JP5471729B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet that repels water droplets.

Conventionally, in order to prevent contamination of the decorative sheet, proposals have been made to increase the antifouling property and water repellency of the decorative sheet surface.
For example, Patent Document 1 proposes a decorative sheet having, as a surface layer, an olefin resin layer containing a silicone polymer-introduced olefin resin obtained by chemically bonding a high molecular weight silicone polymer.
Patent Document 2 discloses a cosmetic having excellent stain resistance, having a transparent surface protective layer formed from an aqueous composition containing an aqueous emulsion of a (meth) acrylic resin composition and an aqueous dispersion of isocyanate. A sheet is proposed.
Furthermore, Patent Document 3 contains a monofunctional silicone (meth) acrylate having an average molecular weight of 100 to 3000 in order to provide a decorative sheet that is excellent in stain resistance and water repellency and that does not deteriorate over time. A decorative sheet having a surface protective layer obtained by crosslinking and curing an ionizing radiation curable resin composition is proposed.
Although these techniques have succeeded in suppressing the contamination of the decorative sheet to a certain extent, it is further required to greatly improve the anti-contamination performance of the decorative sheet.

Japanese Patent Laid-Open No. 11-129420 JP 2007-98660 A JP 2007-276464 A

  Under such circumstances, an object of the present invention is to increase the water repellency of the surface protective layer of the decorative sheet to such an extent that it repels water in order to greatly improve the anti-contamination performance of the decorative sheet.

  As a result of intensive studies to solve the above problems, the present inventor can solve the above problems by using a curable resin composition containing a specific amount of specific silica in the surface protective layer of the decorative sheet. I found out. The present invention has been completed based on such findings.

  That is, the present invention is a decorative sheet comprising at least a base material and a surface protective layer, the surface protective layer comprising a resin component (A) containing a curable resin and silica (B) subjected to a hydrophobic treatment. Is a decorative sheet obtained by crosslinking and curing a curable resin composition having a mass ratio [(A) / (B)] of (1/99) to (40/60).

  According to the present invention, since the surface of the decorative sheet comes to repel water, it is possible to provide a decorative sheet that can prevent the adhesion of aqueous substances to the surface of the decorative sheet and can greatly improve the pollution prevention performance.

It is a schematic diagram which shows the cross section of the decorative sheet of this invention.

The decorative sheet of the present invention is a decorative sheet comprising at least a base material and a surface protective layer, and the surface protective layer is a silica component (B) subjected to a hydrophobic treatment with a resin component (A) containing a curable resin. The curable resin composition having a mass ratio [(A) / (B)] of (1/99) to (40/60) is crosslinked and cured.
A typical structure of the decorative sheet of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing a cross section of a decorative sheet 1 of the present invention. In the example shown in FIG. 1, a colored layer 3 disposed as desired, a primer layer 4 disposed as desired, and a surface protective layer 5 obtained by crosslinking and curing a curable resin composition are laminated on the base material 2 in this order. It has the structure made.

  The base material 2 used for the decorative sheet 1 of the present invention is not particularly limited as long as it is usually used as a decorative sheet, and various plastic films, plastic sheets, metal foils, metal sheets, metal plates, various fibers can be used. Woven fabrics, nonwoven fabrics, papers, wood-based boards such as wood, ceramic materials and the like can be appropriately selected according to the application. Each of these materials may be used alone, but it may be a laminate of any combination, such as a composite of plastic films, a composite of a plastic film and a metal sheet, or a composite of a plastic film and paper. May be.

  Examples of the various plastic films or plastic sheets used as the substrate include those made of various synthetic resins. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 And polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, and the like.

Among the above, the base material is preferably a plastic film made of a polyester resin from the viewpoint of cost, heat resistance, adhesion to the substrate, suitability for electron beam irradiation, durability, and the like, and suppresses the elongation of the surface protective layer 5. A biaxially stretched polyester film is more preferable from the viewpoint of suppressing the occurrence of cracks in the surface protective layer 5.
The polyester resin used here is not particularly limited, and those usually used in the field of decorative sheets can be used. Examples thereof include polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, ethylene terephthalate-isophthalate copolymer, polyarylate, and the like. Among these, polyethylene terephthalate, polybutylene terephthalate, and the like are preferable, and polyethylene terephthalate is particularly preferable.
In addition, the polyester resin can use various homopolymers, copolymer polyester resins to which various copolymer components or modifying components are added for the purpose of softening the resin, polyester thermoplastic elastomers, etc. The biaxially stretched polyester film preferably used as the substrate 2 is prepared by, for example, forming a film by a calendar method, an inflation method, a T-die extrusion method, or the like, and biaxially stretching.

In the present invention, the thickness of the substrate 2 is not particularly limited, but the thickness is usually about 20 to 150 μm, preferably 25 to 100 μm. If thickness is in the said range, sufficient intensity | strength as a decorative sheet can be ensured and the tension | tensile_strength concerning the surface protective layer 5 can fully be relieve | moderated.
In addition, the biaxially stretched polyester resin film preferably used for the substrate 2 preferably has a tensile strength measured in accordance with JIS C2151 of 150 MPa or more.
When the tensile strength is 150 MPa or more, since it is highly rigid, local elongation generated in the bent portion can be suppressed, and extension of the upper surface protective layer can also be suppressed.

Moreover, the base material 2 may contain the coloring agent if desired. Thereby, it is possible not to dispose a colored layer to be described later.
In order to improve the adhesiveness with other layers, the base material 2 is optionally oxidized on one or both sides (corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, etc.) A physical or chemical surface treatment such as a concavo-convex method (sand blast method, solvent treatment method, etc.) can be applied.

  The surface protective layer 5 in the present invention is formed by crosslinking and curing a curable resin composition. This curable resin composition includes a resin component (A) containing a curable resin and silica subjected to hydrophobic treatment (hereinafter, may be referred to as “hydrophobized silica”) (B), and has a mass ratio. [(A) / (B)] is (1/99) to (40/60), preferably (5/95) to (40/60), more preferably (5/95) to (35 / 65), more preferably (10/90) to (35/65), and particularly preferably (10/90) to (30/70). If the mass ratio [(A) / (B)] is (1/99) or more [that is, if the resin component (A) is 1 or more], the hydrophobized silica (B) is difficult to fall off from the surface of the decorative sheet. If the resin component (A) is 5 or more, it is more difficult to fall off, which is preferable. Further, if the mass ratio [(A) / (B)] is (40/60) or less [that is, if the hydrophobized silica (B) is 60 or more], water can be repelled, and the hydrophobized silica ( If B) is 65 or more, it is more preferable because water droplets roll on the decorative sheet surface.

The silica used for the hydrophobized silica (B) may be either wet silica or dry silica. Examples of wet silica include Tokuyama Co., Ltd., trade name “Tokusil” series; Tosoh Silica Co., Ltd., trade name “Nipsil” series; Evonik Industries, trade name “Carplex” series; Spherical silica fine particles with a uniform particle size (0.2 to 12.0 μm) synthesized from silicon alkoxide, manufactured by Ube Nitto Kasei Co., Ltd., trade name “Hi-Pureshka” series, Toagosei Co., Ltd., trade name "HPS" series etc. are mentioned, As a dry-type silica, the product name "Excelica" series by Tokuyama Co., Ltd. etc. are mentioned, for example.
Silica having a wide particle size distribution preferably has a uniform particle size by classification or the like before or after the hydrophobic treatment.

The hydrophobized silica (B) according to the present invention is obtained by treating the above-mentioned silica by a known hydrophobizing treatment method. Various methods are known as the hydrophobizing method.
For example, JP-A-58-60754, JP-A-59-201063, JP-A-2-287458 and the like include hydrophobizing silica powder with a silicone oil-based processing agent, or alkylsilazane-based processing agent, trimethylsilyl. It describes that the silica powder is hydrophobized by treatment with the above-mentioned silicone oil-based treatment agent after treatment with an agent or alkoxysilane.
In addition, JP 2002-256170 A, JP 2004-168559 A, etc. have improved hydrophobicity by a two-stage treatment in which silica powder is treated with a silicone oil-based treating agent and then treated with a trimethylsilylating agent or an alkylsilazane-based treating agent. Silica powder is described.
In JP 2003-149855 A, JP 2003-261321 A, etc., a treatment method for hydrophobizing the silica surface with alkoxysilane, or a silicone oil treatment agent or a silicone oil treatment agent and an alkoxy after treatment with alkoxysilane. A processing method is described in which silane is used in combination.
Further, JP 2003-171117 A, JP 2003-171118 A, etc. disclose 1,3-dimethyl-1,3-bis (trimethylsiloxy) -1,3-dihydroxydisiloxane as a hydrophobizing agent for silica. A treatment method using dimer diol siloxane and / or trimethylsilanol or cyclic siloxane (such as hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane) is described.

Silicone oil treatment agents include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, and methacryl-modified. Silicone oil, mercapto modified silicone oil, phenol modified silicone oil, one-end reactive modified silicone oil, different functional group modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, higher fatty acid ester modified silicone Oil, hydrophilic specially modified silicone oil, higher alkoxy modified silicone oil, higher fat Acid-containing modified silicone oil, modified silicone oil and fluorine-modified silicone oil can be used.
Examples of the trimethylsilylating agent include trimethylsilanol, trimethylmethoxysilane, trimethylchlorosilane, aminomethyltrimethylsilane, dimethylaminotrimethylsilane, and diethylaminotrimethylsilane. Examples of the alkylsilazane treatment agent include hexamethyldisilazane and vinylsilazane. Can be mentioned.
Alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, decyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane. And alkylalkoxysilanes.

As the hydrophobizing treatment method applied to the hydrophobized silica (B) according to the present invention, various coupling agents such as a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zircoaluminum coupling agent, Treatment with a surfactant such as phosphoric acid or fatty acid, oil or fat, wax, stearic acid or the like is also included.
However, those having reactivity with the resin after hydrophobizing treatment such as silane coupling agents do not have the desired hydrophobicity in the portion having reactivity, and the proportion of the portion subjected to hydrophobic treatment in silica is In order to reduce the hydrophobic effect of the entire sheet by lowering, it is preferable to use a hydrophobizing agent that does not have reactivity with the resin after the hydrophobizing treatment.

The average particle diameter of the hydrophobized silica (B) obtained by the above hydrophobizing method is preferably 1 to 20 μm. The average particle size is selected so that silica appears on the surface of the surface protective layer and forms a concavo-convex structure in relation to the coating amount (g / m ² ) of the curable resin composition. From this viewpoint, the average particle diameter of the hydrophobized silica (B) is more preferably 2 to 15 μm. Here, the average particle diameter means an average secondary particle diameter (average aggregate particle diameter) when the primary particles have a secondary aggregate structure, and an average primary particle when the primary particles do not have a secondary aggregate structure. The particle diameter.

  Examples of the curable resin composition in the present invention include an ionizing radiation curable resin composition, a thermosetting resin composition, and the like, and an ionizing radiation curable resin composition is preferable because it can be crosslinked and cured at room temperature. Here, the ionizing radiation curable resin composition has an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, crosslinked and cured by irradiation with ultraviolet rays or electron beams. It refers to a resin composition.

The ionizing radiation curable resin used in the ionizing radiation curable resin composition in the present invention is appropriately selected from polymerizable monomers and polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resin compositions. Can be used.
The polymerizable monomer is preferably a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule, and more preferably a polyfunctional (meth) acrylate. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta Examples include erythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, silicon diacrylate, and silicon hexaacrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of the monofunctional (meth) acrylate include cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and the like. These monofunctional (meth) acrylates may be used alone or in combination of two or more.
In addition, monofunctional (meth) acrylate is contained in the curable resin which concerns on this invention.

Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate And the like.
Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. Etc.

When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, benzophenone, p-phenylbenzophenone, 4,4 Examples include '-diethylaminobenzophenone.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  In the present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. The electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, does not require an initiator for photopolymerization, and can easily control cross-linking curing and obtain stable curing characteristics. Because it is.

  The curable resin according to the present invention may be a thermosetting resin. As this thermosetting resin, either a two-component reaction curable resin or a single curable resin may be used. Specifically, a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, There are polyurethane resins, epoxy resins, amino alkyd resins, melamine-urea cocondensation resins, silicon resins, polysiloxane resins, etc., and if necessary, curing agents such as crosslinking agents and polymerization initiators, polymerization accelerators, What added the solvent, the viscosity modifier, extender, etc. is used. The curing agent is usually an unsaturated polyester resin, polyurethane resin, amine epoxy resin, peroxide such as methyl ethyl ketone peroxide, radical initiator such as azoisobutyl nitrile unsaturated polyester resin, etc. Often used. Further, as the isocyanate, a divalent or higher aliphatic isocyanate or aromatic isocyanate can be used, but an aliphatic isocyanate is desirable from the viewpoint of preventing thermal discoloration and weather resistance.

  The resin component (A) of the curable resin composition according to the present invention may be composed of only a curable resin. However, in addition to the curable resin described above, various thermoplastic resins may impair the object of the present invention. The range, for example, the mass ratio (curable resin / thermoplastic resin) can be appropriately used in the range of (50/50) to (100/0). Examples of the thermoplastic resin used in the present invention include (meth) acrylic resins such as (meth) acrylic acid esters, and these may be used alone or in combination of two or more. When combining 2 or more types, the copolymer of the monomer which comprises these resin may be sufficient, and each resin may be mixed and used.

  Moreover, various additives can be mix | blended with the curable resin composition in this invention according to the desired physical property of the surface protective layer obtained. Examples of the additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, and a coupling agent. , Plasticizers, antifoaming agents, fillers, solvents, colorants and the like.

In the present invention, the curable resin, the thermoplastic resin added as required, and various additives are homogeneously mixed at predetermined ratios to prepare a coating liquid composed of the curable resin composition. The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.
In the present invention, the hydrophobized silica used in such a manner that the coating solution prepared in this way is applied to the surface of the substrate so that the thickness after curing is preferably 1 to 20 μm, more preferably 1 to 10 μm. Is appropriately determined according to the type and average particle size, and is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure coating, to form an uncured resin layer . As a coating amount of a coating liquid, it is 1-20 g / m < ² > normally.

When an electron beam curable resin composition is used as the curable resin composition, the uncured resin layer formed as described above is irradiated with an electron beam to cure the uncured resin layer. The acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but it is preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably an amount that saturates the crosslink density of the resin layer, and is usually selected in the range of 5 to 300 kGy.

  The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a cockroft 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 are used. be able to.

In the decorative sheet of the present invention, a colored layer 3 may be provided on the base material 2 to enhance the design of the decorative sheet, if desired. The colored layer 3 is composed of a pattern layer and / or a concealing layer.
There are no particular restrictions on the type of pattern in the pattern layer. 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 concealing layer is a full surface solid layer.
The method for forming the pattern layer and the hiding layer is not particularly limited. For example, coloring 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 and coating method etc. which used the ink, the coating agent, etc.

Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, Examples include melamine resins. These resins can be used alone or in admixture of two or more.
Examples of the colorant include various inorganic pigments, various organic pigments (including dyes), metal pigments, and pearlescent (pearl) pigments.
Examples of the solvent (or dispersion medium) include petroleum organic solvents, ester organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and chlorine organic solvents.

Examples of the printing method used for forming the pattern layer and the concealing 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. Examples of the coating method include a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, a flow coating method, and a dip coating method.
The thicknesses of the pattern layer and the hiding layer are not particularly limited and can be appropriately set according to product characteristics, but the layer thickness after drying is about 0.1 to 10 μm.

The decorative sheet of the present invention is provided with a primer layer 4 as required in order to increase the adhesion between the substrate 2 and the surface protective layer 5 or to increase the adhesion between the substrate 2 and the colored layer 3 provided as desired. It may be provided.
As the ink used for forming the primer layer 4, an ink in which a filler such as extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like are appropriately mixed is used as necessary. The binder is not particularly limited, and examples thereof include ester resins, urethane resins, acrylic resins, urethane-acrylic copolymer resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, and nitrocellulose resins. These resins can be used alone or in combination of two or more.
Examples of the coating method for the primer layer 4 include the various coating methods and the various printing methods described above.
The thickness of the primer layer 4 is preferably in the range of 0.5 to 20 μm.

The decorative sheet of the present invention is provided on the surface of the substrate 2 opposite to the surface protective layer 5 (that is, the back surface of the substrate 2) as required in order to ensure good adhesion between the decorative sheet and the adherend. The adhesive layer can be laminated.
There is no restriction | limiting in particular as a material used for an adhesive bond layer, A well-known adhesive can be used in the field | area of a decorative sheet. Specific examples thereof include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.
Although there is no restriction | limiting in particular in the thickness of an adhesive bond layer, Usually, the thickness after drying is the range of 1-100 micrometers.

The decorative sheet of the present invention is used as a decorative plate by being attached to a wooden substrate as an adherend, and is used as a decorative steel plate by being attached to a steel plate.
Examples of the wood substrate include wood substrates such as wood plywood, particle board, medium density fiber board (MDF), and high density fiber board (HDF), and a substrate made of a flash structure. Although there is no restriction | limiting in particular about the thickness of a wooden substrate, Usually, it is about 0.2-5 mm.
Moreover, as a steel plate used as a to-be-adhered body, metal materials, such as iron, aluminum, and copper, are mentioned, These may be surface-treated, such as a hot dip galvanization process and an electrogalvanization process. Moreover, the shape of a to-be-adhered body is not specifically limited, For example, shapes, such as a flat plate, a curved surface board, a polygonal column, can be employ | adopted arbitrarily. Although there is no restriction | limiting in particular about the thickness of a steel plate, Usually, it is about 0.2-1 mm. In addition, in order to give the steel plate which is a to-be-adhered body concealment property, you may provide a coating layer by coloring directly to a steel plate.

The decorative plate using the decorative sheet 1 of the present invention can be used for kitchen wall materials, bathroom wall materials, unit bath wall materials, unit bath interior materials, door materials, AV equipment, air conditioner covers, etc. It is suitably used as kitchen wall materials, bathroom wall materials, unit bath wall materials, unit bath interior materials, etc. that require resistance to wetness around the water and moisture.
Similarly, the decorative steel sheet to which the decorative sheet of the present invention is attached is required to have resistance to wetness and moisture around the water, and is easily contaminated, kitchen set material, kitchen wall material, bathroom wall material, unit bath wall material, It is suitably used for unit bath interior materials. In addition, for building interior materials such as walls and ceilings, surface materials for fittings such as doors, door frames, and window frames, surface materials for construction members such as fringes and baseboards, surface materials for furniture such as fences and cabinets, etc. Can also be used.
Further, the decorative sheet itself can be used as a wall material, a laminate material for a building material member, a wrapping material, or the like, without using a wooden substrate or a steel plate as an adherend.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation method)
(1) Contact angle The contact angle (measured water temperature 25 degreeC) prescribed | regulated by JISR3257: 1999 measured using the contact angle measuring machine (Kyowa Interface Science contact angle meter CA-X type) was measured.
(2) Evaluation of water droplet behavior The behavior when water droplets were dropped on the surface was evaluated in four stages according to the following criteria. The larger the evaluation score, the better.
4: When the decorative sheet was tilted at 5 °, water droplets rolled down on the surface of the decorative sheet.
3: When the decorative sheet was tilted at 30 °, water droplets rolled down on the surface of the decorative sheet.
2: When the decorative sheet was tilted at 30 °, water droplets did not roll on the decorative sheet surface, but the water droplets slowly slipped down along the decorative sheet surface.
1: When the decorative sheet was tilted to 30 °, water droplets did not roll on the surface of the decorative sheet and did not slide down slowly.

Production Example 1
Silica obtained by classifying Ube Nitto Kasei Co., Ltd. product name “HI-PRECICA TS” to an average particle size of 3 μm is dried at 150 ° C. for 3 hours, so that the amount of adsorbed moisture is 0.23 mass%. Adjusted. 200 g of this fine silica powder after adjustment was charged into a vibrating fluidized bed (vibrating fluidized phase device manufactured by Chuo Kako Co., Ltd.) and n-octyltriethoxy while being vibrated and flowed with air dehumidified to a moisture content of 0.38% by mass. After spraying 12 g of silane, another 15 g of dimethyl silicone oil was sprayed and fluidly mixed for 30 minutes. Thereafter, it was immediately put into a constant temperature and humidity chamber maintained at a temperature of 25 ° C. and a humidity of 90%, and maintained for 72 hours to produce hydrophobized silica.

Example 1
A biaxially stretched transparent PET film (“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm is used as the base material 2 and its surface is made of urethane as a binder, with titanium oxide, quinacridone red and isoindolinone Using an ink containing a yellow-based colorant, the concealing layer and the abstract pattern pattern layer were gravure printed in that order to form the colored layer 3. On the colored layer 3, a 2 g / m ² (full surface) layer with a coating amount of urethane-acrylic copolymer resin (copolymerization ratio 5: 5) as a binder is gravure-printed. To give a primer layer 4. The thickness of the primer layer 4 was 2 μm.
Next, a curable resin composed of 60 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate as a trifunctional acrylate monomer and 40 parts by mass of dipentaerythritol hexaacrylate as a hexafunctional acrylate monomer on the primer layer 4. An electron beam curable resin composition comprising 40% by mass of the resin component (A) and 60% by mass of hydrophobized silica having an average particle diameter of 3 μm obtained in Production Example 1 was applied at 2 g / m ² by the gravure direct coater method. Worked. After coating, an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated to crosslink and cure the electron beam curable resin composition, whereby the surface protective layer 5 was obtained. Next, curing was performed at 70 ° C. for 24 hours to obtain a decorative sheet 1. The thickness of the surface protective layer 5 was 3.0 μm.
The obtained decorative sheet 1 was evaluated by the above method. The evaluation results are shown in Table 1.

Examples 2 to 4 and Comparative Examples 1 to 4
As shown in Table 1, Examples 2 to 4 and Comparative Example were carried out in the same manner as in Example 1 except that the mass ratio between the curable resin and the hydrophobized silica and the coating amount of the curable resin composition were changed. 1-4 decorative sheets 1 were obtained. The obtained decorative sheet 1 was evaluated by the above method. The evaluation results are shown in Table 1.

  The decorative sheet of the present invention is a decorative sheet, a decorative steel sheet, or a decorative sheet itself, such as kitchen set materials, kitchen wall materials, bathroom wall materials, unit bath wall materials, unit bath interior materials, walls, and ceilings. Interior materials for buildings, surface materials for fittings such as doors, door frames and window frames, surface materials for construction members such as rims and baseboards, surface materials for furniture such as fences and cabinets, AV equipment, air conditioner covers, and building material members Can be used for laminating materials, wrapping materials, etc., but is particularly suitable as kitchen wall materials, bathroom wall materials, unit bath wall materials, unit bath interior materials, etc. that require resistance to wetness around the water and moisture. Used for.

1. Cosmetic sheet Base material 3. 3. Colored layer Primer layer 5. Surface protective layer

Claims (3)

A decorative sheet comprising at least a substrate and a surface protective layer, wherein the surface protective layer is a mass ratio of a resin component (A) containing a curable resin and a hydrophobized silica (B) [(A ) / (B)] Ri is (1/99) - (Na by crosslinking and curing the curable resin composition is 40/60), the average particle size of the silica (B) is 1 to 20 [mu] m, the decorative sheet the silica on the surface of the surface protective layer (B) is characterized Rukoto such to emerge. The decorative sheet according to claim 1, wherein the surface protective layer has a thickness of 1 to 20 μm.   The decorative sheet according to claim 1 or 2, wherein the curable resin composition is an ionizing radiation curable resin composition.

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