JP2015231748A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having no handle loss even under high load, hardly causing boring wound, whitening wound, scratch and dent flaws, and excellent in crack resistance.SOLUTION: There is provided a decorative sheet having at least a thermoplastic resin layer and a top coat layer in this order. (1) The top coat layer has an outermost layer containing ionization radiation curable resin, (2) a thickness of the top coat layer is 20 μm or more, (3) a thickness of the thermoplastic resin layer is 40 to 120 μm, and (4) a ratio of the thickness of the top coat layer to the thickness of the thermoplastic resin layer is 20% or more.

Description

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

  A decorative sheet in which a thermoplastic resin layer is formed on a pattern printing layer is preferably used because it does not disappear even when a high load is applied. However, when a high load is applied to the decorative sheet, there is a problem that the thermoplastic resin layer is rolled up and whitening scratches are generated. Therefore, it has been proposed to provide a two-component curable topcoat layer, an ionizing radiation curable topcoat layer, and the like on the thermoplastic resin layer.

JP 2006-123512 A

  However, a decorative sheet having a two-component curable topcoat layer has a problem that scratches are likely to occur. In addition, a decorative sheet having an ionizing radiation curable top coat layer is resistant to scratches, but when a high load is applied, the decorative sheet has dents (bleaching, whitening and dents) due to dents (elastic deformation) of the thermoplastic resin layer. There is a problem that scratches occur.

  Accordingly, an object of the present invention is to provide a decorative sheet and a decorative material that have no pattern disappearance even under a high load, are not easily damaged by scratching, whitening, abrasion and dent, and have excellent crack resistance. .

  As a result of intensive studies to achieve the above object, the present inventor has found that a decorative sheet can achieve the above object when a specific one is used as the thermoplastic resin layer and the top coat layer, respectively. The invention has been completed.

That is, the present invention relates to the following decorative sheet.
1. A decorative sheet having at least a thermoplastic resin layer and a topcoat layer in order,
(1) The top coat layer has an outermost layer containing an ionizing radiation curable resin,
(2) The thickness of the top coat layer is 20 μm or more,
(3) The thermoplastic resin layer has a thickness of 40 to 120 μm,
(4) The ratio of the thickness of the topcoat layer to the thickness of the thermoplastic resin layer is 20% or more.
A decorative sheet characterized by that.
2. The decorative sheet according to Item 1, wherein the thermoplastic resin layer has a tensile elastic modulus measured according to JIS K7161 of 400 to 1200 MPa.
3. Item 3. The decorative sheet according to Item 1 or 2, wherein the thermoplastic resin layer is an olefin resin.
4). Item 4. The decorative sheet according to any one of Items 1 to 3, further comprising a pattern layer, an adhesive layer, a thermoplastic resin layer, and a topcoat layer in this order on the substrate sheet.
5). Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the outermost layer has a Martens hardness of 40 to 140 N / mm ² .
6). A cosmetic material obtained by sticking the decorative sheet according to any one of Items 1 to 5 to a wooden substrate.

  Hereinafter, the decorative sheet of the present invention will be described in detail.

The decorative sheet of the present invention is a decorative sheet having at least a thermoplastic resin layer and a topcoat layer in order,
(1) The top coat layer has an outermost layer containing an ionizing radiation curable resin,
(2) The thickness of the top coat layer is 20 μm or more,
(3) The thermoplastic resin layer has a thickness of 40 to 120 μm,
(4) The ratio of the thickness of the topcoat layer to the thickness of the thermoplastic resin layer is 20% or more.

  The decorative sheet of the present invention having the above-described characteristics is that the thermoplastic resin layer and the topcoat layer satisfy the above specific conditions, respectively, so that the pattern does not disappear even under a high load, and the scuff, whitening, dent, and scratches Is difficult to stick and has excellent crack resistance (impact resistance).

  The configuration of the decorative sheet of the present invention is not limited as long as the decorative sheet has at least a thermoplastic resin layer and a topcoat layer in order. For example, a decorative sheet in which a colored hiding layer, a pattern layer, an adhesive layer, a thermoplastic resin layer, and a topcoat layer are sequentially laminated on a base material sheet can be used. Hereinafter, each layer constituting the decorative sheet will be described as a representative example.

(Base material sheet)
It does not specifically limit as a base material sheet, The thing normally used in the field | area of a decorative sheet can be used. For example, 1) paper such as thin paper, fine paper, kraft paper, Japanese paper, titanium paper, resin-impregnated paper, inter-paper reinforced paper, 2) made of wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, etc. Woven or non-woven fabric, 3) thermoplastic resin and the like.

  As the thermoplastic resin, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polybutene, polymethylpentene, polycarbonate, polyethylene naphthalate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, Thermoplastic resins such as ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-propylene-butene copolymer, ionomer, polyacrylic acid ester, polymethacrylic acid ester, polyolefin thermoplastic elastomer, etc. Can be used. These resins can be used alone or in combination of two or more.

  The base material sheet may be colored. In this case, it is possible to add a colorant (pigment or dye) to the above thermoplastic resin or the like 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.

  When the base sheet is a thermoplastic resin, one or both surfaces thereof may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, etc., as necessary. . For example, when performing a corona discharge treatment, the surface tension of the substrate sheet surface may be 30 dyn / cm or more, preferably 40 dyn / cm or more. The surface treatment may be performed according to a conventional method for each treatment.

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

  When a back surface primer layer is provided on the back surface side of the base sheet, the material (including additives), coating method, coating amount, thickness, and the like are the same as those of the primer layer described later.

(Pattern pattern layer)
A pattern layer can be formed on the substrate sheet as necessary.

  The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly 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, a colored ink or coating 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 by the printing method etc. which used the agent. As the ink, an aqueous composition can also be used from the viewpoint of reducing the VOC of the decorative sheet.

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

  Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer resins, polyvinyl resins. Examples include butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose resins, fiber derivatives, rubber resins, and polycarbonate resins. Moreover, the copolymer which has these resins as a main component can also be used. In addition, these resin can be used individually or in mixture 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 Inorganic solvents and the like, such as water; chlorinated organic solvents. These solvents (or dispersion media) can be used alone or in admixture of two or more.

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

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

(Colored hiding layer)
A colored concealment layer may be further formed between the base sheet and the pattern layer as necessary. The colored masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. In the present invention, a colored concealment layer may be further formed to stabilize the concealability.

  As the ink for forming the coloring hiding layer, a known ink capable of hiding coloring can be used.

  The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.

  The thickness of the colored concealing layer is not particularly limited and can be set as appropriate according to the product characteristics. The layer thickness during coating is about 0.2 to 10 μm, and the layer thickness after drying is about 0.1 to 5 μm.

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

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field | area of a decorative sheet. Examples of known adhesives in the decorative sheet field include thermoplastic resins such as polyamide resins, acrylic resins, vinyl acetate resins, and polycarbonate resins, and thermosetting resins such as urethane resins. Moreover, the copolymer which has these resins as a main component can also be used. In addition, these adhesive agents can be used individually by 1 type or in mixture 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.

  A well-known printing method can be employ | adopted for formation of an adhesive bond layer. For example, methods such as 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 can be employed.

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

(Thermoplastic resin layer)
In the decorative sheet of the present invention, a thermoplastic resin layer is formed. The said thermoplastic resin layer can be formed on a base material sheet, a pattern pattern layer, an adhesive bond layer etc., for example.

  The thickness of the thermoplastic resin layer is 40 to 120 μm. More preferably, it is 60-100 micrometers. When the thickness is less than 40 μm, it is easy to cause a scuffing and whitening wound, and when it exceeds 120 μm, a whitening wound and a dent scratch are likely to occur.

  The tensile elastic modulus of the thermoplastic resin layer is preferably 400 to 1200 MPa, and more preferably 800 to 1100 MPa. If the tensile modulus of the thermoplastic resin layer is within the above range, the crack resistance (impact resistance) and the like are particularly excellent. The tensile elastic modulus can be appropriately set by 1) mixing two or more kinds of the above resins having different tensile elastic moduli, 2) mixing an elastomer with the above resin, and the like.

  The tensile elastic modulus in this specification is a value measured in accordance with JIS K7161. Specifically, using a tensile tester (Tensilon universal tester RTC-1250A), both ends (A and B of FIG. 1) of the test sample (thermoplastic resin layer) punched into the shape shown in FIG. 50 mm / min. It is the value calculated | required by measuring the tensile elasticity modulus (MPa) at the time of pulling at the speed | rate.

  The resin constituting the thermoplastic resin layer is not particularly limited. For example, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid. Examples include ester copolymers, ionomers, polymethylpentene, polyacrylates, polymethacrylates, polycarbonates, and cellulose triacetates. Of these, olefin resins such as polyethylene and polypropylene are preferable.

  As polypropylene, a homopolymer of propylene or a copolymer containing propylene as a main component can be used. For example, homopolypropylene resin, random polypropylene resin, and block polypropylene resin can be used. As the polypropylene, commercially available products (eg, Prime Polymer Co., Ltd. (Prime TPO “J-5900”, Prime Polypro “F219DA”), etc.) can be used.

  The said resin can be used individually or in combination of 2 or more types.

  For the thermoplastic resin layer, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, soft ingredients as necessary Various additives such as rubber (for example, rubber) may be included.

  The method for forming the thermoplastic resin layer is not limited, for example, a method in which a preformed sheet or film is laminated to an adjacent layer, a resin composition that can form a thermoplastic resin layer is melt-extruded, and the thermoplastic resin layer is combined with the adjacent layer. There are methods such as laminating. Examples of a method for laminating a sheet or film formed in advance include a laminating method by a dry laminating method.

  The thermoplastic resin layer may be subjected to a surface treatment such as a corona discharge treatment, an ozone treatment, a plasma treatment, an ionizing radiation treatment, or a dichromic acid treatment as in the case of the above-described base sheet. About the conditions of a corona discharge process, it is the same as that of the above-mentioned base material sheet.

(Topcoat layer)
The decorative sheet of the present invention has a topcoat layer on the thermoplastic resin layer.

  The topcoat layer is a layer having an outermost layer containing at least an ionizing radiation curable resin, and refers to all layers formed on the thermoplastic resin layer. Specifically, a topcoat layer composed of a single outermost layer, a topcoat layer composed of a plurality of layers (for example, a primer layer described later and two topcoat layers composed of an outermost layer; a primer layer, a lower layer described later) 3 topcoat layers comprising the outermost layer). When the outermost layer in the top coat layer does not contain an ionizing radiation curable resin, scratches are generated.

  The thickness (thickness) of the top coat layer is 20 μm or more. Preferably it is 20-50 micrometers, More preferably, it is 25-35 micrometers. On the other hand, when the said thickness is less than 20 micrometers, the dent deformation | transformation of a thermoplastic resin layer cannot be suppressed, and a whitening damage | wound is easy to produce.

  The ratio of the thickness of the topcoat layer to the thickness of the thermoplastic resin layer (= (thickness of topcoat layer / thickness of thermoplastic resin layer) × 100) is 20% or more. Preferably, it is 20 to 50%. On the other hand, when the ratio is less than 20%, the dent deformation of the thermoplastic resin layer cannot be suppressed as in the case where the thickness of the topcoat layer is less than 20 μm, and whitening damage is likely to occur.

  Hereinafter, each layer forming the top coat layer will be described in detail.

[Outermost layer]
The outermost layer is formed on the outermost surface of the decorative sheet of the present invention.

  The outermost layer contains at least an ionizing radiation curable resin as a resin component. Substantially, those formed from ionizing radiation curable resins are preferred. 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. Resin can be used. These prepolymers or monomers can be used alone or in combination.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000. For example, when the prepolymer having a radical polymerizable unsaturated group is urethane (meth) acrylate, it is a polyol component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycaprolactone diol, etc.) and a curing agent component. To compounds having terminal isocyanate groups obtained by reacting isocyanate components (tolylene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, etc.), such as 2-hydroxyethyl acrylate (HEA) or 2-hydroxyethyl methacrylate (HEMA) By reacting the (meth) acrylate group, it is obtained as a monofunctional or polyfunctional (meth) acrylate compound having a (meth) acryloyl group at the terminal.

  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 ethylene glycol diacrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexaacrylate, dipentaerythritol hexa (meth) acrylate and the like.

  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.

  In addition to the ionizing radiation curable resin, various resins can be used in combination on the outermost layer as the resin component. Examples of the resin that can be used in combination include unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea cocondensation resin, silicon resin, A thermosetting resin such as a polysiloxane resin can be used.

  The outermost layer can be cured by irradiation with ionizing radiation. As the ionizing radiation, 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 amount of electron beam irradiation is preferably about 2 to 15 Mrad, and more preferably 2 to 5 Mrad.

  In addition, the outermost layer may be a weathering agent, a plasticizer, a stabilizer, a filler, a dispersant, a dye, a matting material, a UV absorber, a light stabilizer, a colorant such as a pigment, a solvent, or the like as necessary. An additive may be included.

  The outermost layer is, for example, a resin composition containing an ionizing radiation curable resin on a thermoplastic resin layer (if the topcoat layer has a primer layer, a lower layer, etc.), such as a gravure coat, a roll coat, etc. After coating by a known coating method, it can be formed by irradiating with ionizing radiation and curing the resin.

  The thickness of the outermost layer is not particularly limited as long as the thickness of the topcoat layer is 20 μm or more, and can be appropriately set according to the characteristics of the final product, but is preferably 3 to 30 μm, more preferably 10 to 30 μm.

The hardness of the outermost layer is not particularly limited, but the Martens hardness is preferably 40 to 140 N / mm ² . When the Martens hardness is within the above range, it becomes more difficult to bend and whitening.

In addition, the Martens hardness in this specification is a value measured using a surface film physical property tester (PICODENTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows. is there. 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 pyramid-shaped 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 ~ 0 mN 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 outermost layer, the Martens hardness of the cross section of the outermost layer was measured. In this case, the decorative sheet is embedded with a resin (cold-curing type epoxy two-component curable resin) and allowed to cure for 24 hours or more at room temperature, and then the cured embedded sample is mechanically polished to form the outermost layer. The cross section was exposed, and the Martens hardness of the cross section was measured by pushing a diamond indenter into the cross section (at a position avoiding the fine particles when the fine particles such as the filler were included in the outermost layer).

  Martens hardness can be set by appropriately blending an ionizing radiation curable resin. For example, when urethane acrylate is used as the ionizing radiation curable resin, a desired Martens hardness can be obtained by appropriately blending a bifunctional urethane acrylate and a hexafunctional urethane acrylate, or using only a trifunctional urethane acrylate having a molecular weight of about 1500. You can get it. Here, the bifunctional urethane acrylate means a urethane acrylate having two radically polymerizable acryloyl groups in one molecule. Similarly, trifunctional urethane acrylate and hexafunctional urethane acrylate mean urethane acrylates having three and six radically polymerizable acryloyl groups in one molecule, respectively.

〔Underlayer〕
The decorative sheet of the present invention can be provided with a lower layer on the back surface side of the outermost layer as necessary.

  The lower layer may be not only a single layer but also a plurality of layers of two or more layers.

  The lower layer is not particularly limited as a resin component, but preferably contains an ionizing radiation curable resin or a two-component curable urethane-based resin, and more preferably contains a two-component curable urethane-based resin. Substantially those formed from these resins are preferred.

  The ionizing radiation curable resin is not particularly limited, and for example, a resin similar to the ionizing radiation curable resin exemplified in the outermost layer can be used.

  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.

  For the lower layer, an ionizing radiation curable resin or a two-component curable urethane-based resin can be used as the resin component, and the same resins as those that can be used together in the outermost layer described above.

  When an ionizing radiation curable resin is included as a resin component constituting the lower layer, the ionizing radiation curable resin is cured by irradiation with ionizing radiation. Therefore, a decorative sheet excellent in scratch resistance, impact resistance and the like can be obtained.

  The type and conditions of the ionizing radiation are the same as the ionizing radiation in the outermost layer described above.

  The lower layer contains various additives such as weathering agents, plasticizers, stabilizers, fillers, dispersants, dyes, matting materials, UV absorbers, light stabilizers, pigments, and other solvents as necessary. May be included.

  The lower layer is, for example, coated on the thermoplastic resin layer (if the top coat layer has a primer layer, the primer layer) by a known coating method such as gravure coating or roll coating. After the process, it can be formed by appropriately curing the resin.

  The thickness of the lower layer is not particularly limited as long as the thickness of the topcoat layer is 20 μm or more, and can be appropriately set according to the properties of the final product, but is preferably 1 to 30 μm, and more preferably 5 to 15 μm.

[Primer layer]
A primer layer can be formed between the thermoplastic resin layer and the outermost layer (a lower layer when a lower layer is provided on the top coat layer) as necessary. By forming the primer layer, the adhesion between the thermoplastic resin layer and the outermost layer (or lower layer) can be improved.

  The primer layer is a solution of vinyl chloride-vinyl acetate copolymer, acrylic resin, polyester resin, polyurethane resin (two-component curing type comprising isocyanate curing agent and various polyols), chlorinated polypropylene, chlorinated polyethylene, polycarbonate resin, etc. It is formed by coating. Moreover, the copolymer which has these resins as a main component can also be used. For example, a polyurethane-acrylic (polyol) copolymer, a polycarbonate-based urethane-acrylic (polyol) copolymer, and the like can be used.

  In addition, the said resin which comprises a primer layer can be used individually by 1 type or in mixture of 2 or more types.

  In addition to the above resin, additives such as fillers such as silica fine powder, ultraviolet absorbers, and light stabilizers may be added to the primer layer. The primer layer is formed by applying these compositions and drying and curing as necessary. Specifically, it is formed by applying the primer composition by a method such as gravure coating or roll coating and drying (curing) it.

  Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 1-4 micrometers.

  A patterned low gloss printing layer may be provided on the primer layer as necessary. After the outermost layer is applied, the region provided with the low gloss printing layer becomes less glossy than the other regions, and the design is such that the region is recognized as a concave portion by the optical illusion.

(Other forms)
As described above, a decorative sheet (so-called doubling sheet) in which a colored hiding layer, a pattern layer, an adhesive layer, a thermoplastic resin layer, and a topcoat layer are sequentially laminated on a base sheet has been described as a representative example. Form may be sufficient. For example, even if the decorative sheet of the present invention is a decorative sheet (so-called back print sheet) in which a colored hiding layer, a pattern layer, a thermoplastic resin layer, and a top coat layer are laminated in order, the same as in the case of a doubling sheet. The effect of.

Manufacturing method of decorative sheet The decorative sheet of the present invention is obtained by forming a topcoat layer having an outermost layer on a thermoplastic resin layer. For example, by laminating a pattern layer (and colored hiding layer), an adhesive layer, a thermoplastic resin layer, a primer layer and a lower layer on a base sheet, and then forming an outermost layer containing an ionizing radiation curable resin can get.

  When the lower layer contains an ionizing radiation curable resin, the lower layer and the outermost layer can be cured by one irradiation with ionizing radiation after the lower layer and the outermost layer are laminated. It is also possible to irradiate with ionizing radiation after forming the lower layer, then laminate the outermost layer on the cured lower layer, and again irradiate with ionizing radiation to cure the outermost layer.

  Moreover, when embossing a decorative sheet, it may be after forming the outermost layer or before forming it. For example, as specific embodiments, 1) a pattern layer, a thermoplastic resin layer, a primer layer, a lower layer and an outermost layer may be formed on a base sheet, and finally embossed. Moreover, as another aspect, 2) After forming a pattern layer, a thermoplastic resin layer, a primer layer, and a lower layer in order on a base material sheet, embossing may be performed and the outermost layer may be finally formed. As another specific embodiment, 3) a pattern layer and a thermoplastic resin layer are sequentially formed on the base sheet, and then embossed, and then a lower layer is provided, and finally the outermost layer is formed. Also good.

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

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

Cosmetic Material A decorative material can be obtained by bonding the decorative sheet of the present invention to various adherends. The material of the adherend is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, wood 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, single board, plywood, particle board, medium density wood fiber board (MDF), high density wood fiber board (HDF), insulation board, etc. made of cedar, straw, firewood, lawan, teak, etc. A board, a laminated board, etc. are mentioned.

  In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  Although it does not specifically limit about joining to the decorative sheet of this invention, and the said various to-be-adhered materials, For example, it can join via an adhesive agent. 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. For example, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, polyurethane, ethylene-vinyl acetate copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, Examples include natural rubber. These adhesives can be used alone or in combination of two or more.

  The adhesive may contain a colorant to such an extent that the effect of the present invention is not affected. Examples of the colorant include inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, and carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, Examples include organic pigments (including dyes) such as Induslen Blue RS and aniline phosphorus, metal pigments such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate, etc. It is done. These can be used alone or in combination of two or more. The content of the colorant can be set as appropriate depending on the color density, but is preferably about 1 to 20% by weight in the adhesive.

  The thickness of the adhesive is not limited, but is preferably about 0.1 to 50 μm.

  The decorative material manufactured in this way is, for example, interior decoration materials for buildings such as walls, ceilings and floors, surface decorative panels for furniture such as window frames, doors and handrails, furniture or cabinets for light electrical appliances, OA equipment, etc. It can be used for a surface decorative board.

  In the decorative sheet of the present invention, the thermoplastic resin layer and the topcoat layer satisfy specific conditions, respectively, so that the pattern does not disappear even under a high load, and it is difficult to bend, whiten, dent and scratch. Excellent crackability (impact resistance).

It is a schematic diagram (top view) which shows the shape at the time of measuring the tensile elasticity modulus of a sample in this specification. In the figure, R60 indicates the degree of curvature. 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. It is a schematic diagram which illustrates the layer structure of the decorative sheet (doubling sheet) of this invention. It is a schematic diagram which illustrates the layer structure of the decorative sheet (back print sheet) of this invention.

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

Example 1
A primer layer (back surface primer layer) was provided on the back surface of the base material sheet made of a colored polypropylene film having a thickness of 60 μm. Subsequently, the pattern layer was formed by printing on the front surface of the base material sheet to obtain a printed film. On the other hand, a transparent polypropylene film (thermoplastic resin layer) having a thickness of 40 μm and a tensile elastic modulus of 1000 MPa is prepared, and uniformly applied to the film using a polyester urethane-based adhesive at 15 g / m ² (during curing). The printing film was laminated by a dry laminating method so that the adhesive and the pattern layer of the printing film were in contact with each other.

Corona discharge treatment is applied to the front surface of the thermoplastic resin layer, and a primer layer (layer thickness: 2 μm) is formed by uniformly applying a urethane acrylic primer at 2 g / m ² (during curing). Then, a resin composition composed of a urethane acrylate oligomer (ionizing radiation curable resin) was applied and dried to form an uncured coating film. Thereafter, in an environment having an oxygen concentration of 200 ppm or less, the uncured resin layer is irradiated with an electron beam under conditions of an acceleration voltage of 200 keV and 3 Mrad to cure the resin, and the outermost layer (ionizing radiation curable resin layer, layer thickness: 18 μm). ) To form a decorative sheet.

  Furthermore, an adherend in which MDF having a thickness of 2.7 mm and an average specific gravity of 0.7 and a plywood having a thickness of 9 mm are bonded together is prepared, and an emulsion-based adhesive is applied to the adherend, and the adhesive and the aforementioned The decorative sheet was laminated so that the back primer layer of the decorative sheet was in contact with each other, and a decorative material was obtained.

Examples 2-7, 9-12 and Comparative Examples 1-6
Except for appropriately changing each physical property (the thickness of the outermost layer, the thickness of the thermoplastic resin layer, the tensile elastic modulus of the thermoplastic resin layer, etc.), the same as in Example 1 as shown in Tables 1 to 3 below. A decorative sheet and a decorative material were prepared.

Example 8
After the corona discharge treatment is applied to the back side of a transparent polypropylene film (thermoplastic resin layer) having a thickness of 120 μm and a tensile modulus of 1000 MPa, a pattern layer is formed by printing, and the back side of the pattern layer is oxidized. A colored hiding layer containing titanium was formed.

After embossing and corona discharge treatment on the front surface of the thermoplastic resin layer, a primer layer (layer thickness: 2 μm) was applied uniformly using a urethane acrylic primer at 2 g / m ² (during curing). ) Was formed. Next, a resin composition composed of a urethane acrylate oligomer (ionizing radiation curable resin) was applied and dried on the primer layer to form an uncured coating film. Thereafter, the resin was cured by irradiating an electron beam under the same conditions as in Example 1 to form an outermost layer (ionizing radiation curable resin layer, layer thickness: 30 μm), and a decorative sheet was produced.

  Further, the decorative sheet was laminated on the adherend by the same method as in Example 1 to obtain a decorative material.

Example 13
In the same manner as in Example 1, after obtaining a laminate comprising a back primer layer, a base sheet, a pattern layer, an adhesive layer and a thermoplastic resin layer, a two-component curable urethane resin was applied to form a lower layer (layer (Thickness: 10 μm) was formed. Subsequently, the resin composition consisting of urethane acrylate oligomer (ionizing radiation curable resin) was applied and dried to form an uncured coating film. Thereafter, in an environment with an oxygen concentration of 200 ppm or less, the uncured resin layer is irradiated with an electron beam under the conditions of an acceleration voltage of 200 keV and 3 Mrad to cure the resin, and the outermost layer (ionizing radiation curable resin layer, layer thickness: 10 μm). ) To form a decorative sheet.

  Further, the decorative sheet was laminated on the adherend by the same method as in Example 1 to obtain a decorative material.

Examples 14-17 and Comparative Examples 7-10
As shown in Tables 4 to 5 below, in the same manner as in Example 13, except that the physical properties (the resin component of the outermost layer, the thickness of the outermost layer, the thickness of the lower layer, the thickness of the thermoplastic resin layer, etc.) are appropriately changed. A decorative sheet and a decorative material were prepared.

Example 18
Except that the thickness of the thermoplastic resin layer was 60 μm, a laminate comprising a back primer layer, a base sheet, a pattern layer, an adhesive layer, a thermoplastic resin layer and a primer layer was obtained in the same manner as in Example 1. Thereafter, a two-component curable urethane resin was applied to form a lower layer (layer thickness: 10 μm). Subsequently, the resin composition consisting of urethane acrylate oligomer (ionizing radiation curable resin) was applied and dried to form an uncured coating film. Thereafter, in an environment having an oxygen concentration of 200 ppm or less, the uncured resin layer is irradiated with an electron beam under conditions of an acceleration voltage of 200 keV and 3 Mrad to cure the resin, and the outermost layer (ionizing radiation curable resin layer, layer thickness: 20 μm). ) To form a decorative sheet.

  Further, the decorative sheet was laminated on the adherend by the same method as in Example 1 to obtain a decorative material.

Examples 19 to 21 and Comparative Example 11
A decorative sheet and a decorative material as shown in Tables 6 to 7 below were prepared in the same manner as in Example 18 except that each physical property (thickness of the thermoplastic resin layer and the like) was changed as appropriate.

Test Methods The following tests were performed on the decorative materials obtained in Examples 1 to 21 and Comparative Examples 1 to 11.

≪Whitening wound test≫
The test was conducted using a Hoffman scratch tester manufactured by BYK-GARDNER, USA. Specifically, a scratch blade (φ7 cylindrical blade) was set so as to be in contact with the decorative material surface at an angle of 45 °, and the tester was moved on the decorative material. When the load (weight) is 1000 g, it is evaluated as ◎ when there is no scratch at all, ○ when there is no scratch but there is a slight change in appearance, △ when there is a slight scratch, and × when it is scratched did.

≪Scratch test≫
The surface of the decorative material was evaluated by rubbing 10 reciprocations at a load of 1500 g / cm ² using steel wool (Bonster # 0000: manufactured by Nippon Steel Wool Co., Ltd.). The thing which did not get a damage | wound was evaluated as (circle) and the thing with a damage | wound was evaluated as x.

≪Crack evaluation test≫
According to the JIS K5600 DuPont impact test, a shooting mold having a hemispherical tip with a radius of 6.3 mm is allowed to stand on the decorative material surface, and a weight of 500 g load is dropped from the height of 20 cm onto the shooting mold. It was evaluated by. The above test was performed 5 times on one decorative material, and the case where there was no crack on the surface of the decorative material was evaluated as ◯, the case where the crack occurred 1-3 times, the case where the crack occurred 4 times or more was evaluated as ×. did.

≪Dent scratch test≫
The test was conducted using a pencil hardness tester. Specifically, in the case where the test machine is positioned horizontally, JIS K5600-5-5 is used except that the test machine is set so as to apply a load of 1000 g to the tip of a pencil having a pencil hardness of “H”. The test was conducted according to 4. After the test, the case where there was no conspicuous dent was evaluated as ◯, the case where there was a dent was evaluated as Δ, and the case where the dent was conspicuous was evaluated as x.

The results are shown in Tables 1-7 below. In the table, “electron beam” and “two-component curing” of the resin component indicate that the following components were used as the resin component, respectively.
[Resin component showing “electron beam”]
• Bifunctional urethane acrylate (polyol component is polyester diol, glass transition point 25 ° C., molecular weight 1500) 80 parts by weight • Hexafunctional aliphatic urethane acrylate (glass transition point 200 ° C. or higher, molecular weight 1500)
20 parts by weight [resin component showing “two-component curing”]
・ Acrylic polyol 100 parts by weight ・ Hexamethylene diisocyanate (HMDI) -based curing agent 10 parts by weight

≪When the topcoat layer consists of a primer layer and the outermost layer≫

≪When the top coat layer consists of the lower layer and the outermost layer≫

≪When the topcoat layer consists of a primer layer, a lower layer and an outermost layer≫

That is, the present invention relates to the following decorative sheet.
1. A decorative sheet having at least a thermoplastic resin layer and a topcoat layer in order,
(1) The top coat layer comprises a plurality of layers, and has an outermost layer containing an ionizing radiation curable resin, a lower layer having a thickness of 5 μm or more and a primer layer having a thickness of 4 μm or less on the back side of the outermost layer in order .
(1) The top coat layer has an outermost layer containing an ionizing radiation curable resin,
(2) The thickness of the top coat layer is 20 μm or more,
(3) The thermoplastic resin layer has a thickness of 40 to 120 μm,
(4) The ratio of the thickness of the topcoat layer to the thickness of the thermoplastic resin layer is 20% or more.
A decorative sheet characterized by that.
2. The decorative sheet according to Item 1, wherein the thermoplastic resin layer has a tensile elastic modulus measured according to JIS K7161 of 400 to 1200 MPa.
3. Item 3. The decorative sheet according to Item 1 or 2, wherein the thermoplastic resin layer is an olefin resin.
4). Item 4. The decorative sheet according to any one of Items 1 to 3, further comprising a pattern layer, an adhesive layer, a thermoplastic resin layer, and a topcoat layer in this order on the substrate sheet.
5). Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the outermost layer has a Martens hardness of 40 to 140 N / mm ² .
6). A cosmetic material obtained by sticking the decorative sheet according to any one of Items 1 to 5 to a wooden substrate.

Claims (6)

A decorative sheet having at least a thermoplastic resin layer and a topcoat layer in order,
(1) The top coat layer has an outermost layer containing an ionizing radiation curable resin,
(2) The thickness of the top coat layer is 20 μm or more,
(3) The thermoplastic resin layer has a thickness of 40 to 120 μm,
(4) The ratio of the thickness of the topcoat layer to the thickness of the thermoplastic resin layer is 20% or more.
A decorative sheet characterized by that.   The decorative sheet according to claim 1, wherein a tensile elastic modulus of the thermoplastic resin layer measured according to JIS K7161 is 400 to 1200 MPa.   The decorative sheet according to claim 1 or 2, wherein the thermoplastic resin layer is an olefin resin.   The decorative sheet according to any one of claims 1 to 3, further comprising a pattern layer, an adhesive layer, a thermoplastic resin layer, and a topcoat layer in this order on the substrate sheet. The outermost layer of the Martens hardness is 40~140N / mm ^2, the decorative sheet according to claim 1.   A decorative material obtained by sticking the decorative sheet according to any one of claims 1 to 5 to a wooden substrate.