JP6020618B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet.

  A decorative sheet having a surface protective layer made of an ionizing radiation curable resin on the outermost surface is excellent in physical properties such as wear resistance, impact resistance, stain resistance, and scratch resistance, and is suitable as a sheet for flooring, for example. It is used for. Here, the ionizing radiation curable resin is appropriately blended with a prepolymer, an oligomer and / or a monomer containing a radical polymerizable double bond capable of undergoing a polymerization crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. It will be. Such a decorative sheet is disclosed in Patent Document 1, for example.

JP 2008-267126 A

  However, since the decorative sheet described in Patent Document 1 still has insufficient scratch resistance, development of a decorative sheet having excellent scratch resistance is desired.

  For example, there is a method of improving the scratch resistance by increasing the thickness of the surface protective layer containing an ionizing radiation curable resin as compared with a conventional decorative sheet. However, when the thickness of the surface protective layer is increased (thickened), there is a problem that impact resistance is lowered and coating film cracking is likely to occur. Moreover, according to the said thick film, the solvent contained in the resin composition for forming a surface protective layer becomes difficult to dry, As a result, the said solvent becomes easy to remain in a surface protective layer. Furthermore, when a matte material is included in the surface protective layer for the purpose of imparting design properties to the decorative sheet, it is difficult for the matte material to be present on the surface in the surface protective layer, resulting in a matte effect. There is a problem that it is not obtained and the designability is lowered.

  Accordingly, an object of the present invention is to provide a decorative sheet having excellent scratch resistance and impact resistance.

  As a result of intensive studies, the inventor has found that a decorative sheet can achieve the above-mentioned purpose when having a specific layer structure and containing a specific resin in the outermost surface protective layer. The invention has been completed.

That is, this invention relates to the following decorative sheet and its manufacturing method, and a decorative board and its manufacturing method.
1. A decorative sheet having, in order, at least a first surface protective layer, a primer layer, and a second surface protective layer on a substrate sheet,
(1) Each of the first surface protective layer and the second surface protective layer contains an ionizing radiation curable resin as a resin component,
(2) The sum of the thickness of the first surface protective layer and the thickness of the second surface protective layer is 20 μm or more,
(3) The second surface protective layer contains silica,
(4) The primer layer has a thickness of 7 to 10 μm and contains an acrylic polyol resin .
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the thickness of the second surface protective layer is 1 to 20 µm.
3. A decorative material, wherein the decorative sheet according to Item 1 or 2 is bonded onto an adherend.
4). A method for producing a decorative sheet having, in order, at least a first surface protective layer, a primer layer, and a second surface protective layer on a base sheet,
(1) Each of the first surface protective layer and the second surface protective layer contains an ionizing radiation curable resin as a resin component,
(2) The sum of the thickness of the first surface protective layer and the thickness of the second surface protective layer is 20 μm or more,
(3) The second surface protective layer contains silica,
(4) The primer layer has a thickness of 7 to 10 μm and contains an acrylic polyol resin .
A method for producing a decorative sheet, comprising the following steps (i) to (v):
(i) Step 1 of applying a composition 1 for forming the first surface protective layer containing the ionizing radiation curable resin on a laminate including a base sheet;
(ii) Step 2 of forming the first surface protective layer by irradiating the applied composition 1 with ionizing radiation;
(iii) Step 3 of forming the primer layer by applying a composition for forming the primer layer on the first surface protective layer;
(iv) applying a composition 2 for forming the second surface protective layer containing the ionizing radiation curable resin and the silica on the primer layer; and
(v) Step 5 of forming the second surface protective layer by irradiating the applied composition 2 with ionizing radiation,
A method for producing a decorative sheet, comprising:
5. A method for producing a decorative material, comprising bonding an adherend and a decorative sheet obtained by the method described in Item 4 above.

  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 first surface protective layer, a primer layer, and a second surface protective layer in this order,
(1) Each of the first surface protective layer and the second surface protective layer contains an ionizing radiation curable resin as a resin component,
(2) The sum of the thickness of the first surface protective layer (hereinafter also referred to as h ₁ ) and the thickness of the second surface protective layer (hereinafter also referred to as h ₂ ) is 20 μm or more.
It is characterized by that.

  The decorative sheet of the present invention having the above characteristics has a specific layer structure, and the first surface protective layer and the second surface protective layer satisfy specific conditions, respectively, so that it has excellent scratch resistance and impact resistance. The surface protective layer has excellent adhesion (interlayer adhesion between the first surface protective layer and the second surface protective layer).

  The configuration of the decorative sheet of the present invention is not limited, and may be any decorative sheet in which at least a first surface protective layer, a primer layer, and a second surface protective layer are laminated on a base sheet. For example, a decorative sheet in which a pattern layer, a colored concealing layer, an adhesive layer, a thermoplastic resin layer, a first surface protective layer, a primer layer, and a second surface protective layer are sequentially laminated on a substrate sheet can be used. Hereinafter, each layer constituting the decorative sheet will be described as a representative example.

(Substrate 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, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polybutene, polymethylpentene, polycarbonate, polyethylene naphthalate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid Examples thereof include thermoplastic resins such as copolymers, ethylene-acrylic acid ester copolymers, ethylene-propylene-butene copolymers, ionomers, acrylic acid esters, methacrylic acid esters, and polyolefin-based thermoplastic elastomers. The said base material sheet can use these resin individually or in combination of 2 or more types.

  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.

  One or both surfaces of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface may be 30 dyne or more, preferably 40 dyne 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 primer layer is provided on the back side of the base sheet, the material (including additives), coating method, and the like are the same as those of the primer layer (second primer layer) described later. Although the thickness of a back surface primer layer is not limited, Usually, about 1-3 micrometers is preferable.

(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 etc. 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 resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These resins can be used alone or in admixture of two or more.

  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. The layer thickness at the time of coating is preferably about 1 to 15 μm, and the layer thickness after drying is preferably 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, the base sheet is colored, but a colored concealing layer may be further formed to stabilize the concealing property.

  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 appropriately set according to the product characteristics. The layer thickness during coating is preferably about 0.2 to 10 μm, and the layer thickness after drying is preferably about 0.1 to 5 μm.

(Adhesive layer)
An adhesive layer may be formed as necessary in order to enhance the adhesion between the thermoplastic resin layer and the pattern layer 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 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.

  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 about 1-20 micrometers is good.

(Thermoplastic resin layer)
A thermoplastic resin layer can be formed on the adhesive layer as necessary.

  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, acrylic acid esters, methacrylic acid esters, polycarbonates, and cellulose triacetates. These resins can be used alone or in combination of two or more.

  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 the laminating method include a laminating method by a dry laminating method.

  Although the thickness of a thermoplastic resin layer is about 20-200 micrometers normally, it may exceed the said range according to the use etc. of a decorative sheet.

(First surface protective layer)
In the decorative sheet of the present invention, a first surface protective layer is formed on the front surface of the thermoplastic resin layer.

  The first surface protective layer contains at least an ionizing radiation curable resin as a resin component. Therefore, scratch resistance, impact resistance, etc. as a decorative sheet can be enhanced.

  The ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds capable of undergoing a crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. Can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.

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

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000. 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 an acrylate group, it is obtained as a bifunctional (meth) acrylate compound having an acryloyl group at both ends.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

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

  In the first surface protective layer, various resins can be used in combination with the ionizing radiation curable resin as a 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.

  Although the hardening method of a 1st surface protective layer is not specifically limited, For example, irradiating the said ionizing radiation is mentioned.

  By irradiation with ionizing radiation, at least the ionizing radiation curable resin contained in the first surface protective layer can be crosslinked and cured. 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, more preferably 3 to 7 Mrad.

  The first surface protective layer may use a matting material for the purpose of further enhancing the matting effect (matting) of the surface. As the matting material, the same matting material as described in the section of the second surface protective layer described later can be used. The content of the matting material can be the same as the content described in the section of the second surface protective layer.

  The first surface protective layer further includes a UV absorber, a light stabilizer, an antibacterial agent, a colorant such as a solvent, a dye, and a pigment, an anti-foaming agent, a leveling agent, Various additives such as a thixotropic agent can be added. About the said ultraviolet absorber, light stabilizer, antibacterial agent, and antiwear material, the thing similar to what was described in the term of the 2nd surface protective layer mentioned later can be used.

  About the formation method of the 1st surface protective layer containing ionizing radiation curable resin, what is necessary is just to follow a well-known method. For example, a composition (coating material) containing an ionizing radiation curable resin may be prepared and applied by a known coating method such as a gravure coating method or a roll coating method. The coating amount of the composition in this case is not particularly limited, and may be set as appropriate so that the thickness of the surface protective layer falls within the above range.

The thickness (h ₁ ) of the first surface protective layer is within the range of values described later, that is, the sum of the thickness of the first surface protective layer and the thickness of the second surface protective layer (ie, h ₁ + h ₂ ). Although it does not specifically limit and it can set suitably according to the characteristic of a final product, Usually, 1-30 micrometers, Preferably about 1-20 micrometers is good.

(Primer layer)
When the second surface protective layer is formed directly on the front surface of the first surface protective layer, a strain (internal stress) is caused between the adjacent layers due to a difference in stress generated when the ionizing radiation curable resin of each layer is cured. ) Occurs, and sufficient adhesion cannot be obtained between the surface protective layers. Therefore, the above problem is solved by forming a primer layer (hereinafter also referred to as a second primer layer) between the first surface protective layer and the second surface protective layer. That is, by forming the primer layer, excellent adhesion can be imparted between the first surface protective layer and the second surface protective layer. Further, since the primer layer is not cured by ionizing radiation, it is more flexible than the first surface protective layer and the second surface protective layer, and has the effect of alleviating distortion between the surface protective layers. Therefore, not only adhesion but also excellent impact resistance is imparted.

  Examples of the material for forming the primer layer include polyester resin, polyurethane resin, acrylic resin, polycarbonate resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral resin, nitrocellulose resin, acrylic-urethane copolymer ( In addition to resins such as acrylic-urethane resins) and two-component curable urethane resins, compounds such as alkyl titanates and ethyleneimines can also be used. Among these, it is preferable to use at least one selected from the group consisting of acrylic resins and acrylic-urethane resins. The materials for forming these primer layers can be used alone or in combination of two or more. The primer layer includes any of colorless and transparent, colored and transparent, translucent and the like.

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

  The primer layer may further contain a known additive in the primer agent, if necessary. For example, by including a hexamethylene diisocyanate curing agent in the primer agent, the adhesion between the first surface protective layer and the second surface protective layer described later can be further improved.

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

  The thickness of the primer layer is not particularly limited, but may be 1 to 10 μm, more preferably 2 to 4 μm. If the thickness of the primer layer is too large, the impact resistance will decrease.

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

(Second surface protective layer)
In the decorative sheet of the present invention, a second surface protective layer is formed on the front surface of the primer layer.

The second surface protective layer (and the first surface protective layer) contains at least an ionizing radiation curable resin as a resin component, and the sum of the thickness of the first surface protective layer and the thickness of the second surface protective layer (that is, h ₁ + h ₂ ) is 20 μm or more, so that the decorative sheet of the present invention is excellent in scratch resistance and impact resistance. Furthermore, when the second surface protective layer contains a matting material, the matting material is likely to be present on the surface layer of the decorative sheet, and as a result, design can be effectively imparted.

The total thickness (h ₁ + h ₂ ) of the first surface protective layer and the second surface protective layer is at least 20 μm or more, more preferably 30 μm or more. The upper limit of h ₁ + h ₂ is preferably about 60 μm.

The thickness (h ₂ ) of the second surface protective layer is not particularly limited as long as h ₁ + h ₂ is within the above range, and can be appropriately set according to the properties of the final product, but is usually 1 to 30 μm, preferably 1 About 20 μm is preferable.

  Similar to the first surface protective layer, the second surface protective layer contains at least an ionizing radiation curable resin as a resin component. As the ionizing radiation curable resin, a resin similar to the ionizing radiation curable resin described in the section of the first surface protective layer can be used.

  In addition to the ionizing radiation curable resin, various resins can be used in combination for the second surface protective layer. As the resin that can be used in combination, a resin similar to the resin described in the section of the first surface protective layer (for example, a thermosetting resin) can be used.

  Matte materials include inorganic matte materials such as silica, calcium silicate, aluminum silicate, magnesium silicate, kaolin, mica, talc, titanium dioxide, calcium carbonate, barium carbonate, α-alumina, chromium oxide, iron oxide, diamond, etc. And organic matte materials such as polyurethane, polystyrene, polyamide, polyvinyl chloride, acrylic and other fine particle polymers. Among these, silica is preferable from the viewpoint that the matting effect per weight of the matting material is high. In addition, the said mat | matte material can be used 1 type, or 2 or more types.

  The average particle size of the matting material is not particularly limited and can be appropriately set according to the thickness of the second surface protective layer, but is usually 1 to 30 μm, preferably about 1 to 20 μm. Here, the average particle diameter means a particle diameter (D50) corresponding to a cumulative frequency of 50%. The average particle diameter can be measured by a known method such as a laser diffraction method, a Coulter counter method, or a sedimentation method.

  When the matting material is contained in the second surface protective layer, the content can be set as appropriate, but it is 1 to 30 parts by weight with respect to 100 parts by weight of the resin component forming the second surface protective layer. Is preferable, and it is more preferable that it is 1-25 weight part.

  For the second surface protective layer, if necessary, UV absorbers, light stabilizers, antibacterial agents, solvents, dyes, pigments and other colorants, gloss modifiers, antiwear agents, fillers such as fillers, antifoaming Various additives such as an agent, a leveling agent and a thixotropy imparting agent can be added.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylate, and triazine. Further, when the resin layer is cured by irradiating with ultraviolet rays, as photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-amino oxime ester, tetramethylthiuram monosulfide, thioxanthones, aromatic As a photopolymerization accelerator (sensitizer) such as diazonium salt, aromatic sulfonium salt, metallocene, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be used.

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

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

  Examples of the anti-wear material include inorganic anti-wear materials such as silica, wollastonite, and alumina, and resin-type anti-wear materials such as acrylic. When the antiwear material is contained, the content is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin component.

  About the formation method and hardening method of a 2nd surface protective layer, it can be set as the method similar to the method described in the term of the said 1st surface protective layer.

  The decorative sheet of the present invention may be provided with a primer layer (hereinafter also referred to as a first primer layer) between the thermoplastic resin layer and the first surface protective layer, as necessary. By providing the primer layer, the formation of the first surface protective layer can be facilitated. The primer layer includes any of colorless and transparent, colored and transparent, translucent and the like.

  With respect to various additives such as the material for forming the first primer layer, the matting agent, and the weathering agent, the same materials and additives as those described for the second primer layer can be used.

  The method for forming the first primer layer is the same as the method described in the section of the second primer layer (or the first surface protective layer).

  The thickness of a 1st primer layer is not specifically limited, About 1-10 micrometers is good.

Manufacturing method of decorative sheet In the decorative sheet of the present invention, the first surface protective layer, the primer layer (second primer layer) and the second surface protective layer are formed so that the second surface protective layer is the outermost surface. Is obtained. For example, after laminating a pattern layer (and colored hiding layer), an adhesive layer, a thermoplastic resin layer, a first primer layer, a first surface protective layer and a second primer layer on a base sheet, on the outermost surface It is obtained by forming the second surface protective layer.

  The first surface protective layer can be cured after the first surface protective layer, the second primer layer, and the second surface protective layer are all laminated, and then cured after the first surface protective layer is laminated. The second primer layer and the second surface protective layer are preferably laminated on the cured first surface protective layer. By this method, the second primer layer can be efficiently laminated on the first surface protective layer.

  Moreover, when embossing of a decorative sheet is given, it may be after forming a 2nd surface protective layer, and may be before forming a 2nd surface protective layer. For example, as specific embodiments, 1) a pattern layer, a thermoplastic resin layer, a first primer layer, a first surface protective layer, a second primer layer, and a second surface protective layer are formed on the base sheet, and finally May be embossed. Moreover, as another aspect, 2) After forming an image pattern layer, a thermoplastic resin layer, a 1st primer layer, a 1st surface protective layer, and a 2nd primer layer in order on a base material sheet, embossing is given, and the last A second surface protective layer may be formed. As still another specific embodiment, 3) a pattern layer, a thermoplastic resin layer, a first primer layer, and a first surface protective layer are sequentially formed on the base sheet, and then embossed, Two primer layers may be provided and finally the second surface protective layer may be formed.

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

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

Cosmetic Material A cosmetic material can be obtained by bonding the decorative sheet to various adherends so that the second surface protective layer of the decorative sheet of the present invention is the outermost surface. 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, a single board, plywood, particle board, fiber board, laminated timber and the like made of cedar, straw, firewood, lauan, teak and the like can be mentioned.

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

  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. 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 can be used alone or in combination of two or more.

  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.

  The decorative sheet of the present invention has a specific layer structure, and each of the first surface protective layer and the second surface protective layer satisfies specific conditions. Therefore, the decorative sheet is excellent in scratch resistance and impact resistance. Excellent in properties.

It is a schematic diagram which illustrates the layer structure of the decorative sheet of this invention.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
A primer layer was provided on the back surface of a base sheet made of a colored polypropylene film having a thickness of 60 μm. Next, a pattern layer was formed on the front surface of the base sheet by printing, and an adhesive layer was further formed on the pattern print pattern layer. A polypropylene resin sheet was laminated on the adhesive layer by extrusion lamination to form a thermoplastic resin layer.

  A resin composition comprising a urethane acrylate oligomer (ionizing radiation curable resin) after forming a first primer layer (layer thickness: 2 μm) by coating a two-component curable urethane resin on the thermoplastic resin layer. Was coated 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 was irradiated with an electron beam under conditions of an acceleration voltage of 125 KeV and 5 Mrad to cure the resin, thereby forming a first surface protective layer (layer thickness: 15 μm). .

  A corona discharge treatment was applied to the front surface of the first surface protective layer, and then a two-component curable acrylic-urethane resin was applied to form a second primer layer (layer thickness: 2 μm). Furthermore, after a resin composition comprising 100 parts by weight of a urethane acrylate oligomer (ionizing radiation curable resin) and 14 parts by weight of silica (average particle size 13 μm) is coated and dried to form an uncured coating film, The electron beam was irradiated to the 2nd surface protective layer on the same conditions as the electron beam irradiated when forming 1 surface protective layer.

Example 2
A decorative sheet was prepared in the same manner as in Example 1 except that the thickness of the second primer layer was 4 μm.

Example 3
A decorative sheet was prepared in the same manner as in Example 1 except that the thickness of the second primer layer was 7 μm.

Example 4
A decorative sheet is prepared in the same manner as in Example 1 except that the second primer layer (layer thickness: 2 μm) is formed by applying an acrylic polyol resin instead of the two-component curable acrylic-urethane resin. did.

Example 5
A decorative sheet was prepared in the same manner as in Example 4 except that the thickness of the second primer layer was 4 μm.

Example 6
A decorative sheet was prepared in the same manner as in Example 4 except that the thickness of the second primer layer was 7 μm.

Example 7
A decorative sheet was prepared in the same manner as in Example 1 except that the silica content was 8 parts by weight with respect to 100 parts by weight of the urethane acrylate oligomer (ionizing radiation curable resin).

Comparative Example 1
A decorative sheet was prepared in the same manner as in Example 1 except that the second primer layer was not formed.

Comparative Example 2
Resin comprising 100 parts by weight of urethane acrylate oligomer (ionizing radiation curable resin) and 14 parts by weight of silica as a resin composition for forming the first surface protective layer without forming the second surface protective layer and the second primer layer. A decorative sheet was prepared in the same manner as in Example 1 except that the composition was used.

Reference example 1
A decorative sheet was formed by the same method as in Comparative Example 2 except that the thickness of the first surface protective layer was 15 μm.

<Evaluation Test Example 1 (Designability Test)>
The surface gloss values of the decorative sheets obtained in Examples 1 to 7, Comparative Examples 1 and 2 and Reference Example 1 were measured using a 60-degree gloss meter (“GMX-202”, manufactured by Murakami Color Research Laboratory Co., Ltd.). It was measured.

<Evaluation Test Example 2 (Scratch Resistance: Pencil Hardness Test)>
For the decorative sheets obtained in Examples 1 to 7, Comparative Examples 1 and 2 and Reference Example 1, a scratch hardness tester (“PSH540-40IT”, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, and JIS K5600- The test was carried out according to 5-4. Those that can be evaluated as hardness H or higher were evaluated as ◎, those that could be evaluated as hardness HB or higher as ○, and those that did not satisfy hardness 2B as ×.

<Evaluation Test Example 3 (Scratch Resistance: Hoffman Scratch Test)>
The scratch resistance of the decorative sheets obtained in Examples 1 to 7, Comparative Examples 1 and 2 and Reference Example 1 was confirmed using a Hoffman scratch tester (BYK-Gardnar).

  Specifically, a scratch blade (a cylindrical edge portion having a diameter of 7 mm) is set so as to contact the surface protective layer of the decorative sheet at an angle of 45 degrees, and the surface is moved by pulling the scratch blade. Rubbed. At that time, it was confirmed whether or not the surface protective layer was damaged by changing the load applied to the scratch blade by 100 g in the range of 300 to 700 g.

  The case where no scratch was observed at a load of 1000 g was evaluated as ◎, the case where no scratch was observed at a load of 500 g, and the case where a scratch was clearly noticeable at a load of 500 g were evaluated as x.

<Evaluation Test Example 4 (Shock Resistance Test)>
A DuPont impact resistance test was performed on Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1 in accordance with JIS K 5600-5-3. Specifically, a weight of 500 g is dropped from a height of 300 mm above the indenter vertically against an r = 6.3 mm hemispherical indenter (a hemispherical surface is in contact with the decorative material) placed on the floor decorative material surface. It was confirmed whether or not the surface protective layer was cracked. The case where the crack of the decorative sheet could not be visually observed was evaluated as ◯, the case where the crack was slightly observed was evaluated as Δ, and the case where the clear crack was observed was evaluated as ×.

<Evaluation Test Example 5 (Adhesion Test)>
For the second surface protective layer side of the decorative sheets obtained in Examples 1 to 7, Comparative Examples 1 to 2 and Reference Example 1, cellophane tape (cello tape (registered trademark), industrial 18 mm width, manufactured by Nichiban Co., Ltd.) ) Was peeled off at an angle of 45 degrees, and the decorative sheet and the cellophane tape were visually observed. Regarding the decorative sheet, the case where peeling of the coating film was not observed was evaluated as “◯”, the case where slight peeling was observed as “Δ”, and the case where remarkable peeling was observed as “×”.

In addition, the said adhesive test is a decorative sheet of the following (1)-(2):
(1) A decorative sheet immediately after production,
(2) Using the super accelerated weathering tester (“I Super UV Tester”, manufactured by Iwasaki Electric Co., Ltd.) (hereinafter referred to as S-UV) for the decorative sheet of (1) above, temperature 63 ° C. humidity 50 Under the condition of% RH, the light was irradiated for 20 hours with light having an illuminance of 60 mW / cm ² (365 nm), and then the decorative sheet after repeating the cycle of 4 hours of condensation for 200 hours was performed. .

  The test results are shown in Table 1 below. In Table 1, A / U indicates a two-component curable acrylic-urethane copolymer (resin), AP indicates an acrylic polyol resin, and U indicates a two-component curable urethane resin.

Claims (5)

A decorative sheet having, in order, at least a first surface protective layer, a primer layer, and a second surface protective layer on a substrate sheet,
(1) Each of the first surface protective layer and the second surface protective layer contains an ionizing radiation curable resin as a resin component,
(2) The sum of the thickness of the first surface protective layer and the thickness of the second surface protective layer is 20 μm or more,
(3) The second surface protective layer contains silica,
(4) The primer layer has a thickness of 7 to 10 μm and contains an acrylic polyol resin .
A decorative sheet characterized by that.   The decorative sheet according to claim 1, wherein the thickness of the second surface protective layer is 1 to 20 µm.   A decorative material obtained by bonding the decorative sheet according to claim 1 or 2 onto an adherend. A method for producing a decorative sheet having, in order, at least a first surface protective layer, a primer layer, and a second surface protective layer on a base sheet,
(1) Each of the first surface protective layer and the second surface protective layer contains an ionizing radiation curable resin as a resin component,
(2) The sum of the thickness of the first surface protective layer and the thickness of the second surface protective layer is 20 μm or more,
(3) The second surface protective layer contains silica,
(4) The primer layer has a thickness of 7 to 10 μm and contains an acrylic polyol resin .
A method for producing a decorative sheet, comprising the following steps (i) to (v):
(i) Step 1 of applying a composition 1 for forming the first surface protective layer containing the ionizing radiation curable resin on a laminate including a base sheet;
(ii) Step 2 of forming the first surface protective layer by irradiating the applied composition 1 with ionizing radiation;
(iii) Step 3 of forming the primer layer by applying a composition for forming the primer layer on the first surface protective layer;
(iv) applying a composition 2 for forming the second surface protective layer containing the ionizing radiation curable resin and the silica on the primer layer; and
(v) Step 5 of forming the second surface protective layer by irradiating the applied composition 2 with ionizing radiation,
A method for producing a decorative sheet, comprising:   The manufacturing method of a cosmetic material which joins a to-be-adhered material and the decorative sheet obtained by the method of Claim 4.