusting layer to 1 cm ² of the surface on the surface protective layer side of the decorative sheet is 50% with respect to the front surface of the primer layer (the makeup to be finally produced) A pattern-like gloss adjusting layer was formed so that the area occupied by the gloss adjusting layer when viewed from the front surface of the sheet was 50%. The gloss adjusting layer is a matte ink (printing ink in which 10 parts by mass of silica particles are blended with 100 parts by mass of polyester urethane printing ink having a number average molecular weight of 3000 and a glass transition temperature (Tg) of 62.8 ° C. The composition was used by applying a wood grain conduit pattern so that the thickness of the gloss adjusting layer after drying was 2 μm by a gravure printing method.
Next, after a surface protective layer was formed on the entire surface of the gloss adjusting layer, an embossed pattern was further formed on the surface protective layer side. The surface protective layer and the embossed pattern were each formed by the same method as in Example 1.
Next, after forming a backer layer on the back surface of the base material sheet, a back surface primer layer was further formed on the back surface of the backer layer. The backer layer and the back primer layer were each formed by the same method as in Example 1.

  Thus, a decorative sheet of Example 2 was obtained.

Incidentally, prior to applying the surface protective layer-forming resin composition was measured for a gloss value when the light enters at an incident angle of 60 ° relative to the luster control layer, the luster value (G _A) 2 Met. In addition to the decorative sheet, a decorative sheet similar to the decorative sheet of Example 2 except that no gloss adjusting layer was formed was prepared for measuring the gloss value of the surface protective layer. When the gloss value when light was incident on the surface protective layer of the measurement decorative sheet at an incident angle of 60 ° was measured, the gloss value (G _P ) was 13. The gloss value (incident angle 60 °) of the gloss adjusting layer and the surface protective layer in the decorative sheet of Example 2 was determined based on the gloss value described above. The gloss value (incident angle 60 °) was measured using PG-3D manufactured by Nippon Denshoku Industries Co., Ltd.

Example 3
First, a base sheet, a pattern layer, an adhesive layer, a transparent resin layer, and a primer layer were formed. Each of the layers was formed by the same method as in Example 1.
Next, a gloss adjusting layer (thickness after drying: 2 μm) was formed on the entire front surface of the primer layer. In addition, when forming the gloss adjusting layer, the same ink as the mat ink used in Example 2 was used.
Next, on the gloss adjusting layer, the ratio of the area of the surface protective layer to 1 cm ² of the surface of the decorative sheet on the surface protective layer side is 30% (in the region where the gloss adjusting layer is exposed). A patterned surface protective layer was formed so that the area ratio (exposed area ratio of the low-gloss layer) was 70%. In forming the surface protective layer, the same resin composition as the surface protective layer-forming resin composition used in Example 1 was used. Further, the electron beam curable resin was cured by the same method as in Example 1.
Next, an embossed pattern was formed on the surface protective layer side. The embossed pattern was formed by the same method as in Example 1.
Next, after forming a backer layer on the back surface of the base material sheet, a back surface primer layer was further formed on the back surface of the backer layer. The backer layer and the back primer layer were each formed by the same method as in Example 1.

  Thus, a decorative sheet of Example 3 was obtained.

Incidentally, prior to applying the surface protective layer-forming resin composition was measured for a gloss value when the light enters at an incident angle of 60 ° relative to the luster control layer, the luster value (G _A) 2 Met. In addition to the decorative sheet, a decorative sheet similar to the decorative sheet of Example 3 was prepared for measuring the gloss value of the surface protective layer except that no gloss adjusting layer was formed. When the gloss value when light was incident on the surface protective layer of the measurement decorative sheet at an incident angle of 60 ° was measured, the gloss value (G _P ) was 13. The gloss value (incident angle 60 °) of the gloss adjusting layer and the surface protective layer in the decorative sheet of Example 3 was determined based on the gloss value described above. The gloss value (incident angle 60 °) was measured using PG-3D manufactured by Nippon Denshoku Industries Co., Ltd.

Examples 4-13
(1) The resin component constituting the backer layer and / or (2) the thickness of the backer layer was appropriately changed as shown in Tables 2 and 3. (3) As shown in Tables 2 and 3, the embossed embossed pattern was appropriately changed to wood grain 1-5 shown in Table 4. Further, (4) the Martens hardness of the backer layer was appropriately changed as shown in Tables 2 and 3. Other than that was carried out similarly to Example 1, and prepared the decorative sheet of Examples 4-13. Note that (1) the Martens hardness of the backer layer can be changed by changing the resin component constituting the backer layer. In Tables 1-3, resins A, C, and D are homopolypropylene, and resin B is polyethylene terephthalate (PET).

Comparative Examples 1-4
A decorative sheet of Comparative Examples 1 to 4 was obtained in the same manner as in Example 1 except that (1) the resin component constituting the backer layer and / or (2) the thickness of the backer layer was appropriately changed. Note that (1) the Martens hardness of the backer layer can be changed by changing the resin component constituting the backer layer.

≪Evaluation method 1: Surface condition of decorative board 1 (Surface unevenness expression suppression evaluation of adherend) ≫
An aqueous emulsion adhesive (Rikabond BA-10L (main agent): BA-11B (curing agent) manufactured by Chuo Rika Kogyo Co., Ltd.) was applied to a cork board at 6 to 7 g / scale angle, a decorative sheet was laminated, and 3 at room temperature. A decorative board was prepared by curing for days. The surface state of the decorative board was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if the evaluation is A or higher, the surface state has no problem in actual use conditions.
A: The uneven shape of the adherend is not exposed.
B: The uneven shape of the adherend is slightly exposed.
C: The uneven shape of the adherend is clearly exposed.

≪Evaluation method 2: Embossed state of decorative sheet (Embossing shape evaluation) ≫
The state of the embossed pattern on the decorative sheet was visually observed and evaluated according to the following evaluation criteria. In the following evaluation criteria, an evaluation of A or higher is an embossed state in which there is no problem in an actual use situation.
A: The embossed pattern remains clearly.
B: The embossed pattern has disappeared slightly.
C: The embossed pattern has almost disappeared.

≪Evaluation method 3: Embossed state of decorative board (Emboss crush evaluation) ≫
The embossed state of the decorative board, that is, the embossed crushing after laminating the decorative sheet on the adherend was evaluated. Specifically, an aqueous emulsion adhesive (Rikabond BA-10L (main agent): BA-11B (curing agent)) manufactured by Chuo Rika Kogyo Co., Ltd. is applied to particle boards at 6 to 7 g / angle, and a decorative sheet is laminated. Then, a decorative board was prepared by curing at room temperature for 3 days. The embossed state of the decorative board was visually observed and evaluated according to the following evaluation criteria. In the following evaluation criteria, an evaluation of B or higher is an embossed state in which there is no problem in the actual use situation.
A: The embossed pattern is not crushed.
B: The embossed pattern is slightly crushed.
C: The embossed pattern is almost crushed.

<< Evaluation Method 4: Curling resistance of decorative sheet >>
The decorative sheet was wound around a paper tube having a diameter of 3 inches (= 76.2 mm) and left at room temperature for 1 week. The decorative sheet was unwound and the curled state was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if the evaluation is A or higher, the curl resistance has no problem in the actual use situation.
A: The decorative sheet is hardly curled.
B: The decorative sheet is slightly curled.
C: The decorative sheet is clearly curled.

<< Evaluation Method 5: Roll State of Cosmetic Sheet (Evaluation of Roll Shape and Crack on Surface of Cosmetic Sheet) >>
A roll-shaped decorative sheet was obtained by winding 100 m of a sheet having a width of 3 (= 909.09 mm) around a paper tube having a diameter of 3 inches (= 76.2 mm). The roll-shaped decorative sheet was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if the evaluation is B or more, there is no problem in the actual use situation.
A: The roll shape is an undistorted circle, and there is no crack on the decorative sheet surface.
B: The roll shape is a slightly distorted circle, and the decorative sheet surface has no cracks.
C: (1) The roll shape is a distorted circle, (2) Even if the roll shape is not distorted, the decorative sheet surface is cracked, or (3) The decorative sheet is made into a roll in the first place. I can't.

≪Evaluation method 6: Surface state 2 of decorative board (Surface unevenness expression suppression evaluation of adherend with rougher surface roughness) ≫
An adherend having a surface roughness greater than that of the cork board (an adherend having a surface roughness Rz that is at least twice that of a normal adherend) was prepared. Next, an aqueous emulsion adhesive (Rikabond BA-10L (main agent): BA-11B (curing agent)) manufactured by Chuo Rika Kogyo Co., Ltd. was applied on the adherend in an amount of 6 to 7 g / scale angle. Each decorative sheet was prepared by laminating each of the decorative sheets 1 to 3 and further curing at 3 days. The surface state of each decorative board was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if the evaluation is B or more, the surface state has no problem in the actual use situation.
A +: The uneven shape of the adherend is not exposed.
A: The uneven shape of the adherend is slightly exposed.
B: The uneven shape of the adherend is slightly exposed.
C: The uneven | corrugated shape of a to-be-adhered material has exposed rather than the case of said B evaluation.

≪Evaluation method 7: Evaluation of design properties of decorative sheet≫
First, each decorative board was produced by the same method as that described in Evaluation Method 6 above. Next, 20 adult men and women observed the appearance of each decorative panel, and evaluated whether or not the texture of wood could be expressed according to the following evaluation criteria. In addition, in the following evaluation criteria, if the evaluation is B or more, the surface state has no problem in the actual use situation.
A +: More than 90% of adult men and women who judge that the texture of wood can be expressed.
A: More than 70% of adult men and women who judge that the texture of wood can be expressed.
B: More than 50% of adult men and women who judge that the texture of wood can be expressed.
C: Less than 50% of adult men and women who judge that the texture of wood can be expressed.

  The results are shown in Tables 1 to 3 below.

1. Cosmetic sheet 2. 2. base material sheet Pattern layer 4. 4. Transparent resin layer 5. Surface protective layer 6. Backer layer Gloss adjustment layer

Claims (7)

A decorative sheet in which at least a transparent resin layer and a surface protective layer are sequentially laminated on the base sheet, and at least a backer layer is laminated on the back surface of the base sheet,
(1) Ten-point average roughness Rz _jis of the surface of the decorative sheet is 40 μm or more,
(2) The surface protective layer contains an ionizing radiation curable resin,
(3) The base sheet, the transparent resin layer, and the backer layer each include a non-halogen thermoplastic resin,
(4) The backer layer has a thickness of 120 to 250 μm,
(5) Martens hardness of the backer layer is 50~80N / mm ^2,
(6) The backer layer is laminated by extruding the backer layer forming resin composition in a molten state with respect to the back surface of the base sheet.
A decorative sheet characterized by that.   The decorative sheet according to claim 1, wherein a gloss adjusting layer is formed on the transparent resin layer, and the gloss adjusting layer is formed adjacent to the surface protective layer.   A roll-like product obtained by winding the decorative sheet according to claim 1 in a roll shape.   A decorative board in which a decorative sheet according to claim 1 or 2 or a decorative sheet obtained by unwinding the roll-shaped article according to claim 3 is laminated on an adherend. A method for producing a decorative sheet in which at least a transparent resin layer and a surface protective layer are sequentially laminated on a base material sheet, and at least a backer layer is laminated on the back surface of the base material sheet, the following steps: 1-3:
(i) A laminated sheet having at least a transparent resin layer and a surface protective layer in this order on a base sheet,
The surface protective layer contains an ionizing radiation curable resin,
Step 1 of obtaining a laminated sheet, wherein the base sheet and the transparent resin layer both contain a non-halogen thermoplastic resin,
(ii) Step 2 of _setting the ten-point average roughness Rz _jis of the surface of the laminated sheet to 40 μm or more by embossing from above the surface protective layer of the laminated sheet; and
(iii) by extruding the resin composition for forming a backer layer in a molten state with respect to the back surface of the base sheet,
The backer layer comprises a non-halogen thermoplastic resin;
The backer layer has a thickness of 120 to 250 μm,
The Martens hardness of the backer layer is 50 to 80 N / mm ² .
Step 3 of laminating the backer layer,
In order. The manufacturing method of the decorative sheet characterized by the above-mentioned. A method for producing a decorative sheet in which at least a transparent resin layer and a surface protective layer are sequentially laminated on a base material sheet, and at least a backer layer is laminated on the back surface of the base material sheet, the following steps: 1-4:
(i) A laminate having at least a transparent resin layer on a substrate sheet,
Step 1 for obtaining a laminate in which the base sheet and the transparent resin layer each include a non-halogen thermoplastic resin;
(ii) Step 2 of embossing from above the transparent resin layer of the laminate;
(iii) By coating a resin composition for forming a surface protective layer containing an ionizing radiation curable resin on the transparent resin layer,
A laminated sheet having at least a transparent resin layer and a surface protective layer on a substrate sheet,
Step 3 of obtaining a laminated sheet having a ten-point average roughness Rz _jis of 40 μm or more on the surface of the laminated sheet, and
(iv) by extruding the resin composition for forming a backer layer in a molten state with respect to the back surface of the base sheet,
The backer layer comprises a non-halogen thermoplastic resin;
The backer layer has a thickness of 120 to 250 μm,
The Martens hardness of the backer layer is 50 to 80 N / mm ² .
Step 4 of laminating the backer layer,
In order. The manufacturing method of the decorative sheet characterized by the above-mentioned.   The manufacturing method of the decorative board which laminates | stacks the said decorative sheet on a to-be-adhered material so that the surface protection layer of the decorative sheet obtained by the manufacturing method of the decorative sheet of Claim 5 or 6 may become an outermost surface layer.