JP6107912B2 - Decorative sheet for floor and method for producing the same - Google Patents

Description

  The present invention relates to a floor decorative sheet and a method for producing the same.

  For the purpose of obtaining a floor decorative sheet having a large uneven shape (for example, with a floating grain) as a floor decorative sheet, the surface protective layer is coated with an ionizing radiation curable resin, cured, and then embossed. A method is known in which wood grain-like irregularities are formed on the surface of a decorative sheet for flooring. However, even such a decorative sheet for floors having a large uneven shape has a problem that the slip resistance is not sufficient.

  Therefore, in order to further improve the slip resistance of the surface of the decorative sheet for flooring, a resin containing particles having a particle diameter larger than the thickness of the surface protective layer is applied to the surface protective layer, cured, and then embossed. A method for forming irregularities on the surface of a decorative sheet for floors by applying the above is known. However, even with such a method, the embossing crushes particles having a particle diameter larger than the thickness of the surface protective layer exposed on the surface of the decorative sheet for flooring, so that sufficient slip resistance cannot be obtained. There was a problem.

  In addition, in order to prevent the particles having a particle diameter larger than the thickness of the surface protective layer constituting the decorative sheet for flooring from being crushed, the floor decorative sheet is pre-embossed to form irregularities, A method is known in which a resin containing particles having a particle diameter larger than the thickness of the surface protective layer is applied to the surface protective layer of the decorative sheet for use and cured. However, even in such a method, in a decorative sheet for floors having a large uneven shape (for example, having a floating grain), a surface protective layer cannot be formed in the concave portion of the uneven shape, and therefore surface properties (for example, scratch resistance) It was difficult to ensure sufficient properties and weather resistance.

  In addition, in order to provide a smooth and warm tactile sensation (peach skin feeling) similar to solid wood in a decorative sheet, a resin composition comprising synthetic resin beads having an average particle size of 10 to 30 μm on the surface of the decorative sheet body A peach skin-like decorative sheet is known in which the formed surface protective layer is formed, and the average film thickness of the portion excluding the synthetic resin beads protruding on the surface of the surface protective layer is 3 to 6 μm (Patent Document 1). . However, such a decorative sheet is merely for the purpose of improving the smooth and warm feel similar to that of solid wood, and is not an embossed decorative sheet. No improvement has been made on the improvement of the physical properties and other surface properties (for example, scratch resistance and weather resistance).

JP 2004-262105 A

  A floor decorative sheet having a large unevenness (for example, a floating decorative grain), and a floor decorative sheet and a floor decorative material excellent in slip resistance while maintaining surface properties (for example, scratch resistance and weather resistance). The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have, on the base sheet, at least a transparent resin layer, a first surface protective layer, and a second surface protective layer in order, 2 In the decorative sheet for floors in which the surface protective layer is the outermost surface layer, an uneven pattern is formed on the surface of the decorative sheet for floors, and the average roughness Rz of the uneven pattern is 60 μm or more, It has been found that the two-surface protective layer can solve the above problems by including particles having a particle diameter larger than the thickness of the second surface protective layer.

  Further, in the method for producing a decorative sheet for floors, a transparent resin layer is laminated on a base sheet, a first surface protective layer is laminated on the transparent resin layer, and the main surface of the first surface protective layer is formed. The above problem can also be achieved by embossing from the front surface and laminating the second surface protective layer containing particles having a particle diameter larger than the thickness of the second surface protective layer on the first surface protective layer. I found that it could be solved.

  Furthermore, the floor decorative sheet of the present invention, the touch feeling when the surface is touched with the skin, can be brought closer to a real tree than the conventional floor decorative sheet.

  The present invention has been completed based on such findings.

That is, this invention relates to the following decorative sheet for floors, and its manufacturing method.
1. A decorative sheet for floors having at least a transparent resin layer, a first surface protective layer, and a second surface protective layer in this order on a base sheet, wherein the second surface protective layer is the outermost surface layer,
(1) An uneven pattern is formed on the surface of the floor decorative sheet,
(2) The concavo-convex pattern is a floating wood grain whose deepest part reaches the transparent resin layer,
(3) The decorative sheet for floors, wherein the second surface protective layer contains particles having a particle diameter larger than the thickness of the second surface protective layer.
2. The floor decorative sheet according to Item 1, wherein the first surface protective layer and the second surface protective layer contain at least one of an ionizing radiation curable resin and a two-component curable urethane resin.
3. The decorative sheet for floor according to Item 1 or 2, wherein a second primer layer is formed between the first surface protective layer and the second surface protective layer.
4. The decorative sheet for floor according to any one of Items 1 to 3, wherein a first primer layer is formed between the transparent resin layer and the first surface protective layer.
5. A flooring decorative material obtained by bonding the base sheet side of the flooring decorative sheet according to any one of Items 1 to 4 to an adherend.
6. On the base sheet, at least a transparent resin layer, a first surface protective layer, and a second surface protective layer are provided in this order, and the second surface protective layer is the outermost surface layer, and an uneven pattern is formed on the surface. The uneven pattern is a method for producing a decorative sheet for floors, which is a floating grain that has the deepest part reaching the transparent resin layer,
(1) Step 1 of laminating a transparent resin layer on a substrate sheet,
(2) Step 2 of laminating a first surface protective layer on the transparent resin layer,
(3) Step 3 of embossing from the front surface of the first surface protective layer; and (4) Particles having a particle diameter larger than the thickness of the second surface protective layer on the first surface protective layer. The manufacturing method of the decorative sheet for floors which includes the process 4 of laminating | stacking the said 2nd surface protective layer containing this in order.
7. After the step 1, a step of forming a first primer layer between the transparent resin layer and the first surface protective layer, and after the step 3, the first surface protective layer and the second surface layer. The method for producing a floor decorative sheet according to Item 6, further comprising a step of forming a second primer layer between the surface protective layer and the surface protective layer.
8. After obtaining the Lucas cosmetic sheet by the method according to the claim 6 or 7, the substrate sheet side of that, a method of manufacturing a combined decorative material bonded to the adherend.

  The decorative sheet for floors of the present invention has a concavo-convex pattern formed on the surface, the average roughness Rz of the concavo-convex pattern is 60 μm or more, and the second surface protective layer that is the outermost surface layer is the second surface protective layer. By including particles whose particle diameter is larger than the thickness of the protective layer, the surface physical properties (for example, scratch resistance and weather resistance, etc.) are maintained in a decorative sheet for floors having a large uneven shape (for example, with floating grain). However, it is excellent in slip resistance.

It is a figure which shows an example (layer structure conceptual diagram) of embodiment of the decorative sheet for floors of this invention.

  Hereinafter, the decorative sheet for flooring and the decorative material for flooring of the present invention will be described in detail.

The decorative sheet for flooring of the present invention,
On the base sheet, at least a transparent resin layer, a first surface protective layer, and a second surface protective layer in this order, the second surface protective layer is a decorative sheet for floors,
(1) An uneven pattern is formed on the surface of the floor decorative sheet,
(2) The average roughness Rz of the concavo-convex pattern is 60 μm or more,
(3) The second surface protective layer includes particles having a particle diameter larger than the thickness of the second surface protective layer.

  Hereinafter, each structure of the decorative sheet for flooring of this invention is demonstrated.

Base sheet The floor decorative sheet of the present invention includes a base sheet, and at least a transparent resin layer, a first surface protective layer, and a second surface protective layer are sequentially laminated on the surface (front surface). The

  As a base material sheet, what was formed, for example with the 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. Among these, polyolefins such as polypropylene are preferable.

  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.

  Examples of the filler include silica, clay, calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including a filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. About 0-100 weight part is preferable with respect to 100 weight part of resin components, and, as for content of a filler, about 10-50 weight part is more preferable.

  Although the thickness of a base material sheet can be suitably set with the use of a final product, a usage method, etc., generally 50-250 micrometers is preferable and 50-100 micrometers is more 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.

Back surface primer layer A back surface primer layer may be provided on the back surface of the above-described base material sheet, if necessary. For example, it is advantageous when a decorative material for floors is produced by bonding a base sheet and an adherend.

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

  Although the thickness of a back surface primer layer is not specifically limited, Usually, 0.1-10 micrometers, Preferably it is about 1-5 micrometers.

Pattern Pattern Layer The decorative sheet for floors of the present invention may be provided with a pattern pattern layer on the surface (front surface) of the base sheet, if desired.

  The design pattern layer imparts a desired design (design) to the floor decorative sheet, and the type of design is not limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The method for forming the pattern layer is not particularly limited. For example, printing using ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form in the base-material sheet | seat surface by a method.

  Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, 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 further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  As binder resin, polyester urethane resin, polyester urethane resin with hydrophilic treatment, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate A polymer, a rosin derivative, an alcohol adduct of a styrene-maleic anhydride copolymer, a cellulose resin, or the like can be used in combination.

  More specifically, for example, polyurethane-polyacrylic resin, polyacrylamide resin, poly (meth) acrylic acid resin, polyethylene oxide resin, poly N-vinylpyrrolidone resin, water-soluble polyester resin, water-soluble Polyamide resins, water-soluble amino resins, water-soluble phenol resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, etc. can be used. Further, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin modified or mixed resin, and other resins can also be used. The binder resin can be used alone or in combination 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 (also referred to as a colored concealment layer), for example, a gravure coating method, a gravure reverse coating method, a roll coating method, a knife coating method, an air knife coating method, a die coating Various coating methods such as a method, a lip coat method, a comma coat method, a kiss coat method, a flow coat method, and a dip coat method are also included.

  In addition to the above, for example, 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. are used or combined with other forming methods. It may be used.

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

Adhesive Layer The floor decorative sheet of the present invention may be provided with an adhesive layer on the surface (front surface) of the base sheet between the pattern layer and the transparent resin layer, if desired.

  The adhesive layer may be transparent or translucent as long as the pattern layer can be recognized. Moreover, the adhesive agent used by an adhesive bond layer is not specifically limited, According to the component etc. which comprise a pattern layer or a transparent resin layer, it can select suitably. Examples of the adhesive known in the field of floor decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives are 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.

  Moreover, well-known easy adhesion processes, such as a corona discharge process, a plasma process, a degreasing process, and a surface roughening process, can also be given to an adhesion surface as needed.

  The adhesive layer can be formed, for example, by applying the adhesive on the pattern layer, drying it once, and then laminating a transparent resin. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

  The thickness of the adhesive layer varies depending on the transparent protective layer, the type of adhesive used, and the like, but generally may be about 0.1 to 30 μm.

Transparent resin layer In the decorative sheet for floor of the present invention, a transparent resin layer is laminated between the surface (front surface) of the base sheet and the first surface protective layer.

  The resin constituting the transparent resin layer is not limited as long as it is transparent when the lower pattern pattern layer is present, or is translucent within a range where the lower pattern pattern layer can be visually recognized. Examples of such resins include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid ester copolymer. , Ionomer, polymethylpentene, polyacrylate, polymethacrylate, polycarbonate, cellulose triacetate and the like. The said resin can be used individually or in combination of 2 or more types. Moreover, the copolymer which has these resins as a main component can also be used.

  Among the above, polyolefin resins such as polypropylene are preferable. More preferably, it is a polyolefin resin having stereoregularity. When using a polyolefin resin, it is desirable to form a transparent resin layer by extruding a molten polyolefin resin.

  As the polyolefin resin, either a homopolymer or a copolymer can be used. For example, in the case of a polypropylene resin, homopolypropylene resin, random polypropylene resin, block polypropylene resin and the like can be mentioned. As the polyolefin resin, a commercially available product (for example, Prime Polymer Co., Ltd. (Prime TPO “J-5900”, Prime Polypro “F219DA”), etc.) can be used.

  For the transparent resin layer, if necessary, a filler, matting agent, foaming agent, flame retardant, lubricant, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, radical scavenger, soft component Various additives such as rubber (for example, rubber) may be included.

  The thickness of the transparent resin layer is not particularly limited, but if the thickness of the transparent resin layer is too thin, the wear resistance is lowered. On the other hand, if it is too thick, problems such as fluffing at the time of cutting occur, preferably less than 150 μm, more preferably 40-100 μm, and even more preferably 60-80 μm.

  If necessary, the transparent resin layer may be subjected to corona discharge treatment on the surface (front surface) in order to enhance the adhesion with the upper primer layer.

First primer layer In the floor decorative sheet of the present invention, a first primer layer may be provided between the transparent resin layer and the first surface protective layer, if desired. The first primer layer has a function of improving the adhesion (adhesion) between the transparent resin layer and the first surface protective layer. Moreover, it has an effect which makes it difficult to produce a fine crack and whitening in the extending | stretching part of a 1st surface protective layer. Moreover, formation of the first surface protective layer can be facilitated by providing the first primer layer. The first primer layer is not particularly limited as long as it is transparent, and includes any one of colorless and transparent, colored and transparent, and translucent.

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

  The first 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 resin layer and the first surface protective layer can be further improved by including a hexamethylene diisocyanate curing agent in the primer agent. Various weathering agents such as an ultraviolet absorber and a light stabilizer may be added to the first primer layer.

  The first primer layer can be formed by a direct coating method, for example, gravure coat, gravure reverse coat, gravure offset coat, spin coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen Wire bar coating, flow coating, comma coating, flow-through coating, brush coating, spray coating, and the like can be used.

  The thickness of the first primer layer is preferably about 0.1 to 10 μm. When it is 0.1 μm or more, the effect of preventing the surface protective layer from cracking, breaking, whitening, etc. can be sufficiently exerted. On the other hand, if the thickness of the first primer layer is 10 μm or less, it is preferable that when the first primer layer is applied, the coating film is stable in drying and curing, so that the moldability does not fluctuate. From the above points, the thickness of the first primer layer is more preferably 0.1 to 10 μm.

First surface protective layer In the decorative sheet for flooring of the present invention, a transparent resin layer and first and second surface protective layers are sequentially laminated on the surface (front surface) of the base material sheet.

  By forming the first surface protective layer (lower surface protective layer), the surface physical properties such as scratch resistance and weather resistance of the decorative sheet for floors can be improved.

  The first surface protective layer is located below the second surface protective layer, and while exhibiting scratch resistance, the entire surface protective layer does not become brittle and has excellent impact resistance, so that the layer thickness is 3 to 30 μm. It is preferable that it is 5-15 micrometers. In particular, when the thickness of the first surface protective layer is less than 3 μm, there is a tendency that sufficient scratch resistance cannot be obtained. On the other hand, when the thickness of the first surface protective layer exceeds 30 μm, the rigidity of the entire decorative sheet is increased, and it tends to be broken and the workability of the laminate and the like tends to decrease.

  The first surface protective layer may use a matting material for the purpose of further enhancing the matting effect (matting) of the surface. Matte materials include inorganic matte materials such as silica, calcium silicate, aluminum silicate, magnesium silicate, kaolin, mica, talc, titanium dioxide, calcium carbonate, barium carbonate, α-alumina, chromium oxide, iron oxide, diamond, etc. And organic matte materials such as polyurethane, polystyrene, polyamide, polyvinyl chloride, acrylic and other fine particle polymers. 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 matting material is not particularly limited and can be appropriately designed according to the thickness of the first surface protective layer, but is usually 1 to 30 μm, preferably about 1 to 15 μm. Here, the average particle diameter means a particle diameter (D50) corresponding to a cumulative frequency of 50%. The average particle diameter can be measured by a known method such as a laser diffraction method, a Coulter counter method, or a sedimentation method.

  When the matting material is contained in the first surface protective layer, the content can be appropriately designed, but it is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin component forming the surface protective layer. 1 to 25 parts by weight is more preferable.

  In order to improve the weather resistance, it is preferable to add an ultraviolet absorber and a light stabilizer to the first surface protective layer.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylate, and triazine. In addition, when the resin layer is cured by irradiating with ultraviolet rays, as photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-aminoxime ester, tetramethylthiuram monosulfide, thioxanthones, aromatic N-butylamine, triethylamine, tri-n-butylphosphine, etc. can be used as photopolymerization accelerators (sensitizers) such as group diazonium salts, aromatic sulfonium salts, and metathelons.

  Examples of the light stabilizer include hindered amine light stabilizers. More specifically, bis- (2,2,6,6-tetramethyl-4piperidinyl) sebacate, bis- (N-methyl 2,2,6,6-tetramethyl-4-piperidinyl) sebacate, etc. Examples thereof include compounds disclosed in Japanese Patent Publication No. 4-82625.

  It is preferable that the resin component constituting the first surface protective layer contains at least one of an ionizing radiation curable resin and a two-component curable urethane resin. Substantially those formed from these resins are preferred. When forming a transparent surface protective layer with ionizing radiation curable resin or two-component curable urethane resin, it is easy to improve the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet. .

  The ionizing radiation curable resin is not particularly limited, and a prepolymer (including an oligomer) and / or a monomer containing a functional group capable of undergoing a polymerization and crosslinking reaction by irradiation with ionizing radiation such as ultraviolet rays and electron beams as a main component. A transparent resin 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. As these weight average molecular weights, about 250-100000 are preferable normally. As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

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

  As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.

  As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

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

  The first surface protective layer may contain a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye or a pigment, a solvent, or the like, if necessary.

  For example, the first surface protective layer is formed by applying at least one of an ionizing radiation curable resin and a two-component curable urethane resin on a transparent polypropylene resin layer by a known coating method such as gravure coating or roll coating. After the process, it can be formed by curing the resin. In the case of an ionizing radiation curable resin, the resin is cured by electron beam irradiation.

Second primer layer In the decorative sheet for floor of the present invention, a second primer layer may be provided between the first surface protective layer and the second surface protective layer, if desired. The second primer layer has a function of improving the adhesion (adhesion) between the first surface protective layer and the second surface protective layer. Moreover, it has the effect of making it difficult for fine cracks and whitening to occur in the stretched portion of the second surface protective layer. In addition, the second surface protective layer can be easily formed by providing the second primer layer. The second primer layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and translucent.

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

  The second 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 first surface protective layer and the second surface protective layer can be further improved by adding a hexamethylene diisocyanate-based curing agent to the primer agent. Various weathering agents such as an ultraviolet absorber and a light stabilizer may be added to the second primer layer.

  The second primer layer can be formed by a direct coating method, for example, gravure coat, gravure reverse coat, gravure offset coat, spin coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen Wire bar coating, flow coating, comma coating, flow-through coating, brush coating, spray coating, and the like can be used.

  The thickness of the second primer layer is preferably about 0.1 to 10 μm. When it is 0.1 μm or more, the effect of preventing the surface protective layer from cracking, breaking, whitening, etc. can be sufficiently exerted. On the other hand, if the thickness of the second primer layer is 10 μm or less, it is preferable that when the second primer layer is applied, the coating film is stable in drying and curing, so that the moldability does not vary. From the above points, the thickness of the second primer layer is more preferably 0.1 to 10 μm.

Second surface protective layer In the floor decorative sheet of the present invention, a transparent resin layer and first and second surface protective layers are sequentially laminated on the surface (front surface) of the base sheet. When forming the second primer layer, a second surface protective layer is laminated on the surface of the second primer layer.

  By forming the second surface protective layer (upper surface protective layer), the surface physical properties such as scratch resistance and weather resistance of the decorative sheet for flooring can be improved, and the slip resistance can be improved.

  The second surface protective layer is the outermost layer and includes particles having a particle diameter larger than the thickness of the second surface protective layer. When the second surface protective layer contains particles having a particle diameter larger than the thickness of the second surface protective layer, the slip resistance of the second surface protective layer can be improved.

  Examples of the particles contained in the second 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. And organic material powders such as nylon or beads. The particles are preferably at least one selected from the group consisting of silica and allyl beads. In addition, the said particle | grain can be used 1 type, or 2 or more types. By including such particles, the tactile sensation when the surface is touched with the skin can be made closer to a real tree, and a floating feeling (a wood grain with a large uneven shape) can be provided.

  The average particle diameter of the particles is at least equal to or greater than the thickness of the second surface protective layer, and is preferably less than “thickness of the second surface protective layer + 40 μm” in order to maintain the scratch resistance described later, The thickness of the protective layer is more preferably 30 μm or less. When the average particle diameter of the particles is equal to the thickness of the second surface protective layer, the second surface protective layer has no convex portion formed by the particles (that is, the thickness of the convex portion formed by the particles is 0 μm). In some cases, and there may be convex portions formed by the particles. About the average particle diameter of particle | grains, 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 content of the particles in the second surface protective layer is preferably 3 to 50 parts by weight, and 5 to 30 parts by weight with respect to 100 parts by weight of the resin component forming the second surface protective layer. More preferably.

  In the floor decorative sheet of the present invention, the above-described particles are preferably present in the second surface protective layer as long as the effects of the present invention are not hindered. The smaller the proportion of particles protruding from the surface of the second surface protective layer, the better the surface performance such as scratch resistance.

  The second surface protective layer is formed of organic particles such as inorganic particles such as α-alumina, chromium oxide, iron oxide, and diamond, and synthetic resin beads such as cross-linked acrylic for the purpose of further improving the scratch resistance in addition to the particles described above. Powder particles such as resin particles may be added. Various shapes of powder particles are used, and particularly when a spherical shape or a shape similar to a spherical shape is used, the scratch resistance is good. The average particle diameter of the powder particles is preferably equal to or less than the coating thickness (thickness of the second surface protective layer), and the addition amount is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin component. The above-mentioned powder particles can be used alone or in combination of two or more.

  In addition to the above powder, the second 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 second surface protective layer.

  When the matting material and the particles are simultaneously added to the second surface protective layer, the average particle size (df) of the particles, the average particle size (dm) of the matting material, and the coating film thickness (second The relationship of the surface protective layer thickness (D) is 0 <dm <D ≦ df.

  Here, the preferable specific aspect regarding the average particle diameter of particle | grains, the average particle diameter of a matte material, and the thickness of a 2nd surface protective layer (coating film) is shown below. For example, when the thickness of the second surface protective layer is 5 μm, the average particle size of the particles is preferably 6 to 10 μm, and when the matte material is also contained, the average particle size of the matte material is 1 to 4 μm. preferable. When the thickness of the second surface protective layer is 15 μm, the average particle size of the particles 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 second surface protective layer is 50 μm, the average particle size of the particles 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 ^{50m 2 / g, 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, and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the resin component.

  The layer thickness of the second surface protective layer is not particularly limited as long as it is smaller than the particle diameter of the contained particles. However, the second surface protective layer does not become brittle while exhibiting scratch resistance, and impact resistance is improved. Is preferable, the layer thickness is preferably 5 to 35 μm, more preferably 10 to 20 μm. In particular, when the thickness of the second surface protective layer is less than 5 μm, there is a tendency that sufficient scratch resistance cannot be obtained.

  As the resin component constituting the second surface protective layer, it is preferable to contain at least one of an ionizing radiation curable resin and a two-component curable urethane resin. Substantially those formed from these resins are preferred. When forming a transparent surface protective layer with ionizing radiation curable resin or two-component curable urethane resin, it is easy to improve the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet. .

  The ionizing radiation curable resin is not particularly limited, and a prepolymer (including an oligomer) and / or a monomer containing a functional group capable of undergoing a polymerization and crosslinking reaction by irradiation with ionizing radiation such as ultraviolet rays and electron beams as a main component. A transparent resin 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. As these weight average molecular weights, about 250-100000 are preferable normally. As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

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

  As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.

  As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

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

  Moreover, in order to improve weather resistance, it is preferable to add an ultraviolet absorber and a light stabilizer to the second surface protective layer.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylate, and triazine. In addition, when the resin layer is cured by irradiating with ultraviolet rays, as photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-aminoxime ester, tetramethylthiuram monosulfide, thioxanthones, aromatic N-butylamine, triethylamine, tri-n-butylphosphine, etc. can be used as photopolymerization accelerators (sensitizers) such as group diazonium salts, aromatic sulfonium salts, and metathelons.

  Examples of the light stabilizer include hindered amine light stabilizers. More specifically, bis- (2,2,6,6-tetramethyl-4piperidinyl) sebacate, bis- (N-methyl 2,2,6,6-tetramethyl-4-piperidinyl) sebacate, etc. Examples thereof include compounds disclosed in Japanese Patent Publication No. 4-82625.

  An antibacterial agent may be added to the second 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 of the second surface protective layer.

  The second surface protective layer may include a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye and a pigment, a solvent, and the like, as necessary.

  For example, the second surface protective layer is formed by coating at least one of an ionizing radiation curable resin and a two-component curable urethane resin on a transparent polypropylene resin layer by a known coating method such as gravure coating or roll coating. After the process, it can be formed by curing the resin. In the case of an ionizing radiation curable resin, the resin is cured by electron beam irradiation.

  In particular, it is preferable that the second surface protective layer is formed at least on the convex portions of the concavo-convex portions formed on the surface of the decorative sheet for floors, which will be described later, because the anti-slip property can be improved.

Uneven pattern and average roughness Rz on the surface of the decorative sheet for floors
Since the decorative sheet for floors of the present invention can improve anti-slip properties, an uneven pattern is formed on the surface, and the average roughness Rz of the uneven pattern is 60 μm or more. Moreover, by providing such a concavo-convex pattern, the tactile sensation when touching the surface with the skin can be brought closer to a real tree, and the floating feeling (graininess with large concavo-convex shape) can be improved. .

  The uneven pattern can be formed, for example, by embossing from the surface protective layer side of the floor decorative sheet.

  Embossing is performed to give a desired texture such as a wood grain pattern to the decorative sheet for flooring. For example, after the surface protective layer is heated and softened, it is pressed and shaped with an embossed plate having a concavo-convex pattern of a desired shape, and then textured by cooling and fixing. Embossing can be performed with a known single wafer or rotary embossing machine. Examples of the embossed concavo-convex pattern include a wood grain conduit groove, a float pattern (a concavo-convex pattern of a raised annual ring), a hairline, a grain, and a satin texture.

  The concavo-convex pattern and the average roughness Rz on the surface of the decorative sheet for flooring, as represented by JIS B 0601 (1994), indicate the average roughness of a total of 10 points of 5 convex portions and 5 concave portions, The value is 60 μm or more. Since the anti-slip property can be improved, the average roughness Rz is preferably about 60 μm or more, and preferably about 90 μm or more. Further, the upper limit of the average roughness Rz is preferably about 140 μm, preferably about 130 μm, because when the decorative sheet is laminated on the adherend, if the uneven shape is too large, the adhesiveness with the substrate is lowered. More preferred.

Method for producing floor decorative sheet On the base sheet described above, at least a transparent resin layer, a first surface protective layer and a second surface protective layer are provided in this order, and the second surface protective layer is the outermost surface layer. The decorative sheet for floors of the present invention, in which an uneven pattern is formed on the surface, and the average roughness Rz of the uneven pattern is 60 μm or more,
(1) Step 1 of laminating a transparent resin layer on a substrate sheet,
(2) Step 2 of laminating a first surface protective layer on the transparent resin layer,
(3) Step 3 of embossing from the front surface of the first surface protective layer; and (4) Particles having a particle diameter larger than the thickness of the second surface protective layer on the first surface protective layer. Is manufactured by a manufacturing method including the process 4 of laminating | stacking the said 2nd surface protective layer containing this in order.

  Hereinafter, the production method of the present invention will be described in detail.

(1) Step 1
In step 1, a transparent resin layer is laminated on the base sheet.

  The method for laminating the transparent resin layer on the base sheet is not limited. For example, there are a method of laminating a preformed sheet or film on an adjacent layer, a method of melt-extruding a thermoplastic resin composition capable of forming a transparent resin layer, and laminating together with the adjacent layer. Examples of the laminating method include a laminating method by a dry laminating method. In addition, the said transparent resin layer may be formed so that it may adhere | attach with a transparent adhesive layer with respect to the sheet | seat on which the base material sheet, the pattern pattern layer, and the transparent adhesive layer were laminated | stacked in order, for example.

  When the base sheet is provided with a pattern layer on the surface (front surface) of the base sheet, if necessary, the surface (front surface) is used to increase the adhesion of the ink that forms the pattern layer. ) May be subjected to corona discharge treatment. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method. If the pattern layer is difficult to adhere, a primer layer may be interposed between the layers as necessary.

  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. For example, it is advantageous when a decorative material for floors is produced by bonding a base sheet and an adherend.

  The floor decorative sheet of the present invention may be provided with an adhesive layer on the surface (front surface) of the base sheet between the pattern layer and the transparent resin layer, if desired.

  Moreover, it is preferable to form a 1st primer layer between the said transparent resin layer and a 1st surface protective layer after the said process 1 from the reason that it has a function which improves adhesiveness (adhesion). Furthermore, the transparent resin layer may be subjected to a corona discharge treatment on the surface (front surface) as necessary in order to enhance the adhesion with the upper first primer layer.

(2) Step 2
In step 2, a first surface protective layer is laminated on the transparent resin layer.

  As a method for forming the first surface protective layer, a known method such as gravure printing can be employed. By forming the first surface protective layer (lower surface protective layer), the surface physical properties such as scratch resistance and weather resistance of the decorative sheet for floors can be improved.

(3) Process 3
In step 3, embossing is performed from the front surface of the first surface protective layer.

  Embossing is performed to give a desired texture such as a wood grain pattern to the decorative sheet for flooring. For example, after heat-softening the first surface protective layer, it is pressed and shaped with an embossed plate having a concavo-convex pattern of a desired shape, and texture is imparted by cooling and fixing. Embossing can be performed with a known single wafer or rotary embossing machine. Examples of the embossed concavo-convex pattern include a wood grain conduit groove, a float pattern (a concavo-convex pattern of a raised annual ring), a hairline, a grain, and a satin texture.

  Moreover, it is preferable to form a 2nd primer layer between the said 1st surface protective layer and a 2nd surface protective layer after the said process 3 from the reason that it has a function which improves adhesiveness (adhesion).

(4) Step 4
In step 4, the second surface protective layer containing particles having a particle diameter larger than the thickness of the second surface protective layer is laminated on the first surface protective layer.

  By forming the second surface protective layer (upper surface protective layer), the surface physical properties such as scratch resistance and weather resistance of the decorative sheet for flooring can be improved, and the slip resistance can be improved.

Backer layer The decorative sheet may further have a synthetic resin layer (also referred to as a backer layer) having a thickness of 100 μm or more in the lowermost layer (a layer that adheres to the back surface of the base sheet). In addition, a backer layer means the buffer layer aiming at shock absorption etc. in the decorative material for floors. By forming the backer layer, further impact resistance can be secured.

  Examples of the material constituting the backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, and high heat-resistant polyalkylene terephthalate [for example, a part of ethylene glycol is 1,4- Polyethylene terephthalate substituted with cyclohexanedimethanol or diethylene glycol, so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, poly Examples include arylate, polyimide, polystyrene, polyamide, and ABS. These resins can be used alone or in combination of two or more.

  The upper limit of the thickness of the backer layer is not limited, but about 600 μm is appropriate.

Flooring decorative material A flooring decorative material can be obtained by bonding and adhering an adherend to the back surface of the decorative sheet for flooring of the present invention.

  The material of various adherends is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, woody materials, and plastic materials. Specifically, in inorganic non-metallic systems, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, Non-ceramic ceramic materials such as gypsum and gypsum slag, ceramic materials such as earthenware, ceramics, porcelain, setware, glass, and glazing. In a metal system, metal materials (metal steel plate), such as iron, aluminum, and copper, are mentioned, for example. In the wood system, for example, a single board, plywood, particle board, fiber board, laminated timber and the like made of cedar, straw, firewood, lauan, teak and the like can be mentioned. In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  The shape of such an adherend is not particularly limited, and may be a flat plate in consideration of installation on a flooring or the like.

  In order to bond the adherend and the decorative sheet, for example, an adhesive can be used. Examples of the adhesive 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 as active ingredients. Any known adhesive can be used.

  After joining the adherend and the decorative sheet, for example, according to the characteristics of the final product, cutting, use of a tenoner, sane processing, provision of V-shaped grooves, chamfering on four sides, and the like may be performed.

  Drawing 1 is a figure showing an example (layer composition conceptual diagram) of an embodiment of a decorative sheet for floors of the present invention.

  In FIG. 1, the back surface primer layer 1 is formed in the back surface of the base material sheet 2, and the pattern pattern layer 3 is formed in the front surface. Further, an adhesive layer 4, a transparent resin layer 5, a first primer layer 6, a first surface protective layer 7, a second primer layer 8, and a second surface protective layer 9 are sequentially laminated on the pattern layer 3. Has been. The second surface protective layer includes particles 10 having a particle diameter larger than the thickness of the second surface protective layer.

  In FIG. 1, the second primer layer 8 (and the second surface protective layer 9) is not applied to the recess formed by embossing, and the first surface protective layer (lower layer) 7 is exposed in the recess. Show.

  Moreover, it can be set as the decorative material for floors by sticking an adherend on the back surface of the decorative sheet for flooring, and joining.

  Next, the present invention will be specifically described with reference to experimental examples. However, the present invention is not limited to the examples.

Examples and Comparative Examples A primer layer was provided on the back surface of a base sheet made of a colored polypropylene film having a thickness of 60 μm. Next, a pattern layer was formed on the front surface of the base sheet by printing, and an adhesive layer was further formed on the pattern print pattern layer. On the adhesive layer, an 80 μm thick transparent resin layer (with polypropylene resin) was laminated by extrusion lamination. After the corona discharge treatment was applied to the surface of this transparent resin layer, a first primer layer was formed by applying a two-component curable urethane resin. The surface is coated with 15 μm of ionizing radiation curable resin by a roll coating method, and then cured by irradiating with an electron beam under an acceleration voltage of 175 keV and 5 Mrad using an electron beam irradiation apparatus in an environment with an oxygen concentration of 200 ppm or less. Thus, the first surface protective layer was formed.

  The first surface protective layer (ionizing radiation curable resin side) is heated with an infrared non-contact heater to soften the base sheet and the transparent resin layer, and then immediately embossed with hot pressure to create a grainy texture. The pattern was shaped (Rz (10-point average roughness) = 92 to 107 μm).

  A corona discharge treatment was applied to the surface of the shaped concavo-convex pattern, and then a two-component curable urethane resin was applied to form a second primer layer. An ionizing radiation curable resin containing silica particles having an average particle diameter of 20 μm is applied to the surface by a gravure coating method, and then an acceleration voltage of 175 keV and 5 Mrad is applied using an electron beam irradiation apparatus in an environment having an oxygen concentration of 200 ppm or less. A second surface protective layer was formed by irradiating and curing an electron beam under conditions, and a floor decorative sheet (Example 2) was created.

  As an ionizing radiation curable resin contained in the first surface protective layer and the second surface protective layer, a hexafunctional aliphatic urethane acrylate oligomer (glass transition point: 200 ° C. or higher, weight average molecular weight 1500, UA306H manufactured by Kyoeisha Chemical Co., Ltd.) It was used. The hexafunctional urethane acrylate oligomer means a urethane acrylate oligomer having six radically polymerizable acryloyl groups in one molecule.

  In the following, an uneven shape (Rz (ten-point average roughness)) with a wood grain pattern was used as an example and a comparative example.

<Evaluation method>
The weather resistance evaluation test was conducted using a decorative sheet for floors. The test of anti-slip property evaluation, scratch resistance evaluation, tactile sensation and floating feeling was performed by laminating the produced floor decorative sheet on a medium density wood fiber board (MDF) (adhesive material) having a thickness of 2.7 mm. Is.

(1) Evaluation of slip resistance The slip resistance value (CSR) by socks was measured using a Tokyo Institute of Technology slip tester (OY-PSM). The evaluation criteria are as follows.
○ +: C.I. S. R value of 0.37 or more ○: C.I. S. R value of 0.35 to less than 0.37 Δ: C.I. S. R value less than 0.33 to 0.35 x: C.I. S. R value less than 0.33

(2) Scratch resistance evaluation The scratch resistance of the decorative sheets for floors produced in Examples and Comparative Examples was confirmed using a Hoffman scratch tester (BYK-Gardnar). Specifically, a scratch blade (a cylindrical edge portion having a diameter of 7 mm) is set so as to contact the surface protective layer of the decorative sheet for flooring at an angle of 45 degrees, and the scratch blade is moved so as to be pulled. The surface was rubbed. At that time, the load applied to the scratch blade by 100 g in the range of 300 to 700 g load was changed to confirm whether or not the surface protective layer was damaged. The evaluation criteria are as follows.
○: Scratches are not seen at 500g load △: Scratches are seen at 500g load ×: Scratches are clearly noticeable at 500g load

(3) Weather resistance evaluation A weather resistance test was performed using a super UV tester. Specifically, the illuminance is 60 mW / cm ² (365 nm) under the condition of a temperature of 63 ° C. and a humidity of 50% RH using a super accelerated weathering tester (“I Super UV Tester”, manufactured by Iwasaki Electric Co., Ltd.). The appearance of the decorative sheet was visually changed after 200 hours of a cycle in which light was irradiated for 20 hours and then condensed for 4 hours. The evaluation criteria are as follows.
○: Deterioration such as whitening is not observed after 200 hours of irradiation ×: Deterioration such as whitening is observed after 200 hours of irradiation

(4) Tactile sensation Twenty-five adults and men in their 40s evaluated the wooden texture of the surface of the decorative sheets for floors prepared in Examples and Comparative Examples. The evaluation criteria are as follows.
10 or more adult men and women who feel that the tactile sensation is close to that of a real tree is ○, 8-9 is ○-, 6-7 is △, and 5 or less Was marked with x.

(5) Floating sensation Fifteen adult males and females in their 20s to 40s evaluated the floating sensation on the surface of the decorative sheets for floors prepared in Examples and Comparative Examples. The evaluation criteria are as follows.
The case where 10 or more adult men and women felt a feeling of floating was rated as ○, the case of 8-9 as ○, and the case of 7 or less as ×.

  The evaluation results are shown in the following table.

  In Comparative Examples 1 and 2, the average roughness Rz of the uneven pattern applied to the surface of the floor decorative sheet was less than 60 μm, and the floating feeling as a floor decorative sheet could not be sufficiently felt.

  In Comparative Examples 3 and 4, the floor decorative sheet was not provided with the first surface protective layer (base EB, lower layer), scratches were observed in the scratch resistance evaluation, and deterioration such as whitening was observed in the weather resistance evaluation. .

  In Comparative Example 5, the floor decorative sheet was not provided with the second surface protective layer (top EB, upper layer) containing particles, and the slip resistance was not sufficient. This shows that even if the first surface protective layer contains particles, the particles are crushed by the subsequent embossing, and the slip-proof property cannot be exhibited in the floor decorative sheet. And even if the average roughness Rz of the concavo-convex pattern applied to the surface of the decorative sheet for flooring is 60 μm or more, since the embossing is performed after forming the first surface protective layer, the slip resistance cannot be sufficiently exhibited. It shows that.

  On the other hand, Examples 1-4 have the floor which has a transparent resin layer, a 1st surface protective layer, and a 2nd surface protective layer in order on a base material sheet, and the said 2nd surface protective layer is an outermost surface layer. In the decorative sheet, (1) an uneven pattern is formed on a surface of the floor decorative sheet, (2) an average roughness Rz of the uneven pattern is 60 μm or more, and (3) the second surface When the protective layer contains particles having a particle diameter larger than the thickness of the second surface protective layer, the uneven shape is large, a floating grain can be provided, and surface properties such as scratch resistance and weather resistance are provided. While maintaining anti-slip properties.

1. 1. Back primer layer 2. base material sheet Pattern layer 4. 4. Adhesive layer 5. Transparent resin layer First primer layer 7. First surface protective layer 8. Second primer layer 9. Second surface protective layer 10. particle

Claims (8)

On the base sheet, at least a transparent resin layer, a first surface protective layer, and a second surface protective layer in this order, the second surface protective layer is a decorative sheet for floors,
(1) An uneven pattern is formed on the surface of the floor decorative sheet,
(2) The concavo-convex pattern is a floating wood grain whose deepest part reaches the transparent resin layer,
(3) The decorative sheet for floors, wherein the second surface protective layer contains particles having a particle diameter larger than the thickness of the second surface protective layer.   The floor decorative sheet according to claim 1, wherein the first surface protective layer and the second surface protective layer contain at least one of an ionizing radiation curable resin and a two-component curable urethane resin.   The decorative sheet for floor according to claim 1 or 2, wherein a second primer layer is formed between the first surface protective layer and the second surface protective layer.   The floor decorative sheet according to any one of claims 1 to 3, wherein a first primer layer is formed between the transparent resin layer and the first surface protective layer.   The flooring decorative material formed by bonding the base sheet side of the flooring decorative sheet according to any one of claims 1 to 4 to an adherend. On the base sheet, at least a transparent resin layer, a first surface protective layer, and a second surface protective layer are provided in this order, the second surface protective layer is the outermost surface layer, and an uneven pattern is formed on the surface. The concave-convex pattern is a method for producing a decorative sheet for floors, which is a floating grain that has the deepest part reaching the transparent resin layer,
(1) Step 1 of laminating a transparent resin layer on a substrate sheet,
(2) Step 2 of laminating a first surface protective layer on the transparent resin layer,
(3) Step 3 of embossing from the front surface of the first surface protective layer; and (4) Particles having a particle diameter larger than the thickness of the second surface protective layer on the first surface protective layer. The manufacturing method of the decorative sheet for floors which includes the process 4 of laminating | stacking the said 2nd surface protective layer containing this in order.   After the step 1, a step of forming a first primer layer between the transparent resin layer and the first surface protective layer, and after the step 3, the first surface protective layer and the second surface protection The method for producing a floor decorative sheet according to claim 6, further comprising a step of forming a second primer layer between the layers. After obtaining the Lucas cosmetic sheet by the method according to claim 6 or 7, the substrate sheet side of that, a method of manufacturing a combined decorative material bonded to the adherend.

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