JP2016168842A - Decorative sheet and decorative plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet free from wiping resistance properly, capable of wiping easily not only dirt generated during housing construction but also oil contamination.SOLUTION: There is provided a decorative sheet 1 having at least a surface protective layer 8 on a substrate sheet 3. In the decorative sheet 1, a wet tension of the surface protective layer is below 30-35 mN/m, and a Martens hardness of the surface protective layer is 70 N/mm2 or more, and the surface protective layer contains a hydrophobically-treated inorganic filler, and a particle size of the inorganic filler is 1-10 μm in the mode diameter.SELECTED DRAWING: Figure 1

Description

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

  Conventionally, decorative sheets have been laminated on the surfaces of various articles in order to impart design properties. For example, a decorative sheet is laminated on a surface of a wall covering material used for a wall surface of a building, a floor decorative material used for a floor surface, and the like.

  The present floor decorative sheet can easily remove most of the dirt during cleaning performed before the delivery of the property after the construction of the house, but there is a problem that it is difficult to remove the dirt attached during the construction of the house. In particular, gypsum powder, which accounts for the majority of difficult-to-remove stains, is white, so that the stains are conspicuous and the particles are small (fine). Therefore, the gypsum powder is a contaminant that is difficult to clean.

  As a conventional technique, a decorative sheet is disclosed in which the surface unevenness shape of the decorative sheet is defined to make it difficult for the contaminants to enter the concave portion, and as a result, prevent easy deterioration (property of cleaning). (Patent Document 1).

JP, 2014-0669507, A

  However, although the said decorative sheet can remove the said contaminant, it does not consider about the wiping property (wiping resistance) at the time of removing stain | pollution | contamination. If the resistance is large when wiping off, it will feel like it gets caught, making it difficult to wipe off the dirt. Further, the wiping property of oil stains (sebum stains and the like) is not taken into consideration, and there is a problem in terms of improving various easy sweeping properties.

  An object of this invention is to provide the decorative sheet which does not have a moderate wiping resistance, and is easy to wipe off not only the stain | pollution | contamination which generate | occur | produces at the time of housing construction but also oil stain | pollution | contamination.

  The inventors of the present invention have conducted extensive research to develop a decorative sheet that has no moderate resistance to wiping off and is easy to wipe off not only dirt such as gypsum powder generated during home construction, but also the wetness of the surface protective layer. It has been found that the above problems can be solved by defining the tension and the resin hardness. The present invention has been completed based on such findings.

That is, the present invention relates to the following decorative sheet and decorative plate.
1. A decorative sheet having at least a surface protective layer on a substrate sheet,
A decorative sheet, wherein the surface protective layer has a wetting tension of 30 mN / m or more and less than 35 mN / m, and the surface protective layer has a Martens hardness of 70 N / mm ² or more.
2. Item 2. The decorative sheet according to Item 1, wherein the surface protective layer contains an inorganic filler that has been hydrophobized.
3. Item 3. The decorative sheet according to Item 2, wherein the hydrophobized inorganic filler has a mode diameter of 1 to 10 µm.
4). The makeup according to Item 2 or 3, wherein the content of the hydrophobic treated inorganic filler is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface protective layer. Sheet.
5. Item 5. The decorative sheet according to any one of Items 2 to 4, wherein the hydrophobized inorganic filler is silica.
6). Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the resin constituting the surface protective layer is an ionizing radiation curable resin.
7). Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the surface protective layer has a thickness of 10 µm or more.
8). A decorative board in which the decorative sheet according to any one of items 1 to 7 is laminated on an adherend.

  The decorative sheet of the present invention has no moderate resistance to wiping, and it is easy not only to wipe off dirt generated during construction of a house, but also to easily wipe off oil dirt. In other words, the decorative sheet of the present invention is excellent in easy cleaning against various types of dirt. Therefore, the decorative sheet of the present invention can be suitably used particularly as a decorative sheet for floors.

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

<< 1. The decorative sheet of the present invention >>
The decorative sheet of the present invention is a decorative sheet having at least a surface protective layer on a base sheet, wherein the surface protective layer has a wetting tension of 30 mN / m or more and less than 35 mN / m and a Martens hardness of 70 N. / Mm ² or more. Even if the decorative sheet having the above characteristics does not have a moderate wiping resistance and dirt (especially, difficult gypsum powder that accounts for the majority of the pollutants) is present on the decorative sheet surface, In addition to easy removal of dirt, oily dirt such as sebum dirt can be easily wiped off. In other words, the decorative sheet of the present invention is excellent in easy cleaning against various types of dirt. Therefore, the decorative sheet of the present invention can be suitably used particularly for floor use.

  Hereinafter, the decorative sheet of the present invention will be described in detail. In the decorative sheet of the present invention, the surface is a so-called “front surface”, and a surface that comes into contact with the adherend when the decorative sheet of the present invention is used by being laminated on the adherend. Is a surface on the opposite side and is a surface visually recognized after lamination. In the present specification, the direction of the surface of the decorative sheet of the present invention may be referred to as “front” or “up”, and the opposite side may be referred to as “back” or “down”.

The decorative sheet of the present invention is a decorative sheet having at least a surface protective layer on a base sheet, wherein the surface protective layer has a wetting tension of 30 mN / m or more and less than 35 mN / m, and the surface protective layer As long as the requirement that the Martens hardness is 70 N / mm ² or more is satisfied, the specific configuration (layer configuration) is not limited. As an example of the decorative sheet of the present invention, a pattern layer 4, an adhesive layer 5, a transparent resin layer 6, a primer layer 7, and a surface protective layer 8 are laminated in this order on a base sheet 3 as shown in FIG. And the decorative sheet 1 which provided the back surface primer layer 2 in the back surface of the base material sheet 3, and was embossed in the outermost surface side is mentioned. Hereinafter, each layer will be specifically described with the decorative sheet 1 having such a layer configuration as a representative example. However, in the following description of each layer, reference numerals are omitted. Moreover, the layer thickness in this specification is the value measured in the place where uneven | corrugated shapes, such as embossing, do not exist in a decorative sheet.

Base sheet The decorative sheet of the present invention has a base sheet.

  The base sheet is a layer in which a pattern layer is sequentially laminated on the surface (front surface). As the base sheet, for example, a sheet (film) formed of a thermoplastic resin is suitable. Specifically, polyethylene, ethylene-α olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer. Olefin resins such as polymer saponified products, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate Examples thereof include phthalates, ionomers, acrylic ester polymers, and methacrylic ester polymers. The said base material sheet is formed by using these resin individually or in combination of 2 or more types. In addition, "(meth) acrylic acid" means acrylic acid and / or methacrylic acid, and the same applies to other portions described as (meth).

  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 or the like. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method. If necessary, the back surface of the base sheet may be subjected to corona discharge treatment, a pattern layer may be formed, a back surface primer layer, a backer layer, etc., which will be described later, may be formed.

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

  A design pattern layer is a layer which gives a desired design (design) to a decorative sheet, and the kind of design etc. are not limited. For example, a wood grain pattern, a leather pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a geometric figure, a character, a symbol, an abstract pattern, and the like can be given.

  The method for forming the pattern layer is not particularly limited. For example, an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin is used. What is necessary is just to form on the base-material sheet | seat surface by the printing method. As the ink, an aqueous composition can be used from the viewpoint of reducing the VOC of the 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. The said binder resin can be used individually or in combination of 2 or more types.

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

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

  The thickness of the pattern layer is not particularly limited and can be appropriately set according to product characteristics, but the layer thickness is about 0.1 to 10 μm.

In order to improve the adhesiveness between the adhesive layer transparent resin layer and the design pattern layer, an adhesive layer may be formed on the design pattern layer. The adhesive layer is preferably a transparent adhesive layer, and the transparent adhesive layer includes any of colorless and transparent, colored and transparent, and translucent.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet. Examples of known adhesives in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives can be used individually by 1 type or in combination of 2 or more types. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  Although the thickness of an adhesive bond layer is not specifically limited, Thickness is about 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

Transparent resin layer The decorative sheet of the present invention may have a transparent resin layer.

  The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. Examples of the resin constituting the transparent resin layer include polyethylene, ethylene-α olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate. Olefin resins such as copolymer, saponified ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polyethylene terephthalate, polybutylene terephthalate, polyamide , Ionomers, acrylic ester polymers, methacrylic ester polymers, polycarbonate, cellulose triacetate, and the like. These resins can be used alone or in combination of two or more.

  The transparent resin layer of the present invention preferably contains an olefin resin typified by a polypropylene resin, and the resin constituting the transparent resin layer is more preferably the olefin resin.

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

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

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

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

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

Surface protective layer The decorative sheet of the present invention has a surface protective layer. The surface protective layer is provided as the outermost layer of the decorative sheet.

  The resin constituting the surface protective layer is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin). In particular, from the viewpoint of scratch resistance due to high surface hardness, convex shape retention, productivity, etc., the surface protective layer preferably contains an ionizing radiation curable resin, and the resin constituting the surface protective layer is an ionizing radiation curable resin. More preferably.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, and the like can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

  Examples of the method for forming the surface protective layer with a thermosetting resin include a method in which a solution of a thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, followed by drying and curing.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more prepolymers, oligomers and monomers having a polymerizable unsaturated bond or epoxy group that can be crosslinked by irradiation with ionizing radiation in the molecule can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.

  Examples of the ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and / or electron beams are desirable.

  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, or a metal halide lamp can be used. The wavelength of ultraviolet light is about 190 to 380 nm.

  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 energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 2 to 15 Mrad.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation curable resins.

  The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the properties of the final product. The thickness of the surface protective layer is preferably 10 μm or more, and more preferably 11 to 30 μm.

The surface protective layer in the decorative sheet of the present invention has a wetting tension of 30 mN / m or more and less than 35 mN / m, and a Martens hardness of 70 N / mm ² or more. By setting the wetting tension and Martens hardness of the surface protective layer within the above ranges, there is no moderate wiping resistance, and it is easy to wipe off dirt at the time of housing construction, and further to wipe off oil dirt.

  The wetting tension of the surface protective layer is 30 mN / m or more and less than 35 mN / m, preferably 30 mN / m or more and 34 mN / m or less.

  Examples of methods for setting the wetting tension of the surface protective layer to 30 mN / m or more and less than 35 mN / m include, for example, 1) a method of adding a hydrophobic treated inorganic filler to the surface protective layer, and 2) adding an appropriate amount of additives such as silicone. It is preferable to adjust the wetting tension by a method of adding an inorganic filler hydrophobized to the surface protective layer.

  The wetting tension in the present specification is a value measured according to JIS K6768 (1999) (plastic-film and sheet-wetting tension test method).

  The inorganic filler is not particularly limited as long as it is hydrophobized. For example, silica, aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, gold sand, glass fiber, etc. Is mentioned.

  The method of hydrophobizing treatment is not particularly limited, and can be performed by a known method. For example, a method of hydrophobizing an inorganic filler with a silicone oil-based treating agent; an inorganic filler is treated with the above-described silicone oil-based treating agent after treating the inorganic filler with an alkylsilazane-based treating agent, a trimethylsilylating agent, and / or an alkoxysilane. Hydrophobic treatment method: Hydrophobic treatment of inorganic filler with silicone oil-based treatment agent, followed by treatment with trimethylsilylating agent or alkylsilazane-based treatment agent; Hydrophobization treatment of inorganic filler with alkoxysilane; Alkoxysilane After treating the inorganic filler by the method of further treating with a silicone oil-based treating agent, or a silicone oil-based treating agent and an alkoxysilane; dimerdiol siloxane, and / or trimethylsilanol or cyclic siloxy And a method of treating an inorganic filler with emissions and the like. In addition to the above hydrophobization method, various coupling agents such as silane coupling agents, titanate coupling agents, aluminate coupling agents; surfactants such as phosphates and fatty acids; oils and fats A method of treating with stearic acid or the like is also exemplified as a method of hydrophobizing treatment. Hereinafter, the above-mentioned products for hydrophobizing untreated inorganic fillers (for example, all treatment agents such as silicone oil-based treatment agents, silane coupling agents, surfactants, etc.) are collectively hydrophobized. Also called an agent.

  The silicone oil-based treatment agent is not particularly limited. For example, straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, Carbinol-modified silicone oil, methacryl-modified silicone oil, mercapto-modified silicone oil, phenol-modified silicone oil, one-end reactive modified silicone oil, different functional group-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, alkyl-modified Silicone oil, higher fatty acid ester-modified silicone oil, hydrophilic specially modified silicone oil, higher alkoxy-modified silicone N'oiru, higher fatty acid containing modified silicone oil, it is possible to use modified silicone oil and fluorine modified silicone oil.

  The alkylsilazane-based treatment agent is not particularly limited, and examples thereof include hexamethyldisilazane and vinylsilazane.

  The trimethylsilylating agent is not particularly limited, and examples thereof include trimethylsilanol, trimethylmethoxysilane, trimethylchlorosilane, aminomethyltrimethylsilane, dimethylaminotrimethylsilane, and diethylaminotrimethylsilane.

  It does not specifically limit as alkoxysilane, For example, the alkoxysilane compound in the below-mentioned silane coupling agent is mentioned.

  The silane coupling agent is not particularly limited. For example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, n-hexyltrimethoxysilane, n- Hexyltriethoxysilane, n-octyltriethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, benzyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, diethoxymethylphenylsilane, allyltriethoxysilane, vinyltri Alkoxysilane compounds such as methoxysilane, vinyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane; trimethylchlorosilane Such as chlorosilane compounds such as diethyl dichlorosilane and the like.

  The titanate coupling agent is not particularly limited, but is isopropyltridecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltri (N-aminoethyl) -Aminoethyl) titanate and the like.

  The aluminate coupling agent is not particularly limited, and examples thereof include acetoalkoxyaluminum diisopropylate.

  The surfactant is not particularly limited, and for example, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. It does not specifically limit as fats and oils, Various well-known fats and oils can be used.

  The method for hydrophobizing the inorganic filler with the various hydrophobizing agents described above is not particularly limited, and can be performed by a known method. For example, a method of adding (for example, spraying) a hydrophobizing agent stock solution or a hydrophobizing agent diluted with water or an organic solvent to an untreated inorganic filler (for example, a dry treatment method); And a method of treating (for example, dipping) in a stock solution of a hydrophobizing agent, an aqueous solution containing a hydrophobizing agent, or an organic solvent containing a hydrophobizing agent, and then drying (wet treatment method). By such treatment, a part or all of the surface of the inorganic filler is coated with (a) the hydrophobic treatment agent, (b) adsorbs the hydrophobic treatment agent, or (c) is coated with the hydrophobic treatment agent. And adsorbing (a combination of (a) and (b)). As a result, a hydrophobic treated inorganic filler is obtained. In addition, you may use the said various hydrophobization processing agent individually by 1 type or in combination of 2 or more types.

  Hydrophobic treated inorganic fillers can be used alone or in combination of two or more. Moreover, various commercial items can be used for the inorganic filler subjected to the hydrophobization treatment.

  Among the hydrophobized inorganic fillers used in the present invention, hydrophobized silica can be used from the viewpoints of physical properties for floor use, coating suitability of the surface protective layer, matting effect on the decorative sheet surface, and the like. preferable.

  The content of the inorganic filler subjected to the hydrophobization treatment in the surface protective layer is 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin (resin component) constituting the surface protective layer from the viewpoint of easy sweepability. It is preferably 1 to 25 parts by mass, and more preferably 5 to 20 parts by mass.

  The particle size (and average particle size) of the hydrophobic filler that has been hydrophobized is not particularly limited. For example, a hydrophobized inorganic filler having a mode diameter (a particle diameter showing the maximum value of the particle diameter distribution and having the largest appearance ratio) of about 1 to 10 μm is preferable, and the mode diameter is 2 to 6 μm. A certain hydrophobized inorganic filler is more preferable. Further, from the viewpoint of improving easy sweepability, it is preferable that the particle diameter of the hydrophobic treated inorganic filler is set to ½ or less of the thickness of the surface protective layer. For example, if the thickness of the surface protective layer is 10 μm, the particle diameter of the inorganic filler is preferably 5 μm or less. The particle diameter (mode diameter) of the hydrophobized inorganic filler of the present invention is a value measured by a light scattering method.

  The shape of the hydrophobized inorganic filler is not particularly limited, and examples thereof include a spherical shape, a cubic shape, a rod shape, a plate shape, and a needle shape.

Martens hardness of the surface protective layer has a 70N / mm ² or more, considering the cracking of the sheet due to the impact scratches generated during such dropped objects, preferably 70N / mm ² or more 200 N / mm ² or less, 70N / Mm ² or more and 140 N / mm ² or less are more preferable.

  As a method for adjusting the Martens hardness of the surface protective layer, for example, 1) Change to a resin having a different hardness (mixing two or more types of curable resins having different hardnesses), 2) To the surface protective layer It can be appropriately adjusted by adding various additives typified by a matting agent or a filler.

In addition, the Martens hardness in this specification is a value measured by the nanoindentation method using a surface film physical property tester (PICODETOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and is a specific measurement. The method is as follows. In this measurement method, using the diamond indenter (Vickers indenter) shown in FIG. 2 (a), the diamond indenter is pushed into the measurement sample as shown in FIG. 2 (b), and the diagonal line of the pyramidal depression formed on the surface is obtained. The surface area A (mm ² ) is calculated from the length of and the hardness is obtained by dividing the test load F (N). As shown in FIG. 2 (c), the indentation conditions were as follows. First, a load of 0 to 5 mN was applied for 10 seconds, and then a 5 mN load was maintained for 5 seconds. Unloading to ~ 0mN is performed in 10 seconds. And the hardness calculated | required by F / A 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 the layer which wants to measure Martens hardness, the Martens hardness of the cross section of the layer which wants to measure Martens hardness was measured. In this case, the decorative sheet is embedded with a resin (cold curing type epoxy two-component curable resin), allowed to stand for 24 hours or more at room temperature to be cured, and then the cured embedded sample is mechanically polished to have a Martens hardness. The cross section of the measurement target surface by exposing the cross section of the layer to be measured and pushing the diamond indenter into the cross section (at a position avoiding the fine particles such as inorganic filler in the measurement target layer) The Martens hardness of was measured.

  If necessary, various additives such as solvents, dyes, pigments and other colorants, matting agents, fillers such as extenders, antifoaming agents, leveling agents, thixotropic agents are added to the surface protective layer. be able to.

  Examples of a method for forming a surface protective layer containing an ionizing radiation curable resin include (1) a resin such as an ionizing radiation curable resin, a hydrophobized inorganic filler, and (2) other, if necessary. After applying a solution (resin composition for forming a surface protective layer) containing a resin, an ultraviolet absorber, an antibacterial agent and the above-mentioned various additives by a coating method such as a gravure coating method or a roll coating method, an ionizing radiation curable type The method of forming a surface protective layer by hardening resin is mentioned.

If necessary, a back primer layer may be provided on the back surface of the back primer layer substrate sheet (the surface opposite to the surface on which the pattern layer is laminated). For example, it is effective when a decorative sheet is produced by laminating the decorative sheet and an adherend.

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

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

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

Backer layer (back side of the pattern layer if the back side of the base sheet has a pattern layer) on the back side of the backer layer base sheet, increase the scratch resistance or reduce the influence of the substrate A synthetic resin layer) may be provided. The scratch resistance refers to a dent scratch when a load is applied partially. Although the decorative sheet of the present invention has sufficient scratch resistance even without providing a backer layer, various performances such as scratch resistance can be further improved by providing a backer layer.

  As a method for forming the backer layer, extrusion molding of a molten resin is suitable, for example, extrusion molding using a T die is suitable.

  As a method of adhering the back surface of the base material sheet and the backer layer, a method of adhering the base material sheet and the backer layer obtained by extruding the molten resin by heat fusion, the base material sheet and the backer layer For example, a method of bonding by providing an adhesive layer (further, if necessary, a primer layer) between them may be used.

  The resin constituting the backer layer is not limited, but a thermoplastic resin such as polyethylene, polypropylene (PP), polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate. (A-PET), highly heat-resistant polyalkylene terephthalate [for example, polyethylene terephthalate in which a part of ethylene glycol is substituted with 1,4-cyclohexanedimethanol, diethylene glycol or the like, so-called trade name PET-G (Eastman Chemical) Company)), polybutylene terephthalate (PBT), polycarbonate, polyarylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate Coalescence, polyimide, polystyrene, polyamide, ABS (acrylonitrile - butadiene - styrene copolymer) and the like. These resins can be used alone or in combination of two or more.

  The thickness of the backer layer can be appropriately set depending on the use of the final product, the method of use, etc., and is generally preferably 100 to 800 μm. Among these, 100-600 micrometers is more preferable.

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

The outermost layer side of the embossed decorative sheet may be embossed as necessary.

  The embossing method is not particularly limited, and for example, a preferable method is to heat and soften the front surface of the surface protective layer, pressurize and shape with an emboss plate, and then cool. Depending on the material of the final product decorative sheet or surface protective layer, for example, the front surface of the transparent resin layer is softened by heating and pressed and shaped with an embossed plate, and then a surface protective layer is formed thereon May be.

  For embossing, a known single-wafer or rotary embossing machine is used. Examples of the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like.

≪2. Decorative plate of the present invention >>
By laminating the decorative sheet on the adherend, a decorative board can be obtained. The adherend is not limited, and the same materials as those used for known decorative panels can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet can be suitably used for a wood material. Specific examples of wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. , Chip boards, or composite substrates on which chip boards are laminated. As the wood material, wood plywood, particle board, medium density fiber board (MDF) is preferably used.

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

  The decorative board manufactured in this way includes, for example, interior materials for buildings such as walls, ceilings, and floors; exterior materials such as balconies and verandas; surface decorative boards and furniture for furniture such as window frames, doors, and handrails; Alternatively, it can be used for a surface decorative plate of a cabinet such as a light electric or OA device. In particular, the decorative board can be suitably used as a floor decorative material.

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

Example 1
A primer layer (back surface primer layer) was provided on the back surface of the base sheet made of a colored polypropylene film having a thickness of 60 μm. Next, a pattern layer was formed on the surface of the substrate sheet by printing, and an adhesive layer was further formed on the pattern printing layer. Next, a transparent polypropylene resin sheet having a thickness of 80 μm was laminated on the adhesive layer by an extrusion laminating method to form a transparent resin layer. Next, the surface of the transparent polypropylene resin sheet was subjected to corona discharge treatment, and then a two-component curable urethane resin was applied to form a primer layer. Next, a surface containing 70 parts by mass of a bifunctional urethane acrylate oligomer α, 30 parts by mass of a hexafunctional aliphatic urethane acrylate oligomer and 14 parts by mass of silica (mode diameter 3 μm) hydrophobized with silicone oil on the surface of the primer layer After applying the resin composition for forming a protective layer by a gravure coating method to form a coating film (13 μm), an electron beam irradiation device is used in an environment with an oxygen concentration of 200 ppm or less under conditions of an acceleration voltage of 175 keV and 5 Mrad. The coating film was cured by irradiating a line to form a surface protective layer. Furthermore, the surface protective layer side was heated with an infrared non-contact type heater to soften the base sheet and the transparent resin layer, and then embossed by hot pressure to shape the uneven pattern of the wood grain conduit pattern . This produced the decorative sheet. The Martens hardness of the surface protective layer measured with the produced decorative sheet was 140 N / mm ² .

Example 2
A decorative sheet was obtained in the same manner as in Example 1 except that hydrophobized silica (mode diameter 3 μm) was used instead of hydrophobized silica having a mode diameter of 5 μm.

Example 3
Except for replacing the Martens hardness of the surface protective layer from 140 N / mm ² to 70N / mm ^2, the same procedure as in Example 1 to obtain a decorative sheet.

Comparative Example 1
A decorative sheet is obtained in the same manner as in Example 1 except that non-hydrophobized silica (untreated silica) (mode diameter: 11 μm) is used instead of hydrophobized silica (mode diameter: 3 μm). It was.

Comparative Example 2
Untreated silica (mode diameter 11 μm) is used in place of the hydrophobized silica (mode diameter 3 μm), the thickness of the surface protective layer is changed from 13 μm to 15 μm, and the Martens hardness is 140 N / mm ² to 110 N / A decorative sheet was obtained in the same manner as in Example 1 except that mm ² was used.

Comparative Example 3
Instead of 14 parts by mass of hydrophobized silica (mode diameter 3 μm), 12 parts by mass of untreated silica (mode diameter 11 μm) is used, the thickness of the surface protective layer is changed from 13 μm to 15 μm, and the Martens hardness is 140 N. / except for replacing the mm ² to 60N / mm ^2, the same procedure as in example 1 to obtain a decorative sheet.

Comparative Example 4
A decorative sheet was obtained in the same manner as in Example 1, except that untreated silica (mode diameter 3 μm) was used instead of the hydrophobized silica (mode diameter 3 μm), and 1 part by mass of silicone was added. It was.

Comparative Example 5
A decorative sheet was obtained in the same manner as in Example 1 except that untreated silica (mode diameter 3 μm) was used instead of the hydrophobized silica (mode diameter 3 μm).

Comparative Example 6
A decorative sheet was obtained in the same manner as in Example 1 except that untreated silica (mode diameter 5 μm) was used instead of the hydrophobized silica (mode diameter 3 μm).

Comparative Example 7
Untreated silica (mode diameter 3 [mu] m) instead of the hydrophobized silica (mode diameter 3 [mu] m), and, except for replacing the Martens hardness of the surface protective layer from 140 N / mm ² to 70N / mm ² is A decorative sheet was obtained in the same manner as in Example 1.

Comparative Example 8
Untreated silica (mode diameter 3 [mu] m) instead of the hydrophobized silica (mode diameter 3 [mu] m), and, except for replacing the Martens hardness of the surface protective layer from 140 N / mm ² to 60N / mm ² is A decorative sheet was obtained in the same manner as in Example 1.

Comparative Example 9
A decorative sheet was obtained in the same manner as in Example 1 except that the Martens hardness of the surface protective layer was changed from 140 N / mm ² to 60 N / mm ² .

In Examples 1 to 3 and Comparative Examples 1 to 9, the Martens hardness of the surface protective layer was measured using a surface film physical property tester (PICODETOR HM-500, manufactured by Fisher Instruments Co., Ltd.). Specifically, using the diamond indenter (Vickers indenter) shown in FIG. 2 (a), the diamond indenter is pushed into the measurement sample as shown in FIG. 2 (b), and the diagonal line of the pyramidal depression formed on the surface The surface area A (mm ² ) was calculated from the length of and the hardness was determined by dividing the test load F (N). As shown in FIG. 2 (c), the indentation conditions were as follows. First, a load of 0 to 5 mN was applied for 10 seconds, and then a 5 mN load was maintained for 5 seconds. Unloading to ˜0 mN was performed in 10 seconds. And the hardness calculated | required by F / A based on the surface area A and the test load F was made into the said Martens hardness. In addition, in order to avoid the influence of the hardness of layers other than the surface protective layer for which the Martens hardness is to be measured, 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 Martens hardness of the cross section of the surface protective layer surface by exposing the cross section of the surface and pushing the diamond indenter into the cross section (at a position avoiding the fine particles such as inorganic filler in the surface protective layer) Was measured.

  The wetting tension of the surface protective layer was measured according to JIS K6768 (1999) (plastic-film and sheet-wetting tension test method). Specifically, a wetting tension test mixture (trade name: Wetting tension test mixture No. 30 to 36, manufactured by Wako Pure Chemical Industries, Ltd.) is used with a paper swab (made by Kawamoto Sangyo Co., Ltd.). Then, it was spread on the front surface of the surface protective layer, and the wetting tension was measured.

(Production of decorative board)
Water-based emulsion adhesive (Rikabond BA-10L (main agent): BA-11B (curing agent) = 100: 2.5 (manufactured by Chuo Rika Kogyo Co., Ltd.) on a medium density wood fiber board (MDF) having a thickness of 2.5 mm The weight ratio)) was uniformly applied at 80 g / m ² , the decorative sheet was bonded, and the plate was cured for 3 days at room temperature.

Evaluation 1: Easy cleaning of gypsum powder First, putty powder (Yayoi Chemical Industry Co., Ltd., Wide Super 60) was cured and ground with # 180 file to obtain gypsum powder. Next, about 0.5 g / scale angle of the gypsum powder was applied to the entire surface of each decorative sheet of Examples and Comparative Examples. Next, the gypsum powder was thinly stretched on the surface of each decorative sheet with a dry rag (towel cloth). Finally, the surface of each decorative sheet after wiping was wiped twice with a rag (towel cloth) moistened with water so that no residue remained due to the gypsum powder. The evaluation criteria are as follows.
+++: No dirt residue ++: Partially minor dirt residue +: Minor dirt residue remaining-: Entire dirt residue

Evaluation 2: Oil (oleic acid) easy-cleaning oleic acid was applied to the entire surface of each decorative sheet of Examples and Comparative Examples at about 10 g / m ² . The surface of each decorative sheet was wiped once with a rag (towel cloth) moistened with water so that the oleic acid did not leave a stain. Evaluation criteria for evaluation 2 are as follows.
+++: No dirt remains ++: Dirt is not noticeable +: Thin dirt is present-: Dirt remains

Evaluation 3: Easiness of sweeping (wiping resistance (sliding property))
Using a Tokyo Institute of Technology slip tester (OY-PSM), the slip resistance value (CSR value) with socks (100% cotton material) was measured. The evaluation criteria are as follows.
++: Evaluation value is less than 0.3 ++: Evaluation value is 0.3 or more and less than 0.4 −: Evaluation value is 0.4 or more

Evaluation 4: Wax application suitability wax (high-tech flooring coat: manufactured by Rinnai Co., Ltd.) was applied to the surface of each decorative sheet (about 10 ml / m ² ), and the surface condition after application was visually evaluated. The evaluation criteria are as follows.
++: Wax is uniformly applied-: Repels wax and cannot be uniformly applied

Evaluation 5: Scratch resistance (Hoffman scratch test)
Evaluation was performed using a Hoffman scratch tester (BYK-Gardner). Specifically, set the scratch blade (the edge portion of a cylinder with a diameter of 7 mm) so as to come into contact with the surface protective layer of the decorative sheet of each decorative plate at an angle of 45 degrees, and move so as to pull the scratch blade And rubbed the surface. At that time, the load applied to the scratch blade by 100 g in the range of 100 to 500 g load was changed to confirm whether or not the surface protective layer was damaged. The evaluation criteria are as follows.
++++: No scratches observed at 500 g ++: No scratches observed at 300 g +: Slightly scratches observed at 300 g−: Scratches clearly evident at 300 g It shows in Table 1 and Table 2.

In addition, the kind of resin in Table 1 and Table 2 is as follows.
Bifunctional α: Bifunctional urethane acrylate oligomer (polyol component is polyester diol, glass transition temperature: 25 ° C., weight average molecular weight 1500)
Bifunctional β: Bifunctional urethane acrylate oligomer (polyol component is polyester diol, glass transition temperature: 25 ° C., weight average molecular weight 1200)
Bifunctional γ: Bifunctional urethane acrylate oligomer (polyol component is polyester diol, glass transition temperature: −55 ° C., weight average molecular weight 5000)
Hexafunctional: Hexafunctional aliphatic urethane acrylate oligomer (glass transition temperature: 200 ° C. or higher, weight average molecular weight 1500, Kyoeisha Chemical Co., Ltd. UA306H)

1. Cosmetic sheet 2. Back primer layer 3. Base sheet 4. Pattern pattern layer 5. Adhesive layer 6. Transparent resin layer 7. Primer layer 8. Surface protective layer 9. Embossed pattern (wood grain plate conduit groove)

Claims (8)

A decorative sheet having at least a surface protective layer on a substrate sheet,
A decorative sheet, wherein the surface protective layer has a wetting tension of 30 mN / m or more and less than 35 mN / m, and the surface protective layer has a Martens hardness of 70 N / mm ² or more.   The decorative sheet according to claim 1, wherein the surface protective layer contains an inorganic filler that has been subjected to a hydrophobic treatment.   The decorative sheet according to claim 2, wherein a particle diameter of the hydrophobized inorganic filler is 1 to 10 µm in mode diameter.   The makeup according to claim 2 or 3, wherein the content of the hydrophobized inorganic filler is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface protective layer. Sheet.   The decorative sheet according to any one of claims 2 to 4, wherein the hydrophobized inorganic filler is silica.   The decorative sheet according to any one of claims 1 to 5, wherein the resin constituting the surface protective layer is an ionizing radiation curable resin.   The decorative sheet according to any one of claims 1 to 6, wherein the surface protective layer has a thickness of 10 µm or more.   A decorative board in which the decorative sheet according to claim 1 is laminated on an adherend.