JP5999876B2 - Decorative sheet and decorative board - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative board.

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

  Conventional decorative sheets generally have a smooth surface. Therefore, when it is used for flooring, flooring, etc., it is slippery when a person walks and there is a risk of falling.

  Therefore, for the purpose of imparting anti-slip properties to the decorative sheet, a flooring in which a thermoplastic polymer is scattered and exposed on the surface has been proposed (Patent Document 1). In addition, flooring materials are known in which anti-slip properties are imparted by adding special fillers to the surface protective layer or embossing the surface of the decorative sheet.

JP 2001-254504 A

  However, when the flooring (decorative board) of Patent Document 1 is used for a lightweight object, for example, a pet such as a dog or a cat, there is a problem that the slip resistance is poor.

  In addition, a decorative sheet in which a filler is added to the surface protective layer or an embossed decorative sheet loses a specific surface irregularity shape, such as the filler surface being scraped when used, and the slip resistance gradually decreases. There is a problem.

  Accordingly, the main object of the present invention is to provide a decorative sheet that is excellent in slip resistance even when the object is a lightweight object, and in which a decrease in slip resistance is suppressed.

  As a result of intensive studies, the present inventor has found that a decorative sheet having a surface protective layer on the outermost surface, and the above object can be achieved when the surface of the surface protective layer satisfies a specific condition. It came to complete.

That is, the present invention relates to the following decorative sheet and decorative plate.
1. A decorative sheet having a surface protective layer on the outermost surface,
(1) The Martens hardness of the surface protective layer is 130 to 150 N / mm ² ,
(2) The surface protective layer has irregularities, and the average interval Sm between the irregularities is 180 μm to 500 μm,
(3) A decorative sheet, wherein the surface protective layer has a maximum height Rz of 20 to 60 μm.
2 . Item 2. The decorative sheet according to Item 1, wherein the Sm is 250 to 350 µm.
3 . Item 3. The decorative sheet according to Item 1 or 2 , wherein Rz is 20 to 50 µm.
4 . Item 4. The decorative sheet according to any one of Items 1 to 3 , wherein the surface protective layer contains an ionizing radiation curable resin.
5 . Item 5. The decorative sheet according to any one of Items 1 to 4 , which has any one of a pattern layer, a transparent thermoplastic resin layer, and a primer layer on a base sheet.
6 . 6. A decorative board in which the decorative sheet is laminated on an adherend so that the surface protective layer of the decorative sheet according to any one of Items 1 to 5 is an outermost surface.

Hereinafter, the decorative sheet and the decorative plate of the present invention will be described in detail.
The decorative sheet of the present invention is a decorative sheet having a surface protective layer on the outermost surface,
(1) The Martens hardness of the surface protective layer is 30 to 170 N / mm ² , (2) the surface protective layer has irregularities, and the average interval Sm of the irregularities is 180 μm to 500 μm,
(3) The maximum height Rz of the surface protective layer is 20 to 60 μm.
It is. When the decorative sheet of the present invention has the above-described characteristics, the object is excellent in anti-slip property even when the object is light, and the decrease in anti-slip property is suppressed.

Layer structure of the decorative sheet of the present invention The decorative sheet of the present invention only needs to have the surface protective layer on the outermost surface, and the specific structure may be appropriately set according to the use of the decorative sheet. For example, a decorative sheet having any one of a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, and a primer layer on a base sheet is mentioned.

  Hereinafter, regarding the decorative sheet of the present invention, on a base sheet, a decorative sheet having a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, a primer layer and the surface protective layer in this order as a representative example I will explain it.

(Substrate sheet)
The substrate sheet has a pattern layer or the like sequentially laminated on its surface (front surface).

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

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

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

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

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

  Although not shown, the decorative sheet of the present invention may be formed by laminating a polyester-based backer material on the back primer layer side of the base material sheet with a transparent adhesive layer adhesive described later by a dry lamination method. When the back primer layer is not provided, a hard polyolefin-based backer material may be laminated on the back side of the thermoplastic resin base sheet by an extrusion laminating method or the like, and the back primer layer may be provided on the back side of the backer material.

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

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

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

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

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

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

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

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

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

The coating amount is desirably in the range of ^{2 to} 30 g / m2. The thickness of the colored masking layer is usually about 0.1 to 20 μm, preferably about 1 to 10 μm.

(Transparent adhesive layer)
In order to enhance the adhesion between the transparent thermoplastic resin layer and the pattern layer, which will be described later, a transparent adhesive layer may be formed. The transparent adhesive layer is not particularly limited as long as it does not impair the design properties, and includes any of colorless and transparent, colored and transparent, translucent and the like.

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

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

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

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

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

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

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

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

  The method for forming the transparent thermoplastic resin layer is not limited, for example, a method in which a preformed sheet or film is laminated to an adjacent layer, a resin composition that can form a transparent thermoplastic resin layer is melt-extruded, and the adjacent layer is adjacent There is a method of laminating together with the layer to be performed. Examples of the laminating method include a laminating method by a dry laminating method.

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

(Surface protective layer)
The decorative sheet of the present invention has a surface protective layer having a Martens hardness (hardness) of 30 to 170 N / mm ² on the outermost surface. The preferred Martens hardness of the surface protective layer is 60 to 150 N / mm ² . If the Martens hardness is within the above range, even if the object is a lightweight object, the object is excellent in anti-slip property, and the decrease in anti-slip property is suppressed. In particular, even after a specific surface irregularity shape to be described later disappears, the slip resistance can be maintained.

In addition, the Martens hardness in this specification is a value measured using a surface film physical property tester (PICODETOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measuring method is as follows. is there. In this measurement method, using the diamond indenter (Vickers indenter) shown in Fig. 1 (a), the diamond indenter was pushed into the measurement sample as shown in Fig. 1 (b), and the diagonal line of the pyramid-shaped depression formed on the surface 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. 1 (c), the indentation conditions were as follows. First, a load of 0 to 5 mN was applied for 10 seconds, then 5 mN was maintained for 5 seconds, and finally 5 Unloading to ~ 0mN is performed in 10 seconds. And the hardness calculated | required by 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 surface protective layer, the Martens hardness of the cross section of the surface protective layer was measured. In this case, the decorative sheet is embedded with a resin (cold-curing type epoxy two-component curable resin), allowed to stand at room temperature for 24 hours or more and cured, and then the cured embedded sample is mechanically polished to provide a surface protective 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 (at a position avoiding the fine particles such as filler when the fine particles such as fillers were included in the layer).

  The Martens hardness of the surface protective layer can be appropriately set by 1) mixing a plurality of resin components, 2) adding an elastomer to the resin, or the like. For example, when using the urethane acrylate described later as a resin component constituting the surface protective layer, a bifunctional urethane acrylate and a hexafunctional urethane acrylate are appropriately blended, or only a trifunctional urethane acrylate having a molecular weight of about 1500 is used. Thus, a desired Martens hardness can be obtained. Here, the bifunctional urethane acrylate means a urethane acrylate having two radically polymerizable acryloyl groups in one molecule. Similarly, trifunctional urethane acrylate and hexafunctional urethane acrylate mean urethane acrylates having three and six radically polymerizable acryloyl groups in one molecule, respectively.

  Moreover, the decorative sheet of the present invention has a specific uneven shape on the surface thereof.

  The average interval (Sm) of the unevenness is 180 μm to 500 μm, and if Sm is within the above range, the object is excellent in slip resistance regardless of whether the object is heavy or light. A preferable range of Sm is 250 to 350 μm.

  The Sm is an index indicating the interval between the irregularities of the surface protective layer, and is extracted from the roughness curve of the surface protective layer by a reference length L in the direction of the average line, one peak and one valley adjacent thereto. Is obtained by calculating the sum of the lengths of the average lines corresponding to. When Sm is small, the surface is fine (the unevenness is dense).

  Moreover, the maximum height (Rz) of the surface protective layer is 20 to 60 μm. Preferably it is 20-53 micrometers, More preferably, it is 20-50 micrometers. When Rz is less than 20, the anti-slip property is inferior when the object is a lightweight object, and when Rz exceeds 60, the scratch resistance is inferior.

  Rz is an index indicating the maximum height of the surface protective layer, and is extracted from the roughness curve of the surface protective layer by a reference length L in the direction of the average line, and the highest peak from the average line of the extracted portion. This represents the sum of the height Ha up to and the depth Hb up to the lowest valley bottom (Rz = Ha + Hb).

  The ten-point average roughness (Rzjis) of the surface protective layer is preferably 10 μm or more, and more preferably 20 to 30 μm.

  Rzjis is an index indicating the roughness of the surface protective layer, and is extracted from the roughness curve of the surface protective layer by a reference length L in the direction of the average line, and the highest peak from the average line of the extracted portion. It is the sum of the average value of the absolute values of the altitude at the top of the mountain from the first to the fifth and the average value of the absolute values of the altitude of the bottom of the valley from the lowest to the fifth.

  The above-mentioned Sm is based on JIS B0601 (1994), and Rz and Rzjis are based on JIS B0601 (2001) surface roughness standards.

  The above-described Sm, Rz, and Rzjis are all obtained by measuring the surface roughness. The surface roughness can be measured using a surface roughness shape measuring instrument, for example, Surfcom 120A (manufactured by Tokyo Seimitsu Co., Ltd.).

  Moreover, it is preferable that the decorative sheet of this invention is 0.37 or more regarding the static friction coefficient of a surface protective layer, and 0.45-0.55 is more preferable.

  Moreover, it is preferable that the dynamic friction coefficient of a surface protective layer is 0.35 or more, and it is more preferable that it is 0.4-0.5.

  The static friction coefficient and the dynamic friction coefficient can be measured in accordance with JIS K 7125. For example, it can be measured using a tensile tester (Tensilon universal tester “RTC-1250A”).

  Sm, Rz and Rzjis of the surface protective layer can be appropriately set by 1) containing a filler to be described later, or 2) performing embossing. The static friction coefficient and the dynamic friction coefficient can be appropriately set by, for example, mixing the plurality of resin components described later in addition to the above methods 1) and 2).

  The surface protective layer is preferably transparent when the pattern layer is formed in the lower layer.

  The surface protective layer is preferably an ionizing radiation curable resin layer formed by resin crosslinking of an ionizing radiation curable resin from the viewpoint of scratch resistance and the like. The ionizing radiation curable resin refers to a resin that crosslinks and cures when irradiated with ultraviolet rays, electron beams, or the like.

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

  Examples of the prepolymer or oligomer include polyester methacrylate, polyether methacrylate, urethane methacrylate, polyol methacrylate, methacrylates such as melamine methacrylate, polyester acrylate, polyether acrylate, urethane acrylate, polyol acrylate, There are acrylates such as melamine acrylate. As the urethane (meth) acrylate, for example, a urethane acrylate oligomer according to Japanese Patent Application Laid-Open No. 2007-118596 may be used.

  Monomers include styrene monomers such as styrene and α-methylstyrene, acrylic acid such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, and phenyl acrylate. Examples include esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, and lauryl methacrylate.

  As substituted amino alcohol esters of unsaturated acids, acrylic acid-2- (N, N-diethylamino) ethyl, methacrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N -Substituted amino alcohol esters of unsaturated acids such as -dibenzylamino) methyl and acrylic acid-2- (N, N-diethylamino) propyl.

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

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

  The thickness of the surface protective layer is not particularly limited as long as it does not interfere with the effects of the present invention, but is preferably 1 to 200 μm, more preferably 1 to 100 μm, and even more preferably 5 to 50 μm. In the present specification, the thickness of the surface protective layer refers to the length from the bottom of the resin forming the surface protective layer to the smooth portion where no convex portion is formed by the filler described later. Moreover, in this specification, the thickness of the convex part formed with a filler means the length from the smooth part of the surface protective layer in which the convex part is not formed with the filler to the top part formed with the filler. Each thickness described above is described in detail in FIG.

  Examples of the filler contained in the surface protective layer include inorganic particles such as silica and silicone resin (powder, beads); acrylic, crosslinked alkyl, crosslinked styrene, inzoguanamine resin, urea-formaldehyde resin, phenol resin, polyethylene, nylon Examples thereof include organic material powders and beads. The filler is preferably at least one selected from the group consisting of silica and acrylic beads. In addition, the said filler can be used 1 type, or 2 or more types.

  The average particle diameter of the filler is at least equal to or greater than the thickness of the surface protective layer, and is preferably less than “thickness of the surface protective layer + 40 μm” in order to maintain scratch resistance described later, and “thickness of the surface protective layer + 30 μm”. The following is more preferable. When the average particle diameter of the filler is equal to the thickness of the surface protective layer, the surface protective layer has no convex portion formed by the filler (that is, the thickness of the convex portion formed by the filler is 0 μm). In addition, there may be a convex portion formed by the filler.

  About the average particle diameter of a filler, it can measure by well-known methods, such as a laser diffraction method, a Coulter counter method, and a sedimentation method. The average particle diameter means a particle diameter (D50) corresponding to a cumulative frequency of 50%.

  The filler content in the surface protective layer is preferably 3 to 50 parts by weight and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the resin component forming the surface protective layer. .

  In the decorative sheet of the present invention, the filler described above is preferably present inside the surface protective layer as long as the effects of the present invention are not hindered. The smaller the proportion of the filler protruding from the surface of the surface protective layer, the better the surface performance such as scratch resistance.

  In addition to the fillers described above, the surface protective layer has an organic resin such as inorganic particles such as α-alumina, chromium oxide, iron oxide and diamond, and synthetic resin beads such as crosslinked acrylic for the purpose of further improving the scratch resistance. Powders such as particles may be added. Various particle shapes of these powders are used. In particular, when a spherical shape or a shape similar to the spherical shape is used, the scratch resistance is good. The average particle diameter of the powder is preferably equal to or less than the coating thickness (surface protective layer thickness), and the addition amount is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin component. One or two or more of the powders described above can be used.

  In addition to the above powder, the surface protective layer may use a matting material for the purpose of further enhancing the matting effect (matting) of the surface.

  Matte materials include silica, calcium silicate, aluminum silicate, magnesium silicate, kaolin, mica, talc, and other inorganic pigments; titanium dioxide, calcium carbonate, barium carbonate, and other inorganic pigments; polyurethane, polystyrene, polyamide, poly And organic pigments such as vinyl chloride and acrylic fine polymer particles. Among these, silica is preferable from the viewpoint that the matting effect per weight of the matting material is high. In addition, the said mat | matte material can be used 1 type, or 2 or more types.

  The average particle size of the matte material is at least less than the thickness of the surface protective layer.

And the matting material, when adding the filler simultaneously in the surface protective layer, the average particle size of the filler (d _f), the average particle diameter of the matting material (d _m), and the thickness of the coating film (surface protection relationship layer thickness (D)) is _{0 <d m <D ≦ d} f.

  Here, the preferable specific aspect regarding the average particle diameter of a filler, the average particle diameter of a matting material, and the thickness of a surface protective layer (coating film) is shown below. For example, when the thickness of the surface protective layer is 5 μm, the average particle size of the filler is preferably 6 to 10 μm, and when the matte material is also contained, the average particle size of the matte material is preferably 1 to 4 μm. When the thickness of the surface protective layer is 15 μm, the average particle size of the filler is preferably 16 to 54 μm, and when the matte material is also contained, the average particle size of the matte material is preferably 1 to 14 μm. When the thickness of the surface protective layer is 50 μm, the average particle size of the filler is preferably 51 to 89 μm, and when the matte material is also contained, the average particle size of the matte material is preferably 1 to 49 μm.

The specific surface area of the matting material is usually ^{50 m} 2 / g or more, 50~350m ² / g are preferred.

  The addition amount of the matting material is usually 20 parts by weight or less, preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the resin component.

  Further, 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. When adding an ultraviolet absorber, the surface protective layer is cured by irradiation with an electron beam. Further, when the resin layer is cured by irradiating with ultraviolet rays, as photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-amino oxime ester, tetramethylthiuram monosulfide, thioxanthones, aromatic As photopolymerization accelerators (sensitizers) such as diazonium salts, aromatic sulfonium salts, metallocenes, n-butylamine, triethylamine, tri-n-butylphosphine and the like are used.

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

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

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

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

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of about 190 to 380 nm can be used.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The acceleration voltage of the electron beam is generally about 100 to 1000 keV, preferably about 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

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

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

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

  Furthermore, you may make a primer agent contain a well-known additive as needed. For example, the adhesion between the transparent thermoplastic resin layer and the surface protective layer can be further improved by adding a hexamethylene diisocyanate curing agent to the primer agent.

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

  Although the thickness of a primer layer is not specifically limited, Usually, it is about 0.1-100 micrometers, Preferably it is about 0.5-15 micrometers.

  Moreover, you may add various weathering agents, such as a ultraviolet absorber and a light stabilizer, to a primer layer.

Manufacturing method of decorative sheet The decorative sheet of the present invention is obtained by having at least the above-mentioned surface protective layer on the outermost surface. For example, it is obtained by laminating a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, and a primer layer on a base sheet, and then forming a surface protective layer on the outermost surface.

  Moreover, when embossing is performed on the decorative sheet, it may be after the surface protective layer is formed or before the surface protective layer is formed. For example, as specific embodiments, 1) a pattern layer, a transparent thermoplastic resin layer, and a primer layer may be sequentially formed on a base sheet, and then a surface protective layer may be formed and finally embossed. . As another specific embodiment, 2) A pattern layer, a transparent thermoplastic resin layer, and a primer layer may be formed in this order on a base sheet, and then embossed, and finally a surface protective layer may be formed. Good. As still another specific embodiment, 3) a pattern layer and a transparent thermoplastic resin layer are formed in order on the base sheet, and then embossed, followed by a primer layer, and finally a surface protective layer. May be formed. When adjusting the Sm, Rz, Rzjis, static friction coefficient and dynamic friction coefficient of the surface protective layer by embossing, it is preferable to perform embossing after forming the surface protective layer.

For the embossing, a known embossed plate is used, and for example, the uneven pattern may be transferred to the pattern printing surface side of the decorative sheet at a sheet temperature of 120 to 160 ° C. and a pressure of 10 to 40 kg / cm ² .

  When performing wiping processing, as described in Japanese Patent Publication No. 58-14312, etc., after applying colored ink on the concavo-convex pattern, wiping is performed, and the concave portion of the concavo-convex pattern is filled with the colored ink. By doing.

  In addition, the said synthetic resin backer material can be formed by extruding molten resin with respect to the base material sheet back surface of the decorative sheet in which the surface protective layer was formed.

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

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

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

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

  The decorative sheet of the present invention is excellent in slip resistance even when the object is a lightweight object, and the decrease in slip resistance is suppressed. Therefore, the decorative board laminated with the decorative sheet of the present invention can be used for various building materials, furniture and the like. In particular, the decorative board of the present invention can be suitably used as a floor decorative material.

FIG. 1 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. FIG. 2 is a cross-sectional view of the decorative sheet of the present invention. FIG. 3 is a conceptual diagram (cross-sectional view) of the layer structure of the decorative sheet of the present invention. FIG. 4 is an example of the measurement results of the surface roughness of the decorative sheet produced in Example 4 before and after the unevenness disappearance promoting treatment. Vertical scale: 20 μm / 10 mm, Horizontal scale: 500 μm / 10 mm FIG. 5 is an example of the measurement results of the surface roughness before and after the unevenness disappearance promotion treatment of the decorative sheet produced in Example 5. Vertical scale: 20 μm / 10 mm, Horizontal scale: 500 μm / 10 mm

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples. Of Examples 1 to 13, Examples 3, 4 and 9 are within the scope of the present invention, and the others are reference examples.

The following components were prepared as components of the resin composition constituting the surface protective layer.
Bifunctional urethane acrylate oligomer A (polyol component is polyester diol, Tg: 25 ° C., molecular weight 1200)
Bifunctional urethane acrylate oligomer B (polyol component is polyether diol, Tg: −55 ° C., molecular weight 5000)
Bifunctional urethane acrylate oligomer C (polyol component is polyester diol, Tg: 25 ° C., molecular weight 1500)
-Hexafunctional aliphatic urethane acrylate oligomer (Tg: 200 ° C or higher, molecular weight 1500, UA306H manufactured by Kyoeisha Chemical Co., Ltd.)
Filler: (average particle size 20 μm silica)
・ Filler: (average particle size 35μm acrylic beads)
・ Matte material: (average particle size 11μm silica)
Moreover, the embossing plate for attaching the following embossing shapes was prepared regarding embossing.
・ Small grain texture (grain texture (thin)),
・ Rough grain texture (grain texture (coarse))
・ Graininess (graininess (medium)) that is intermediate between fine graininess and coarseness.
・ Wood tone

Example 1
After performing corona discharge treatment on the front and back surfaces of the base sheet made of a colored polypropylene film having a thickness of 60 μm, a gravure printing method using a colored ink having an acrylic resin as a binder resin on the base sheet, A 4 μm thick grain pattern layer was formed. Also, a thickness of 2 μm is obtained by a gravure printing method using a resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of acrylic urethane resin and nitrified cotton resin on the surface opposite to the pattern layer of the base sheet. The back surface primer layer was formed. A coating solution made of a two-component curable urethane resin was applied on the pattern layer to form a transparent adhesive layer having a thickness of 2 μm. Further, a polypropylene resin sheet was laminated by extrusion lamination on the adhesive layer to form a transparent thermoplastic resin layer having a thickness of 80 μm. After subjecting the surface of the transparent thermoplastic resin layer to corona discharge treatment, a two-component curable urethane resin was applied on the transparent thermoplastic resin layer to form a primer layer having a thickness of 1 μm. Subsequently, embossing was performed under the conditions of a sheet temperature of 120 ° C. to 160 ° C. and a pressure of 10 to 40 kg / cm ² to form a fine grained emboss shape. Furthermore, a two-component curable urethane resin is applied on the primer layer to form a primer layer having a thickness of 1 μm, and a resin composition constituting the surface protective layer shown below is further applied by a roll coating method. After the film (15 μm) was formed, a surface protective layer was formed by irradiating with an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy) in an environment with an oxygen concentration of 200 ppm or less to prepare a decorative sheet. Moreover, the said decorative sheet was bonded together on the medium density wood fiber board (MDF) of thickness 2.7mm through the adhesive agent, and the decorative board was produced.
[Resin composition constituting surface protective layer]
-Bifunctional urethane acrylate oligomer A 52 parts by weight-Bifunctional urethane acrylate oligomer B 18 parts by weight-Hexafunctional aliphatic urethane acrylate oligomer 30 parts by weight-Filler (20 μm silica) 5 parts by weight

Examples 2-5, 7-13 and Comparative Examples 3, 5 and 6
The decorative sheets as shown in Tables 1 and 2 were used in the same manner as in Example 1 except that the components of the resin composition constituting the surface protective layer and the content thereof, the Martens hardness, the type of embossed shape, and the like were appropriately changed. A decorative board was obtained.

Example 6
In the same manner as in Example 1, a back primer layer, a base sheet, a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, and a primer layer were laminated. Then, after forming a coating film (15 μm) by the roll coating method on the resin composition constituting the surface protective layer shown below, an electron beam is irradiated under the conditions of 175 keV and 5 Mrad (50 kGy) in an environment with an oxygen concentration of 200 ppm or less. By doing so, a surface protective layer was formed. Thereafter, embossing was performed under the conditions of a sheet temperature of 120 ° C. to 160 ° C. and a pressure of 10 to 40 kg / cm ² to form a grained (medium) embossed shape, and a decorative sheet was produced. In addition, a decorative board was produced in the same manner as in Example 1.
[Resin composition constituting surface protective layer]
-Bifunctional urethane acrylate oligomer A 52 parts by weight-Bifunctional urethane acrylate oligomer B 18 parts by weight-Hexafunctional aliphatic urethane acrylate oligomer 30 parts by weight-Matte material (11 μm silica) 10 parts by weight

Comparative Examples 1, 2, and 4
The decorative sheets as shown in Tables 1 and 2 were used in the same manner as in Example 6 except that the components of the resin composition constituting the surface protective layer and the content thereof, the Martens hardness, the type of the embossed shape, and the like were appropriately changed. A decorative board was obtained.

Measurement and evaluation (1)
The following measurements or evaluations were performed on the decorative sheets or decorative plates produced in Examples 1 to 13 and Comparative Examples 1 to 6.

<< Martens hardness measurement >>
The Martens hardness in the cross-sectional direction of the surface protective layer was measured by the method described above. The results are shown in Tables 1 and 2. In addition, the value of the Martens hardness in a table | surface shows the average value of 10 times of measured values.

<< Measurement of Rz, Rzjis, and Sm >>
Rz, Rzjis and Sm values were measured. Said Rz, Rzjis, and Sm are obtained by measuring the surface roughness of a decorative board. The surface roughness was measured according to JIS B0601. As an example, the surface roughness measurement results of the decorative sheets produced in Examples 4 and 5 are shown in FIGS. For the surface roughness measurement, a surface roughness shape measuring instrument (Surfcom 120A manufactured by Tokyo Seimitsu Co., Ltd.) was used. The results are shown in Tables 1 and 2. In the table, Rz, Rzjis, and Sm represent the maximum value and the minimum value in a range by measuring the decorative board three times at different positions.

<< Measurement of static friction coefficient and dynamic friction coefficient >>
The static friction coefficient and the dynamic friction coefficient were measured. The measurement was performed according to JIS K 7125. As the tensile tester, Tensilon universal tester “RTC-1250A” was used. The results are shown in Tables 1 and 2. In addition, the value of the static friction coefficient and dynamic friction coefficient in a table | surface measures three points | pieces in a different position, and shows the average value of the said measured value.

<< Slipproof Evaluation Human >>
Slip resistance (human) was confirmed. Specifically, each decorative sheet is processed into a floor, and for 15 adult men and women in their 20s to 40s, 1) wearing socks, 2) wearing stockings, and / or 3) walking on the floor with bare feet And he was allowed to walk. The same walk was performed on general-purpose wood floors (general veneer painted floors on the market). The results are shown in Tables 1 and 2. The evaluation method is as follows.
◎: More than 10 adult men and women felt more difficult to slide than general-purpose wood floors.
○: More than 8 adult men and women felt difficulty in sliding.
X: The number of adult men and women who felt that it was difficult to slide was 7 or less.

<< Method (Anti-slip evaluation dog) >>
Slip resistance (dog) was confirmed. Specifically, each decorative sheet was floor processed, and small dogs and medium-sized dogs were allowed to walk, normally run, jump, and repeat. The same behavior was applied to general-purpose wood floors. The results are shown in Tables 1 and 2. The evaluation method is as follows.

  ○: Small dogs and medium-sized dogs were not found to be wobbling or slipping compared to general-purpose wooden floors.

  X: Compared with a general-purpose wooden floor, light and slippery feet of small and medium-sized dogs were observed.

Measurement and evaluation (2)
After performing the uneven | corrugated shape disappearance promotion process with respect to the decorative sheet and the decorative board produced in Examples 1-13 and Comparative Examples 5 and 6, the following measurement and evaluation were performed. The above concavo-convex shape disappearance promoting treatment is a sliding treatment with steel wool (Nihon Steel Wool Co., Ltd., material: iron, product number: # 1, quality: intermediate), load 300 g / m ² until the surface of the sheet changes slightly gloss. Carried out.

<< Measurement of Rz, Rzjis, and Sm >>
It carries out similarly to the said measurement and evaluation (1), and shows a measurement result in Table 1,2.

<< Measurement of static friction coefficient and dynamic friction coefficient >>
It carries out similarly to the said measurement and evaluation (1), and a measurement result is shown to Table 1,2.

<< Anti-slip test (OY / PSM) >>
For each decorative board, the slip resistance value (CSR value) by socks was measured using a Tokyo Institute of Technology slip tester (O-Y PSM). The measurement results are shown in Tables 1 and 2.
A: Measurement value is 0.35 or more and 0.50 or less (non-slip)
○: The measured value is 0.30 or more and less than 0.35 (slightly slippery)
X: The measured value is 0.25 or more and less than 0.30 (easy to slip)
XX: The measured value is larger than 0.50 and 0.55 or less (easy to roll)
In addition, it shows that it is easy to slip, so that a numerical value is small, and the range of the slip resistance value which a person feels comfortable is in the range of 0.3-0.5.

<< Anti-slip test (ONO / PPSM) >>
A portable slip tester (ONO / PPSM) is installed on each decorative plate, and after the slip piece is brought into full contact with the measurement location, the handle is immediately rotated (preset time 0 s) and pulled diagonally upward at 18 ° C. Pulling was performed at a loading speed of about 20 kgf (196 N). Then, after confirming that the slip piece clearly starts to move, the pulling is stopped, the maximum tensile load (Pmax) until the stop is read, and the slip resistance coefficient C.I. S. R · D ′ was calculated.

C. S. R · D ′ = Pmax (kgf) / 5 kgf
Here, the combined mass of the ONO · PPSM sliding piece and the weight is 5 kg. The size of the contact surface between the sliding piece and the floor is 6 × 5 cm. The sliding piece is foam rubber (Shore A hardness: 10, thickness: 10 mm, material polyurethane foam) and hemp fabric (plain weave, thickness) : 0.80 mm, material: jute, weave density: 8 × 8 / inch ² ). (Reference) Hidetsugu Ono: Development of portable floor slip tester (ONO / PPSM), Architectural Institute of Japan, No. 585, pp. 51-56, November 2004
The measurement results are shown in Tables 1 and 2.
○: Measurement value is 0.33 or more and 0.55 or less (slip hardly occurs)
X: The measured value is less than 0.33 (slip occurs)
In addition, it shows that it is slippery so that a numerical value is small, and it is 0.33 or more and 0.55 or less that a dog's slip hardly generate | occur | produces. And within the range of 0.55 or less.

Claims (6)

A decorative sheet having a surface protective layer on the outermost surface,
(1) The Martens hardness of the surface protective layer is 130 to 150 N / mm ² ,
(2) The surface protective layer has irregularities, and the average interval Sm between the irregularities is 180 μm to 500 μm,
(3) A decorative sheet, wherein the surface protective layer has a maximum height Rz of 20 to 60 μm. The decorative sheet according to claim 1, wherein the Sm is 250 to 350 μm. The decorative sheet according to claim 1 or 2 , wherein the Rz is 20 to 50 µm. The decorative sheet according to any one of claims 1 to 3 , wherein the surface protective layer contains an ionizing radiation curable resin. The decorative sheet according to any one of claims 1 to 4 , comprising any one of a design pattern layer, a transparent thermoplastic resin layer, and a primer layer on the base sheet. A decorative board in which the decorative sheet is laminated on an adherend so that the surface protective layer of the decorative sheet according to any one of claims 1 to 5 is the outermost surface.

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