JP2000301681A - Decorative sheet and decorative material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet having thermoforming properties, antistaining properties, weatherability, transparency and the easy adhesiveness with the same adherend as those of a decorative sheet using a polyvinyl chloride resin by combining an acrylic resin sheet and an amorphous polyethylene terephthalate resin film. SOLUTION: A colored substrate sheet 11 consisting of an acrylic resin and a colorant is used as a substrate sheet and a pattern layer 12 and an easy adhesive layer 14 are formed on the colored substrate sheet 11 and a transparent amorphous PET film 13 is laminated on the easy adhesive layer by thermal fusion to form a laminated sheet and a transparent topcoat layer 16 comprising a thermosetting resin containing a fluorine group is formed on the transparent amorphous PET film 13 of the laminated sheet and an easy adhesive layer 15 is formed on the rear surface of the colored substrate sheet 11 to form a decorative sheet 1 excellent in thermoforming properties, abrasion resistance, scratch resistance, antistaining properties and weatherability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for interior decoration of buildings, surface decoration of fittings, interior decoration of vehicles, and a decorative material using the same. In particular, even when the surface of a molded article is decorated by vacuum forming using a decorative sheet, the vacuum forming suitability is improved so that a good surface decoration can be achieved.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used as a surface decoration material for interiors such as walls and ceilings of buildings, furniture, cabinets and the like, a polyvinyl chloride sheet is often used as a base sheet. For example, there are a sheet in which a grain pattern or the like is printed on a polyvinyl chloride sheet and a transparent polyvinyl chloride sheet is laminated on the sheet pattern, and a sheet in which a transparent polyvinyl chloride sheet is embossed. As a substitute for the polyvinyl chloride sheet, a decorative sheet using a polyolefin resin sheet such as polyethylene or polypropylene has been proposed (see Japanese Patent Application Laid-Open No. Sho 54-62255).

Further, as a decorative sheet using an acrylic resin sheet, an acrylic resin sheet is used as a base sheet,
A decorative sheet using a polyolefin resin sheet on the surface or a polyvinyl chloride sheet on the base sheet and an acrylic resin sheet on the surface is also used.

[0004]

However, decorative sheets using polyvinyl chloride sheets are said to have a risk of generating hydrochloric acid gas and dioxin when discarded and incinerated. There is a problem with later disposal.
There are also problems such as insufficient heat resistance and contamination of the surface by bleed-out of the plasticizer. In addition, since a decorative sheet using a polyolefin resin sheet such as polyethylene and polypropylene does not have a polar group,
In the case of forming a picture layer, it was necessary to provide an easy-adhesion layer such as a corona discharge treatment or a method of forming a primer layer on the surface of the olefin-based resin sheet in order to improve the adhesive strength with the printing ink. Furthermore, a decorative sheet using a polyolefin-based resin sheet has a problem that, when decorating the surface of a molded product by vacuum forming, the suitability for vacuum forming is inferior to a decorative sheet using polyvinyl chloride.

[0005] Further, when a decorative sheet using an acrylic resin film on the surface is used for surface decoration of a three-dimensional molded article having an irregular shape, the decorative sheet formed by vacuum forming may return due to application of heat. Or a change in surface gloss. Furthermore, when an acrylic resin sheet is used for the base material sheet and a polyolefin resin film is used for the surface film, the elongation is poor, and when performing surface decoration of a three-dimensional molded product by vacuum molding, it is difficult to form a molded product having a complicated shape. It is.

As described above, the conventional decorative sheet has advantages and disadvantages and is not always satisfactory. Ordinarily, decorative sheets used as interior decoration materials such as interior walls such as walls and ceilings of buildings, furniture and cabinets are required to have the following functions. (1) Thermoforming suitability equivalent to a decorative sheet using polyvinyl chloride. In particular, the change in elongation under a constant load due to temperature changes should be as slow and continuous as that of polyvinyl chloride. In addition, physical properties should not be deteriorated even by repeated temperature changes from heating to cooling to heating. (2) creep deformation resistance. Exterior and interior materials are often subjected to a fixed load by fittings and furniture for a long time, and when creep deformation occurs, the loaded portion is turned up or peeled off. Therefore, it is required that the material does not cause creep deformation as much as possible. (3) Cold bending strength. Folding such as V-cut processing in cold regions (when a decorative material laminated with decorative sheets is bent, a V-shaped groove is formed in the decorative material and the bending process is performed, hereinafter simply referred to as V-cut processing). If the stress relaxation is insufficient during the processing, whitening, cracking, breakage, etc. occur in the bent portion.

(4) Organic solvent resistance. When bonding the decorative sheet and the adherend, the decorative sheet is prevented from swelling and deforming due to the solvent in the adhesive. The same applies to a decorative sheet having a multilayer structure. (5) Elongation at break, impact resistance. In order to prevent cracks in the bent part during V-cut processing,
This property is required. (6) It has an appropriate flexural modulus. This is necessary because the followability of the decorative sheet in the bent portion is sufficient. (7) Good transparency. (8) Whitening and turbidity due to recrystallization do not occur even by heating and cooling during embossing or the like. (9) Easy adhesion. (10) Excellent weather resistance.

The present invention has been studied intensively to solve the problems of the conventional decorative sheet using a polyolefin resin and an acrylic resin. As a result, a combination of an acrylic resin sheet and a non-crystalline polyethylene terephthalate resin film has been obtained. By using this method, it is possible to obtain a decorative sheet that has the same thermoformability, stain resistance, weather resistance, transparency, and easy adhesion to adherends as a decorative sheet using a polyvinyl chloride resin. The invention has been reached.

[0009]

Means for Solving the Problems In order to solve the above problems, the configuration of the decorative sheet is as follows. In a decorative sheet comprising a colored base sheet, a picture layer, and a transparent protective layer, the colored base sheet is made of an acrylic resin,
The decorative sheet is characterized in that the transparent protective layer is made of an amorphous polyethylene terephthalate resin. Further, a decorative sheet is characterized in that a picture layer, an easy-adhesion layer, and a transparent amorphous polyethylene terephthalate film are laminated in this order on the colored base sheet. Furthermore, a decorative sheet having a top coat layer having a thickness of 1 to 10 μm formed on the transparent protective layer, wherein the top coat layer is made of a thermosetting resin containing a fluorine group, or an antibacterial agent is added A decorative sheet comprising a resin layer formed as described above. In addition, the decorative sheet is characterized in that an easy-adhesion layer is formed on the colored base sheet side of the decorative sheet. Then, the colored base sheet side of the decorative sheet was adhered to an adherend to obtain a decorative material.

That is, the decorative sheet of the present invention uses a colored sheet made of an acrylic resin as a base sheet, uses a transparent non-crystalline polyethylene terephthalate film as a protective film on the surface, and uses the surface film and a colored base material. A picture layer is provided in the middle of the sheet by printing or the like, and both films are laminated by a heat fusion method. The decorative sheet having the above-described configuration improves the vacuum forming suitability and has the same thermoformability as a decorative sheet using a conventional polyvinyl chloride film. In addition, on the protective layer, a top coat layer made of a thermosetting resin containing a fluorine group is provided to improve physical properties such as abrasion resistance, weather resistance, scratch resistance, and stain resistance of the decorative sheet, Further, an antibacterial agent is added to the top coat layer to impart antibacterial and antifungal properties. In addition, in order to improve the adhesiveness to the adherend, an easy-adhesion layer was formed on the back surface, and the decorative sheet was attached to the adherend to form a decorative material.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the decorative sheet of the present invention. FIG. 2 is a schematic sectional view showing another embodiment of the decorative sheet according to the present invention, in which an easy-adhesion layer is provided on a picture layer. FIG. 3 shows another embodiment of the decorative sheet of the present invention, in which a top coat layer is provided on a non-crystalline polyethylene terephthalate film (hereinafter referred to as a non-crystalline PET film) and an easy-adhesion layer is provided on the back surface. FIG. FIG. 4 is a schematic cross-sectional view of another embodiment of the decorative sheet of the present invention when an antibacterial agent is added to the top coat layer. FIG. 5 is an example of the decorative material of the present invention, and is a schematic cross-sectional view when a decorative sheet having a top coat layer formed thereon is adhered to an adherend. FIG. 6 is a schematic cross-sectional view of another embodiment of the decorative material of the present invention when a decorative sheet having a top coat layer containing an antibacterial agent is adhered to an adherend.

FIG. 7 is an explanatory view for producing the decorative sheet of the present invention. FIG. 8 is an explanatory diagram when a decorative sheet containing an antibacterial agent in the top coat layer (hereinafter referred to as an antibacterial decorative sheet) is prepared. FIG.
FIG. 3 is an explanatory diagram when a decorative sheet of the present invention is prepared, and the decorative sheet is attached to an adherend to prepare a decorative material. FIG. 10 is an explanatory diagram when a decorative sheet is manufactured according to the first embodiment. FIG. 11 is an explanatory diagram for producing a decorative sheet according to the second embodiment. FIG. 12 is an explanatory diagram when the quality of a decorative sheet is determined by a vacuum forming suitability test. FIG. 13 is an explanatory diagram when a V-cut processing suitability test of a decorative material is performed.

As shown in FIG. 1, the decorative sheet 1 of the present invention basically uses a colored sheet made of an acrylic resin as the colored base sheet 11, and the colored base sheet 11
And a transparent amorphous polyethylene terephthalate film (amorphous PET film) as a protective layer. The printed sheet (base sheet) and the transparent amorphous PET film (protected ) Are laminated by thermal fusion. The decorative layer 1 may be provided as the decorative sheet 1 by providing the pattern layer 12 on a transparent amorphous PET film 13 and heat-sealing the colored base sheet 11. As another aspect of the decorative sheet 1, in order to improve the adhesion between the colored base sheet and the non-crystalline PET film, as shown in FIG. Further, an easy-adhesion layer 14 is formed, and is thermally fused to the transparent amorphous PET film 13 to form the decorative sheet 1.
There is something. In this case, the decorative sheet 1 may be formed by forming the easy-adhesion layer 14 and the picture layer 12 on the non-crystalline PET film 13 and laminating the same with the colored base sheet 11;
Alternatively, the decorative sheet 1 may be formed by forming the picture layer 12 on the colored base sheet 11, forming the easy-adhesion layer 14 on the amorphous PET film 13, and laminating both.

Further, as another embodiment of the decorative sheet 1, as shown in FIG. 3, the surface has abrasion resistance, scratch resistance, weather resistance, and the like.
In order to improve physical properties such as stain resistance, a top coat layer 15 made of a thermosetting resin containing a fluorine group is formed on the amorphous PET film 13 as a protective layer,
There is also a decorative sheet 1 in which an easy-adhesion layer 14 is formed on the back surface of the laminated sheet in order to improve the adhesiveness to an adherend. In addition, as shown in FIG. 4, an antibacterial agent 16 may be added to the top coat layer 15 to impart antibacterial and antifungal properties to the decorative sheet to form the antibacterial decorative sheet 1a.

FIGS. 5 and 6 show the decorative material of the present invention.
As shown in FIG. 1, the decorative sheet 1 or the antibacterial decorative sheet 1a is manufactured by attaching the decorative sheet 1 or the antibacterial decorative sheet 1a to an adherend 20 such as a plastic sheet, plywood, or a molded product. That is, as shown in FIG. 5, the pattern layer 12 and the easy-adhesion layer 1
4. Amorphous PET film 13, Top coat layer 15
Is laminated to the adherend 20 by means of heat-sealing or an adhesive via an easy-adhesion layer 14 formed on the back surface of the decorative sheet 1 to form a decorative material 2. In addition, a pattern layer 12, an easy-adhesion layer 14,
An antibacterial decorative sheet 1a in which a non-crystalline PET film 13 and a topcoat layer 15 containing an antibacterial agent 16 are laminated,
The antibacterial cosmetic material 2a is adhered in the same manner as described above.

As the colored base sheet used in the decorative sheet of the present invention, a sheet obtained by adding a coloring agent to the following acrylic resin and forming the sheet to a predetermined thickness by a calendar method or the like is used. The thickness of the colored base sheet is 50 to 10
0 μm is preferred. Examples of the acrylic resin include poly (methyl) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate- (meth) acrylate.
Such as butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, and styrene-methyl (meth) acrylate copolymer; An acrylic resin comprising a homo- or copolymer containing (meth) acrylic acid ester is used. (However, here, (meth) acryl means acryl or methacryl, and will be used in the same meaning hereinafter.)

The coloring agent added to the acrylic resin is
The base sheet is provided with a necessary color as a decorative sheet, and a coloring agent composed of a pigment or a dye is used as necessary. The coloring of the acrylic resin sheet may be transparent coloring or opaque coloring depending on the application. Generally, it is necessary to cover the surface of the adherend, and a colored opaque sheet is preferable. As colorants, inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black, isoindolinone, banza yellow A, quinacridone, permanent red 4R,
Organic pigments or dyes such as phthalocyanine blue, metal pigments such as aluminum and pearls, titanium dioxide-coated mica,
Pearlescent pigments or the like made of foil powder such as basic zinc carbonate are used. If necessary, an inorganic filler may be added, and examples thereof include powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide).

As the transparent protective layer used in the decorative sheet of the present invention, an amorphous polyethylene terephthalate film (amorphous PET film) is used. As non-crystalline polyethylene terephthalate, PETG (trade name) of Eastman Chemical Company and Sealer PT (trade name) of DuPont Mitsui Polychemicals Co., Ltd. can be used, and PETG (trade name) of Eastman Chemical Company is available. It is suitable. Further, as an amorphous polyethylene terephthalate sheet (or film), A-PET sheet (or film) sold by Kanebo Co., Ltd., Teijin Co., Ltd., Toyobo Co., Ltd., Polytech Co., Ltd. is also available. Can be used.

Eastman Chemical's PETG is a polyethylene terephthalate (hereinafter referred to as PET) in which a part of the ethylene glycol component is replaced by 1,4-cyclohexanedimethanol, and terephthalic acid, ethylene glycol and 1,4 -A copolymer of cyclohexane dimethanol, PE by changing the component ratio of ethylene glycol and 1,4-cyclohexane dimethanol.
The crystallinity of T is lost. A transparent film made of PETG has excellent impact strength at low temperatures and good workability, so that a decorative sheet made using this can be bent at room temperature without whitening. PETG has a glass transition point of about 81 ° C.
It is tacky from 0 ° C and can be heat sealed at about 130-140 ° C. Therefore, a decorative sheet can be produced by heat-sealing with a colored acrylic resin sheet used as a base sheet.

Hereinafter, the method for producing the decorative sheet of the present invention will be described. First, the acrylic resin and the coloring agent are used to form a sheet by a known method, thereby producing a colored base sheet 11 as shown in FIG. Next, as shown in FIG.
2 and the easy-adhesion layer 14 are provided to obtain a printed sheet 3. still,
The picture layer 12 and the easy-adhesion layer 14 may be provided on a transparent amorphous PET film used as a protective layer, but in the present invention, provided on the colored base sheet 11.

The picture layer is provided for imparting a design property to the decorative sheet, and is formed by using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet. . Examples of the pattern of the picture layer include a wood grain pattern, a stone grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid printing on the entire surface. As a binder of the printing ink used in the above printing, ethyl cellulose, nitrocellulose, cellulose derivatives such as cellulose acetate butyrate, polymethyl methacrylate, acrylic resins such as polybutyl methacrylate, polyvinyl chloride,
Vinyl resins such as vinyl chloride / vinyl acetate copolymers and polyvinyl butyral are exemplified. As the printing ink, one obtained by mixing one or two or more of the above binder resins is used, and a known pigment, a coloring agent such as a dye, an extender pigment, a filler, an additive, a solvent, and the like are added thereto. Those that have been converted are used. As described above, the colorant used for the colored base sheet can be used as the colorant for the ink.

Further, in order to improve the adhesiveness with the non-crystalline PET film 13,
As shown in (b), the easy-adhesion layer 14 is formed as needed. In addition, the non-crystalline PET film 13
In some cases. The easy-adhesion layer (also called a primer layer or an anchor layer) can be formed by corona discharge treatment, plasma treatment, or the like. However, acrylic resin, urethane resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, It is formed by applying a coating solution in which a resin such as a polyurethane resin, chlorinated polyethylene, or chlorinated polypropylene is dissolved in a solvent. As the resin of the coating liquid, a polyurethane resin is particularly desirable. A coating solution obtained by dissolving the above resin in a solvent is applied by a known method and dried to form an easily adhesive layer, whereby the transparent amorphous PET film 13 is bonded to the pattern layer 12 and the colored base sheet 11. Power can be strong.

Examples of the acrylic resin used for the easy-adhesion layer include poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and (meth) acrylate. Methyl acrylate / (meth) butyl acrylate copolymer, (meth) ethyl acrylate / butyl (meth) acrylate copolymer, ethylene / (methyl) acrylate copolymer, styrene / (meth) acrylic acid Acrylic resin composed of homo- or copolymer containing (meth) acrylic acid ester such as methyl copolymer (here, (meth) acryl means acrylic or methacryl and the same applies hereinafter) Is done.

Polyurethane is mainly composed of polyol (polyhydric alcohol) and isocyanate as a crosslinking agent (curing agent).
Polyurethane. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, and polyether polyol. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4 tolylene diisocyanate, xylene diisocyanate, 4,4
Aromatic isocyanates such as diphenylmethane diisocyanate, or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used.

On the other hand, a film is produced by using a non-crystalline polyethylene terephthalate resin, for example, PETG by a known method such as a melt extrusion method, and as shown in FIG. 7C, a transparent non-crystalline PET film is formed. 13 is obtained.

The colored substrate sheet 11 having the pattern layer 12 and the easy-adhesion layer 14 formed thereon and the transparent amorphous PET film 13 are heat-sealed using a hot press or a hot roll. To form a laminated sheet 4 as shown in FIG. Further, in order to improve the abrasion resistance, abrasion resistance, chemical resistance, stain resistance, etc. of the decorative sheet 1, as shown in FIG. A topsheet layer 15 is formed on the colored sheet sheet 11 side of the laminated sheet 4, and an easy-adhesion layer 14 is formed on the colored base sheet 11 side to form the decorative sheet 1. As a method of laminating a transparent amorphous PET film on the colored base sheet 11 (printed sheet 3) on which the picture layer 12 and the easy-adhesion layer 14 are formed, a non-crystalline polyethylene The terephthalate resin can be melt-extruded by extrusion and laminated.

As the resin used for the top coat layer, an acrylic resin, a thermosetting resin containing a fluorine group, a polyurethane resin, an epoxy resin, a chlorinated polyolefin, an ionizing radiation curable resin, etc. are used. A thermosetting resin or an ionizing radiation-curable resin is preferred. As a method for forming the top coat layer, a method such as gravure coating, roll coating, knife coating, and air knife can be used.

The fluorine-containing thermosetting resin used in the present invention includes a fluorine-based thermosetting resin obtained by blending a polyisocyanate compound or the like as a curing agent with a fluoroolefin-based polymer; A fluorine-containing two-component curable urethane-based resin to which a fluorine compound is added and mixed is used. As a fluorine-based thermosetting resin obtained by blending a polyisocyanate compound or the like as a curing agent with a fluoroolefin-based polymer, a fluorine group having a fluorine content of 10% by weight or more based on a fluoroolefin unit and a hydroxyl group soluble in a solvent is used. And a fluorine copolymer having the formula:

As the fluorine-based additive to be mixed with the two-component curable urethane resin, a perfluoroalkyl group in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms and a hydrophilic group or a lipophilic group in the molecule are used. Surfactant. Then, the surface of the resin is modified by utilizing the surface transferability of the perfluoroalkyl group, and the perfluoroalkyl group is aggregated in the same molecule to improve the surface orientation. With the addition of a small amount, it migrates to the resin surface and modifies the resin surface with fluorine. The addition amount of the fluorine-based surfactant is 0.5 to
By adding 1.0 part by weight, the surface of the resin is modified with fluorine, and the surface of the two-component curable urethane resin is made water- and oil-repellent, stain-resistant, and non-adhesive.

As the ionizing radiation-curable resin used in the present invention, a prepolymer having a polymerizable unsaturated bond or a cationic polymerizable functional group in a molecule (including a so-called oligomer) and / or a composition obtained by appropriately mixing a monomer. And those curable by ionizing radiation are used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, an electron beam or an ultraviolet ray is used.

Specific examples of the ionizing radiation-curable resin include a radical polymerizable unsaturated group such as a (meth) acryloyl group and a (meth) acryloyloxy group, a cationic polymerizable functional group such as an epoxy group, and the like in the molecule. It consists of monomers, prepolymers and oligomers having two or more thiols. These monomers or prepolymers may be used alone or as a mixture of several types. Here, the (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group, and the following (meth) is used in the same meaning.

Examples of the prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, and the like.
Examples include methacrylates such as polyether methacrylate, polyol methacrylate, and melamine methacrylate, acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds. A molecular weight of about 250 to 10,000 is usually used. As the polymer having a radical polymerizable unsaturated group, the degree of polymerization of the polymer is 10,000.
Those having a degree or higher are used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. No.

As examples of the monomer having a cationically polymerizable functional group, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, dipentaerythritol tetrathioglycolate, and the like.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth)
Acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone (meth) acrylate and the like can be used. The molecular weight is 250 to 10
The one of about 000 is used.

Examples of monofunctional monomers having a radical polymerizable unsaturated group include monofunctional monomers of (meth) acrylate compounds, for example, methyl (meth) acrylate,
Ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like can be mentioned.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

When the resin is cured by ultraviolet light or visible light as the ionizing radiation-curable resin, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to.
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin.

Various additives may be added to the ionizing radiation-curable resin as required. As these additives, for example, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, acrylic resin, thermoplastic resin such as cellulose resin, calcium carbonate, barium sulfate, silica,
There are extenders (fillers) composed of fine powders such as alumina, doses, and coloring agents such as pigments.

The coating method of the ionizing radiation curable resin includes gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, dip coat, solid coat by silk screen coat, wire bar coat, Comma coat, spray coat, float coat, pouring coat, brush coating, spray coat, and the like can be used. Among them, a gravure coat is preferable.

As the ionizing radiation irradiating device for curing the ionizing radiation curable resin, an ultraviolet irradiating device or an electron beam irradiating device is used. As the ultraviolet irradiation device, 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, a black light lamp, and a metal halide lamp is used. The wavelength of the ultraviolet light is usually 19
The wavelength range from 0 to 380 nm is mainly used. As the electron beam irradiator, various electron beam accelerators such as a Cockloft-Wald type, a Bande graph type, a resonance transformer type, an insulating core transformer type or a linear type, a dynamitron type, and a high frequency type are used.

When irradiating with an electron beam, the acceleration voltage is 100 to 1000 KeV, preferably 100 to 300 KV.
Irradiation at eV, the absorbed dose is usually 1 to 300 k
It is about Gy (kilo gray). If the absorbed dose is less than 1 kGy, curing of the coating film will be insufficient, and
If it exceeds 0 kGy, the cured coating film and substrate will turn yellow or be damaged. In the case of ultraviolet irradiation, the irradiation amount is preferably in the range of 50 to 1000 mJ / cm ² .
When the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , the curing of the coating film becomes insufficient, and the irradiation amount is 1000 mJ / cm ^2.
If it exceeds 300, the cured coating film will turn yellow. In addition, as a method of irradiating ionizing radiation, first, an ultraviolet ray is irradiated to cure the ionizing radiation-curable resin so that at least the surface is dry to the touch, and thereafter, the coating film is completely cured by irradiating with an electron beam. There is also a way to do this.

As another embodiment of the decorative sheet of the present invention, there is a case where an antibacterial agent is added to the top coat layer on the surface to impart antibacterial property and antifungal property to obtain an antibacterial decorative sheet. Hereinafter, the antibacterial cosmetic sheet will be described. FIG.
As shown in (a), similarly to the above, a pattern layer 12 and an easy-adhesion layer 14 are formed on a colored base sheet 11 made of an acrylic resin.
Is formed to produce a printed sheet 3 and a transparent amorphous PET film 13 is produced. Next, the printing sheet 3 and the non-crystalline PET film 13 were heat-sealed, and
A laminated sheet 4 as shown in FIG.

Next, the non-crystalline PET of the laminated sheet 4
A top coat layer 15 containing an antibacterial agent 16 is formed on the surface of the film 13, and the colored base sheet 1 on the back surface of the laminated sheet 4 is formed.
The anti-bacterial decorative sheet 1a is formed by forming the easy-adhesion layer 14 on the first sheet. As the resin used for the top coat layer 15, the resin used for the above-described top coat layer is used, and as the antibacterial agent, the following is used.

As the antibacterial agent used in the top coat layer, commercially available industrial antibacterial agents can be used. Antibacterial agents include organic antibacterial agents and inorganic antibacterial agents, and any of them can be used in the present invention. Examples of inorganic antibacterial agents include JP-B-63-54013, JP-A-4-300975, and Patent No. 25295.
No. 74, zeolite, apatite, glass, silica gel, phosphate, part or all of ion-exchangeable ions such as zirconium phosphate, silver,
There are ion exchangers substituted with ions of copper, zinc, tin, lead, mercury, cobalt, ammonium and the like. Among them, zeolite and zirconium phosphate, in which some of the ion-exchangeable ions are replaced with silver ions, are preferable from the viewpoint of safety and actual product. The content of the metal ion supported on zeolite and zirconium phosphate is 0.1 in the case of silver ion.
1 to 15% by weight, 0.1 to 8 for copper or zinc ions
% By weight is preferred. There is also an ion exchanger substituted with the above-mentioned metal ion, which is further substituted with an ammonium ion. (Japanese Patent Publication No. 4-28646, Patent No. 2529)
No. 574, etc.)

Organic compounds having antibacterial properties include
sulfa agents such as p-aminobenzenesulfonamide, sulfathiazole, sulfapyridine and sulfapidiazine; dithiocarbamates such as dimethyldithiocarbamate and ethylenebisthiocarbamate; 2- (2
-Furyl) -3- (5-nitro-2-furyl) acrylamide and the like.

Organic compounds having antibacterial and antifungal properties include 10,10′-oxybisphenoxyarsine, trimethoxysilylpropyloctadecyl ammonium chloride, 2- (4-thiazolyl) -benzimidazole, bis (2-pyridylthio) -1-oxide) zinc, 2-N-octyl-4-isothiazolin-3-one, 2,3,5,6-cytochloro-4- (methylthio) -phthalimide, N- (fluorodichloromethylthio) florimide, griseofulvin , Tricomycin, amphotericin B and the like.

Examples of the antibiotic include penicillins such as phenoxymethylpenicillin and dicloxacillin, cephalostins such as cephalothin and cefazolin, streptomycins such as streptomycin sulfate and paromomycin (sulfate), erythromycins such as erythromycin and josamycin, tetracycline, and loritetracycline nitrate. And chloramphenicol such as thiamphenicolamine acetate hydrochloride.

When a topcoat layer containing the above antibacterial agent is formed, the content of the antibacterial agent is 0.01 to 10% by weight.
, But is preferably in the range of 0.1 to 3.0% by weight. If the content of the antibacterial agent is less than 0.01% by weight, a sufficient antibacterial effect cannot be obtained. In addition, the content is 10
If it exceeds 10% by weight, the antibacterial effect is not so high even if it is added more, and the economical disadvantage becomes large.
Further, transparency may be deteriorated. The thickness of the top coat layer containing the antibacterial agent is preferably in the range of 3 to 10 μm. If the thickness of the top coat layer containing the antibacterial agent is 3 μm or less, there is a problem in processing and it is not practical. Also,
When it exceeds 10μ, sufficient antibacterial performance can be exhibited at 10μ or less, which is economically disadvantageous.

The decorative sheet of the present invention is used as a decorative material by being laminated on various adherends, and can be used for various purposes after performing a predetermined molding process. The decorative material of the present invention is produced as follows. That is, as described above, FIG.
(A) As shown in FIG.
Then, the printing sheet 3 is manufactured by forming the easy-adhesion layer 14.
Next, using a transparent amorphous PET film as a protective layer, as shown in FIG.
And a non-crystalline PET film 13 are laminated by heat fusion to produce a laminated sheet 4. Further, on the non-crystalline PET film of the laminated sheet 4, as shown in FIG. The decorative sheet 1 is produced by forming the adhesive layer 14 on the colored base sheet 11 on the back surface. Next, as shown in FIG. 9D, the decorative sheet 1 is attached to an adherend 20 such as a plywood or a three-dimensional molded product, thereby forming a decorative material 2.

The object to be adhered is a plate material such as a flat plate or a curved plate of various materials, a sheet (or film), or various three-dimensionally shaped articles (molded products). For example, the decorative sheet of the present invention can be bonded to a molded product having a curved surface such as an injection molded product. When a three-dimensional molded product is used as the adherend, a vacuum forming method is often used, but the decorative sheet of the present invention has good adhesiveness to the R portion or the reverse R portion of the three-dimensional molded product, and has a good adhesion. It is possible to perform various surface makeup. Further, even on a surface having irregularities, the concave portion is narrowed down and the narrowed portion does not return due to heating, so that a more excellent irregular surface can be formed on the decorative sheet.

As a material to be used as a plate material or a sheet (film) as the adherend, a single wood plate,
Wood plywood, particle board, medium density fiberboard (MD
F), such as wood board, woody board such as wood fiber board, metal such as iron and aluminum, acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS,
Phenolic resin, polyvinyl chloride, cellulosic resin,
Resins such as rubber are exemplified.

As a method of laminating these various adherends,
For example, the following methods can be mentioned. That is, a method of laminating a plate-shaped substrate by pressing with a pressure roller via an adhesive layer therebetween, Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27.
No. 488, etc., a decorative sheet is inserted between the male and female molds for injection molding, the molds are closed, the molten resin is injected and filled from the male gate, and then cooled and the resin is cooled. A so-called simultaneous injection molding laminating method in which a decorative sheet is adhered and laminated on the surface of a molded article at the same time as molding, Japanese Patent Publication No. 56-45768, Japanese Patent Publication No. 60-58.
No. 014, etc., a decorative sheet is placed on the surface of a molded article facing or opposite to the molded article via an adhesive, and the decorative sheet is placed on the surface of the molded article by a pressure difference due to vacuum suction from the molded article side. Lamination, so-called vacuum press lamination method,

As described in JP-B-61-5895, JP-B-3-2666, etc., an adhesive layer is provided between decorative sheets in the longitudinal direction of a columnar substrate such as a column or a polygonal column. A so-called lapping method in which decorative sheets are sequentially adhered to and stacked on a plurality of side surfaces constituting a columnar body by a number of rollers having different directions while being supplied through the so-called lapping method, Japanese Utility Model Publication No. 15-31122. JP-A-48-47
No. 972, etc., a decorative sheet is first laminated on a plate-like base material via an adhesive layer, and then the decorative sheet and the plate-like material are placed on the surface of the plate-like base material opposite to the decorative sheet. Cut a V-shaped or U-shaped groove so that the cross section reaches the interface with the substrate, then apply an adhesive in the groove, bend the groove, and form a box or a columnar body. A so-called V-cut or U-cut processing method for molding may be used.

In particular, as a method of attaching the decorative sheet of the present invention to a three-dimensional object having irregularities, a lapping method, an injection molding simultaneous laminating method, a vacuum press laminating method and the like are preferable among the above methods. The decorative material produced as described above can be used for various applications. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, handrails, surface decoration of cabinets of furniture or light electric / OA equipment, interior decoration of vehicles such as automobiles and trains, aircraft Interior,
It can be used for window glass makeup. Therefore, when the decorative sheet cannot be directly bonded to a material or the like, the decorative sheet is bonded to an adherend via an appropriate easy-adhesion layer or an adhesive layer. However, when the decorative sheet can be bonded to the adherend by heat fusion or the like, the easy-adhesion layer or the adhesive layer may be omitted.

[0056]

The present invention will be described below in more detail with reference to examples. (Example 1) First, as shown in FIG. 10 (a), a base material sheet having a thickness of 80 made of polymethyl methacrylate was used.
A μm colored acrylic sheet (manufactured by Kyowa Leather Co., Ltd .; hereinafter, referred to as a colored PMMA sheet 11a) is prepared, and a gravure ink (manufactured by Showa Ink Industry Co., Ltd., acrylic resin and chloride) are applied to the colored PMMA sheet 11a. A wood pattern is gravure-printed with an ink using a resin in which a vinyl-vinyl acetate copolymer is mixed at a ratio of 50/50 to form a picture layer 12, and two-pack curing is performed on the picture layer 12. A primer solution composed of a mold polyurethane was applied to form an easy-adhesion layer 14, thereby producing a print sheet 3 as shown in FIG. 10B. On the other hand, PETG (trade name) manufactured by Eastman Chemical Co., Ltd. was used as the amorphous polyethylene terephthalate resin, and a film was produced by extrusion using the PETG. As shown in FIG. 10C, a transparent film having a thickness of 60 μm was formed. PETG film 13a
I got

Next, as shown in FIG. 10 (d), the printing film 3 and the transparent PETG film 13a are overlapped, and heated and pressed using a heating roll to perform heat fusion. As shown in Table 2, a laminated sheet 4 was produced. Next, the PETG film 13a is coated with an overprint ink (a mixture of an OPF ink and a curing agent in a ratio of 100: 12, manufactured by Showa Ink Industries, Ltd.) using a fluorine-based acrylic urethane resin as a binder. As shown in FIG. 10E, the top coat layer 15
Was formed on the colored PMMA sheet 11a on the back surface of the decorative sheet, and an easy-adhesion layer 14 made of a two-component curable polyurethane was formed in the same manner as described above, to prepare the decorative sheet 1.

Example 2 As in Example 1, the colored PM
The pattern layer 12 and the easy-adhesion layer 14 were formed on the MA sheet 11a, and the printing sheet 3 as shown in FIG. 11A was produced. Further, as shown in FIG. 11B, a transparent PETG film 13a was produced in the same manner as in Example 1.

Next, as shown in FIG. 11 (c), the printing film 3 and the PETG film 13a are overlapped,
The printing film 3 and the PETG film 13a are heat-pressed and heat-sealed by doubling embossing using an embossing plate, and an embossed pattern 17 is formed on the PETG film 13a, as shown in FIG. The embossed laminated sheet 5 was produced.

Next, a two-part curable wiping ink (manufactured by Showa Ink Industries, Ltd.) was applied by wiping to the PETG film 13a on which the embossed pattern 17 was formed, and as shown in FIG. Recess 17
a was filled with the coloring ink 18. Further, on the wiping-processed PETG film 13a, an overprint ink (a mixture of an OPF ink and a curing agent, manufactured by Showa Ink Industries, Ltd., at a ratio of 100: 12) using a fluorine-based acrylic urethane resin as a binder was used. As shown in FIG. 10 (e), the top coat layer 15 is formed, and then the colored adhesive PMMA sheet 11a on the back of the decorative sheet is coated with the easy-adhesion layer 14 made of a two-component curable polyurethane in the same manner as described above. Was formed, and the decorative sheet 1 was produced.

(Embodiment 3) First, in the same manner as in Embodiment 1, the picture layer 12 and the easy-adhesion layer 15 were added to the colored PMMA sheet 11a.
Was formed to produce a print sheet 3 as shown in FIG. Also, as in Example 1, as shown in FIG. 12B, a transparent PETG film 13 having a thickness of 60 μm was formed.
is prepared, the PETG film 13a and the printing sheet 3 are laminated by a doubling embossing method, and FIG.
As shown in (c), an embossed laminated sheet 5 was produced. Then, the embossed pattern 17
As shown in FIG. 12D, the embossed recesses 17a are formed on the PETG film 13a on which the
Was filled with the coloring ink 18.

Next, an overprint ink (manufactured by Showa Ink Industries, Ltd., which was prepared by mixing an antibacterial OP ink and a curing agent in a ratio of 100: 5) to which an organic antibacterial agent (Minton Thiokol, Inc., Vinazine) was added. ), And 1% by weight of the antibacterial agent 16 as shown in FIG.
12 is formed on the colored PMMA sheet 11a on the back surface of the decorative sheet, and an easy-adhesion layer 14 made of two-component curing type polyurethane is formed.
As shown in (e), an antibacterial cosmetic sheet 1a was produced.

Comparative Example 1 A transparent biaxially stretched isotactic polypropylene film (thickness: 100 μm) having a draw ratio of 3 times was used as the surface film of the protective layer. A decorative sheet was produced in the same manner as in Example 1 using an axially stretched isotactic polypropylene sheet (80 μm in thickness). (Comparative Example 2) Colored P used in Example 1 as a base sheet
A decorative sheet was produced in the same manner as in Example 2 using an MMA sheet and the biaxially stretched polypropylene film used in Comparative Example 1 as a protective layer. (Comparative Example 3) Colored P used in Example 1 as a base sheet
A decorative sheet was produced in the same manner as in Example 2 using an MMA sheet and an unstretched polypropylene film having a thickness of 80 μm as a protective layer.

(Performance Test) The following tests were performed on the decorative sheets prepared in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 to compare the performance.

(Vacuum forming suitability test) As shown in FIG. 13 (a), a size of 100 mm × 100 mm and a thickness of 30 mm
On the central surface of the Lauan plywood 20a at an angle of 90 ° and a depth of 5
A decorative sheet 1 coated with an adhesive was overlapped on a plywood 20a having a groove formed therein, and the decorative sheet 1 was bonded to the plywood 20a by a vacuum forming method. The plywood to which the decorative sheet was adhered was taken out, and the surface and cross section were visually observed. As shown in FIG. 13 (b), when the decorative sheet 1 was neatly inserted into the groove of the plywood 20a, (C)
As shown in the figure, the floating of the decorative sheet 1 from the groove is indicated by ×.
Was determined.

(Cold Heat Repeat Test) A plywood bonded with a decorative sheet prepared by the above vacuum forming method was used as a sample, and this sample was placed in an oven at 80 ± 3 ° C. for 2 hours, and then -20 ± 3.
2 hours in a freezer at 80 ° C. and 2 hours again in an oven at 80 ± 3 ° C. After repeating this 10 times,
The surface and cross section of the sample were visually observed, and FIG.
As shown in FIG. 13, it was determined that the decorative sheet was inserted into the groove as ○, and as shown in FIG. 13C, the decorative sheet was floating from the groove as x.

(V-cut processing suitability test) After bonding the decorative sheet to the Rawan plywood 20a having a thickness of 10 mm using an adhesive, as shown in FIG. Next, a groove 21 having a V-shaped cross section is cut so as to reach the interface between the Lauan plywood 20a and the adhesive layer, and an adhesive is applied to the groove 21.
(B) As shown in FIG.
Oa was bent and bonded in an L-shape (cross section), and the bent portion was visually observed for whitening and cracks. The ambient temperature during processing was set at 10 ° C.

Table 1 shows the results of the above performance tests of the decorative sheets prepared in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3. As can be seen from the results in Table 1, in the vacuum forming test, the decorative sheets prepared in Examples 1, 2, and 3 had sufficient penetration into the grooves and had good vacuum forming suitability. In addition, no lifting occurred in the cold repetition test, and the sheet was satisfactory as a decorative sheet. Further, good results were obtained in the V-cut processing suitability test, and it can be expected that the composition can be used in cold regions.

[0069]

[Table 1]

[0070]

The decorative sheet of the present invention uses an acrylic resin as a base sheet and an amorphous polyethylene terephthalate film as a transparent protective layer on the surface. However, there is no danger of generating harmful gases such as hydrochloric acid gas and dioxin.
Further, the decorative sheet of the present invention uses an acrylic resin sheet for the base sheet and an amorphous polyethylene terephthalate sheet for the protective layer on the surface, so that it is excellent in vacuum forming suitability, and has an uneven shape by the vacuum forming method. When used for surface decoration of a three-dimensional molded article having the same, it is easy to enter the concave portion, and excellent surface decoration can be achieved. Therefore, it can be expected that the decorative sheet of the present invention can be used for a three-dimensional molded article having an uneven shape.

Further, since the decorative sheet of the present invention has a small heat shrinkage upon heating, when used for surface decoration of a three-dimensional molded article having an uneven shape, even if heating and cooling are repeated, the concave part of the three-dimensional molded article is not removed. No floating phenomenon of the entered decorative sheet is observed, and no return is observed in the surface irregularities. That is, the decorative sheet of the present invention has excellent weather resistance. Also,
The decorative sheet of the present invention has good suitability for V-cut processing, and the decorative sheet may be cracked even when bent.
Since whitening does not occur, it is excellent in workability. Further, since the decorative sheet of the present invention can be subjected to embossing and wiping, it is possible to impart design properties equivalent to those of a decorative sheet using a conventional polyvinyl chloride resin.

Further, the antibacterial decorative sheet of the present invention can impart antibacterial performance to its surface by being attached to any substrate such as plastic, paper, wood, metal plate, inorganic material, etc. Antibacterial performance can be imparted to various equipment (electric appliances, cabinets, various appliances, etc.) used in surroundings, places with high temperature and high humidity, hospitals and other places requiring a sanitary environment. In addition, since the antibacterial cosmetic sheet of the present invention can be provided with antibacterial performance by sticking it to existing electric appliances, cabinets, various appliances, etc., the economic burden on preventing bacterial contamination can be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a decorative sheet of the present invention.

FIG. 2 is a schematic cross-sectional view of another embodiment of the decorative sheet of the present invention, in which an easy-adhesion layer is provided on a picture layer.

FIG. 3 shows another embodiment of the decorative sheet of the present invention, wherein the amorphous P
FIG. 3 is a schematic cross-sectional view when a top coat layer is provided on an ET film and an easy-adhesion layer is provided on a back surface.

FIG. 4 is a schematic cross-sectional view of another embodiment of the decorative sheet of the present invention when an antibacterial agent is added to the top coat layer.

FIG. 5 is a schematic cross-sectional view of an example of the decorative material of the present invention when a decorative sheet having a top coat layer formed thereon is adhered to an adherend.

FIG. 6 is a schematic cross-sectional view of a decorative material according to another embodiment of the present invention when a decorative sheet having a top coat layer containing an antibacterial agent is adhered to an adherend.

FIG. 7 is an explanatory diagram for producing a decorative sheet of the present invention.

FIG. 8 is an explanatory diagram for producing an antibacterial decorative sheet in which an antibacterial agent is added to a top coat layer, which is a decorative sheet of the present invention.

FIG. 9 is an explanatory diagram when a decorative sheet of the present invention is prepared, and the decorative sheet is attached to an adherend to prepare a decorative material.

FIG. 10 is an explanatory diagram for producing a decorative sheet according to Example 1.

FIG. 11 is an explanatory diagram for producing a decorative sheet according to Example 2.

FIG. 12 is an explanatory diagram when a decorative sheet is produced according to Example 3.

FIG. 13 is an explanatory diagram when judging the quality of a decorative sheet by a vacuum forming suitability test.

FIG. 14 is an explanatory diagram when a V-cut processing suitability test of a decorative material is performed.

[Explanation of symbols]

 Reference Signs List 1 decorative sheet 1a antibacterial decorative sheet 2 decorative material 3 printed sheet 4 laminated sheet 5 embossed laminated sheet 11 colored base sheet 11a colored PMMA sheet 12 picture layer 13 non-crystalline PET film 13a PETG film 14 easy adhesion layer 15 top coat layer Reference Signs List 16 antibacterial agent 17 embossed pattern 17a embossed recess 18 colored ink 20 adherend 20a plywood 21 V-shaped groove

Continued on the front page F-term (reference) 4F100 AK15 AK17C AK22 AK25A AK25C AK42B AK51G AL01 AL01C AR00D AT00A BA02 BA03 BA04 BA07 BA10A BA10B BA10C BA10D CA12C CB00 CB00D GB08 GB48 GB81 HB00 J12BJL10 J01L

Claims (7)

[Claims] 1. A decorative sheet comprising a colored base sheet, a picture layer, and a transparent protective layer, wherein the colored base sheet is made of an acrylic resin, and the transparent protective layer is made of an amorphous polyethylene terephthalate resin. A decorative sheet characterized by the following. 2. The decorative sheet according to claim 1, wherein a pattern layer, an easy-adhesion layer, and a transparent amorphous polyethylene terephthalate film are laminated on the colored base sheet in this order. 3. A thickness of 1 to 10 μm on the transparent protective layer.
2. A m-topcoat layer is formed.
Or the decorative sheet according to claim 2. 4. The decorative sheet according to claim 3, wherein the top coat layer is made of a fluorinated acrylic resin. 5. The decorative sheet according to claim 3, wherein the top coat layer comprises a resin layer containing an antibacterial agent. 6. The decorative sheet according to claim 1, wherein an easy-adhesion layer is formed on the colored base sheet side of the decorative sheet. 7. A decorative material, wherein the colored base sheet side of the decorative sheet according to claim 1 is adhered to an adherend.