JP2000326446A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of being subjected to three- dimensional molding processing and having excellent surface hardness or scratch resistance on its surface, a decorative sheet having three-dimensional design effect and a decorative material having a three-dimensional shape using the same. SOLUTION: In a decorative sheet wherein a surface protective layer 3 is provided on a thermoplastic sheet 1, an ionizing radiation curable resin is used in the surface protective layer. A decorative material having a three-dimensional shape due to a V-cut processing, lapping processing or vacuum molding processing can be produced from this decorative sheet. A pattern having gloss difference or a tuning uneven pattern due to liquid repelling effect is provided to the surface protective layer or an uneven shape is provided thereto and color ink is applied to recessed parts to impart three-dimensional design effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet for use as a decorative surface of a decorative material used for building materials, furniture, housing equipment, etc., and in particular, has a high surface hardness and excellent durability. A decorative sheet for use as a luxury cosmetic material, including a wrapping process, a V-cut process,
The present invention relates to a decorative sheet that can be used for three-dimensional forming such as vacuum forming.

[0002]

2. Description of the Related Art As a conventional decorative sheet, a pattern or the like is printed on the surface of a paper base material such as thin paper or resin-impregnated paper by a gravure printing method or the like, and an aminoalkyd resin or a urethane resin is further printed on the printed surface. There is known a so-called pre-coated decorative paper in which a coating liquid containing a thermosetting resin composition as a main component is coated and cured to provide a surface protective layer.

As such a precoated decorative paper, in addition to one having the above-mentioned surface protective layer provided uniformly on the entire surface, a plurality of types of coating liquids having different surface gloss after coating and curing are used, and the surface protective layer has a gloss difference. (A gloss mat decorative paper) or a method of applying the coating liquid on a pattern made of a liquid-repellent ink containing a liquid-repellent substance such as a silicone compound. There is also one provided with a concave portion (tuned uneven patterned decorative paper). These are used for applications requiring a sense of quality due to their unique excellent three-dimensional design effects.

[0004] In addition, in applications where the requirements for surface hardness and scratch resistance are particularly severe, such as furniture top plates and stair treads, a cured film having a higher hardness is used in place of the above-mentioned thermoplastic resin composition. There is also known a decorative paper using a coating liquid containing, as a main component, an ionizing radiation-curable resin composition that is cured by irradiation with ultraviolet light, an electron beam, or the like.

[0005] However, these precoated decorative papers use a paper base material having poor spreadability, so that it can be sufficiently laminated on a base material for decorative materials having a flat surface shape, Lamination to a decorative material substrate having a shape is generally very difficult, and in particular, three-dimensional molded lamination by vacuum forming or the like to a three-dimensional three-dimensional decorative material substrate is practically impossible. Was. In addition, since the printing substrate is essentially porous paper with poor surface smoothness, the sharpness of the printed pattern is poor,
There was also a problem that the design was inferior.

[0006] As a decorative sheet that can be three-dimensionally formed, a decorative sheet using a thermoplastic sheet such as a plastic film as a base sheet is known. Since a thermoplastic sheet having a smooth surface can be easily obtained, there is also an advantage that a decorative sheet provided with a clear picture by printing can be easily obtained. Since the surface hardness and scratch resistance of the thermoplastic sheet itself are naturally limited due to the thermoplastic property, the thermoplastic sheet mainly contains a thermosetting resin composition such as a two-component curable urethane resin. It is also known that a surface protective layer formed by applying and curing a coating liquid is provided to improve surface hardness and scratch resistance.

However, in such decorative sheets, it is necessary to increase the coating amount of the coating liquid for forming the surface protective layer in order to improve the surface hardness and the scratch resistance. The amount of heat required to evaporate and dry the solvent component or to cure the thermosetting resin composition increases, and as a result, in the evaporative drying and curing process,
The thermoplastic sheet, which is the base material, is exposed to high temperatures, causing deformation and alteration.

In addition, a three-dimensional design effect by a gloss mat pattern or a tuned irregular pattern is applied to a decorative sheet using the thermoplastic sheet by applying the principle of the gloss mat decorative paper or the tuned irregular pattern decorative paper described above. If you try to grant
In the former case, the number of layers of the thermosetting resin composition constituting the surface protective layer is multi-layered, so that the overall coating amount is inevitably increased. Since it is necessary to set a large coating amount of the surface protective layer in order to ensure a sufficient level difference between the surface protective layer and the other parts, in any case, as described above, evaporative drying and curing are performed. Deformation and deterioration of the thermoplastic sheet due to the heat of the process are inevitable.

[0009] Under these circumstances, depending on the conventional decorative sheet, three-dimensional forming such as lapping, V-cut, and vacuum forming can be performed, but a decorative sheet having a high surface hardness and excellent scratch resistance, and a glossy sheet. A decorative sheet excellent in a three-dimensional design effect such as a mat pattern or a synchronized uneven pattern could not be obtained. Therefore, a cosmetic material having a three-dimensional design effect, such as excellent surface hardness and scratch resistance, a gloss mat pattern, a synchronized uneven pattern, etc., on the surface of a cosmetic material substrate having a three-dimensional shape has not been obtained. .

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is a decorative sheet which can be three-dimensionally formed and has excellent surface hardness and scratch resistance. Further, it is an object of the present invention to provide a decorative sheet having a three-dimensional design effect such as a gloss mat pattern and a synchronous uneven pattern, and a decorative material having a three-dimensional shape using the same.

[0011]

Means for Solving the Problems The decorative sheet of the present invention comprises:
A decorative sheet comprising a thermoplastic sheet provided with a surface protective layer, wherein an ionizing radiation-curable resin is used for the surface protective layer. In addition, the decorative sheet of the present invention further includes a decorative sheet provided with a pattern having a difference in gloss on the surface protective layer, a decorative sheet provided with a synchronized uneven pattern on the surface protective layer, and a surface of the thermoplastic sheet. The decorative sheet also includes a decorative sheet provided with a concave and convex shape, a decorative sheet provided with colored ink in concave portions of the concave and convex shape, and a decorative sheet provided with a primer layer between the thermoplastic sheet and the surface protective layer.

The decorative material of the present invention is obtained by attaching the decorative sheet of the present invention to one side of a flat decorative material base material,
The decorative material, characterized in that the surface of the decorative material substrate on the side where the decorative sheet is not affixed is grooved and bent to form a three-dimensional shape, and the decorative sheet of the present invention. And a three-dimensionally molded laminate formed on a surface of a three-dimensionally shaped base material for a decorative material.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The decorative sheet of the present invention contains an ionizing radiation-curable resin composition as a main component on the surface of a thermoplastic sheet 1 formed by printing a desired and appropriate pattern 2 as required. An ionizing radiation-curable coating liquid is applied, and the coating liquid is irradiated with ionizing radiation such as ultraviolet rays or an electron beam to be cured, thereby forming a surface protective layer 3 made of an ionizing radiation-curable resin. (FIG. 1).

With the ionizing radiation-curable resin composition which is the main component of the ionizing radiation-curable coating solution for forming the surface protective layer 3, a polymerization crosslinking reaction can be performed by irradiation with ionizing radiation such as ultraviolet rays or electron beams. Prepolymers, oligomers and / or monomers having at least one radically polymerizable double bond in the molecule are appropriately compounded. Examples of such prepolymers and oligomers include acrylates such as polyester acrylate, urethane acrylate, epoxy acrylate, polyether acrylate, and polyol acrylate, and methacrylates such as polyester methacrylate, urethane methacrylate, epoxy methacrylate, polyether methacrylate, and polyol methacrylate. . As the monomer, n-
Alkyl acrylate, iso-propyl acrylate,
Isobutyl acrylate, t-butyl acrylate,
Cyclohexyl acrylate, β-hydroxyethyl acrylate, diethylene glycol acrylate, polyethylene glycol acrylate, β-hydroxypropyl acrylate, glycidyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate,
Polyethylene glycol diacrylate, dialkylaminoethyl acrylate, 2-cyanoethyl acrylate, β-ethoxyethyl acrylate, aryl acrylate, benzoyloxyethyl acrylate, benzyl acrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl Acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl alcohol and ε-caprolactone adduct acrylate, iso-bornyl acrylate, dicyclopentenyloxyethyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neo-pentyl glycol di Acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, acetal glycol diacrylate, neopentyl glycol hydroxypivalate and ε-caprolactone Diacrylate, trimethylolpropane triacrylate, trimethylolpropane polyethoxylate
Triacrylate, trimethylolpropane / polypropoxylate / triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol and ε-caprolactone adduct hexaacrylate, acryloxyethyl phosphate, fluoroalkyl acrylate, sulfopropyl acrylate And acrylate monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, secondary butyl methacrylate, tertiary butyl methacrylate, hexyl methacrylate, octyl methacrylate, and isooctyl. Methacrylate, 2-ethyl Sill methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-tert-butylaminoethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, nonylphenyl methacrylate, benzyl methacrylate, dibenzyl methacrylate Cyclopentenyl methacrylate, bornyl methacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate Methacrylate, O neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, glycerol methacrylate, methacryloxyethyl phosphate, bis-
And methacrylate monomers such as methacryloxyethyl phosphate.

When the coating film of the above-mentioned ionizing radiation-curable coating liquid is cured by irradiation of ultraviolet rays, the ionizing radiation-curable coating liquid may include, for example, benzoin, benzoin methyl ether, benzoin isopropyl ether and the like. Or its alkyl ethers, acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexylacetophenone; thioxanthones such as thioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal and benzyl methyl ketal And at least one photoradical polymerization initiator selected from benzophenones such as ketals, benzophenone and 4,4-bismethylaminobenzophenone, and azo compounds. If necessary, tertiary amines such as triethanolamine and methyldiethanolamine,
One or more photosensitizers selected from benzoic acid derivatives such as -dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate are used in combination.

Further, colorants, fillers, matting agents, defoaming agents, mold release agents, abrasives, flame retardants, lubricants, antistatic agents, and ultraviolet light are used as accessory components of the ionizing radiation-curable coating liquid. An absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antibacterial agent, a fungicide, a diluting solvent, and other additives may be appropriately contained as necessary. When an ionizing radiation-curable coating liquid containing a diluting solvent is used, it is preferable that the diluting solvent be volatilized and removed after coating, and then irradiated with ionizing radiation for curing.

The method of applying the ionizing radiation-curable coating liquid is not particularly limited. For example, a gravure coating method, a die coating method,
From any conventionally known coating methods such as a lip coating method, a knife coating method, an air knife coating method, a spray coating method, a flow coating method, a roll coating method, and a dip coating method, the properties of an ionizing radiation-curable coating liquid and Thermoplastic sheet 1
What is necessary is just to select and implement an appropriate method that matches the characteristics of the above. Before applying the ionizing radiation-curable coating liquid, an appropriate surface treatment such as a corona treatment, an ozone treatment, a plasma treatment, an ionizing radiation treatment, an acid treatment or an alkali treatment is applied to the coating surface of the thermoplastic sheet 1 in advance. Is applied to increase the wettability, the adhesion between the thermoplastic sheet 1 and the surface protective layer 3 can also be improved.

The thickness of the surface protective layer 3 is not particularly limited, but if it is too thin, the required surface hardness and scratch resistance cannot be achieved, and if it is too thick, the flexibility is reduced and the three-dimensional moldability is impaired. As a result, it is necessary to select a thickness range that balances the two. Specifically, although it depends on the composition of the ionizing radiation-curable resin, the thickness after curing is 1 μm or more and 50 μm or more.
It is desirable to set it to the following range, in particular, 3 μm or more and 2
Most preferably, it is within a range of 0 μm or less.

The type of ionizing radiation used for curing the ionizing radiation-curable resin composition constituting the surface protective layer 3 is not particularly limited. In short, the ionizing radiation-curable resin composition or the photo-radical polymerization added thereto is used. Any ionizing radiation having sufficient energy to act on an initiator or a sensitizer to ionize (radicalize) them and initiate a radical polymerization reaction may be used. Specifically, for example, visible light,
Electromagnetic waves such as ultraviolet rays, X-rays, and γ-rays, and charged particle beams such as electron beams, α-rays, and β-rays can be considered. The most practical is ultraviolet rays or electron beams.

Ultraviolet light sources, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps,
A light source such as a carbon arc lamp can be applied. The irradiation dose is 5
0 to 1000 mJ / cm ² is preferable. 50 mJ / cm ²
If it is less than 1000 mJ, curing may be insufficient.
This is because if it exceeds / cm ² , it causes deterioration of the thermoplastic sheet. Usually, this process is possible at a line speed of 50 to 500 m / min, so that the production efficiency is extremely high.

Various electron beam accelerators such as Cockloft-Walton type, Handigraph type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type and High frequency type are used as the electron beam irradiation source. The applied electron beam irradiation device can be applied. The acceleration voltage of the electron beam irradiated from the electron beam irradiation device is 1
It is preferable that the irradiation amount is 50 to 250 kV and the irradiation amount is about 0.5 to 5 Mrad. If it is less than 0.5 Mrad, curing may be insufficient, while if it exceeds 5 Mrad, the thermoplastic sheet 1 may be deteriorated. Usually this process is 50-500
Since a line speed of m / min is possible, the production efficiency is extremely high.

As the above-mentioned ionizing radiation-curable coating liquid, two or more ionizing radiation-curable coating liquids having different surface gloss after coating and curing are used, and one or more of them are used as desired. When applied in a pattern, a design feeling having a visual three-dimensional effect due to a change in surface gloss can be obtained.

Specifically, for example, a first ionizing radiation-curable coating liquid having a low surface gloss after coating and curing, and a second ionizing radiation-curing coating liquid having a high surface gloss after coating and curing are provided. Is prepared in advance, and the first surface of the thermoplastic sheet 1 is
The low gloss surface protection layer 31 is provided by applying an ionizing radiation curable coating liquid of
A second ionizing radiation-curable coating liquid is partially applied only to a portion where high gloss is desired to be provided, and a patterned high gloss surface protective layer 32 is provided. Thereafter, the entire surface is irradiated with ionizing radiation and cured. By doing so, a pattern having a gloss difference can be formed on the surface protective layer 3 (FIG. 2).

Of course, the low-gloss surface protective layer 31 and the high-gloss surface protective layer 32 are formed by providing the high-gloss surface protective layer 32 on the entire surface and then providing the low-gloss surface protective layer 31 in a pattern. Or both may be provided in a pattern.
Also, the gloss of the ionizing radiation-curable coating liquid is not limited to two types, and it is of course possible to use three or more types. Instead of using three or more types of coating liquids, two or more types of coating liquids are used, and one or more of them are provided in a stepwise or continuous gradation, so that a stepwise or continuous You can also get a nice visual three-dimensional effect.

If the coating liquid to be applied first is liquid at room temperature, it is difficult to apply the next coating liquid thereon in a pattern, so that the coating liquid is applied first. It is preferable to apply the next coating liquid after curing the coating liquid. However, if the previously applied coating liquid is completely cured, the adhesion to the next coating liquid will be reduced, and the next coating liquid will be in an incompletely cured state where fluidity is lost. It is preferable that the coating be applied and then ionizing radiation be re-irradiated to completely cure the coating. Specifically, the incompletely cured state is about 50 to 99% of the radical polymerizable double bond, more preferably 70 to 95%.
It is desirable that the degree is consumed by the polymerization reaction.

The method of controlling the gloss of the ionizing radiation-curable coating liquid is not particularly limited. For example, inorganic particles such as silica, alumina, calcium carbonate, barium sulfate, talc and kaolin, polyester, polycarbonate, A matting agent selected from synthetic resin particles such as polyurethane, acrylic and polyamide, and / or a gloss adjusting agent such as a polishing agent selected from fatty acids, fatty acid esters, metal soaps, low molecular weight polyethylene, and silicone compounds. By blending at an appropriate blending ratio, a desired gloss can be adjusted.

The range of each glossiness may be appropriately set to a desired range according to tastes and applications, but in order to effectively obtain a visual three-dimensional effect due to the difference in gloss, at least the 60-degree reflection glossiness must be set at least. It is desirable that the difference be 10 or more, more preferably 20 or more. Specifically, the 60-degree reflection glossiness of the layer with the lowest gloss (low gloss surface protection layer 31) is 10 or less, and the 60-degree reflection gloss of the layer with the highest gloss (high gloss surface protection layer 32) is 60 or less.
The degree of reflection glossiness is desirably 20 or more, more preferably 30 or more.

The type of the pattern having the difference in gloss is not particularly limited. For example, by making the portion corresponding to the conduit portion of the wood grain low gloss and the other portion having high gloss, as in the case of wood grain of natural wood, It is possible to obtain a three-dimensional design feeling as if the conduit part is deeply depressed.

Examples of the method of applying the ionizing radiation-curable coating liquid in a pattern form include gravure printing, offset printing, gravure offset printing, screen printing, and the like.
The method can be appropriately selected from any conventionally known methods such as a flexographic printing method, a dry offset printing method, and an ink jet printing method.

In addition to the method of providing a pattern having a difference in gloss on the surface protective layer 3 as described above, the provision of a synchronous uneven pattern on the surface protective layer 3 can also impart an excellent three-dimensional design feeling to the decorative sheet. Can be. A typical method of forming a tuning concavo-convex pattern is a method utilizing a liquid repellent effect. In this method, a liquid repellent pattern 33 made of a resin composition containing a liquid repellent made of a material having a low surface tension such as a silicone compound or a fluorine compound is provided on the surface of the thermoplastic sheet 1 in advance, and is formed thereon. The entire surface is coated with an ionizing radiation-curable coating liquid, and is irradiated with ionizing radiation in a state where the coating liquid is repelled on the lyophobic pattern 33 to be cured. This is a method of providing a surface protective layer 3 on the substrate (FIG. 3). If the liquid-repellent pattern 33 is colored in an appropriate color (for example, a pipe color in a wood grain pattern), a concave portion that completely matches (tunes) with the color pattern can be formed on the surface. In this case, the lyophobic pattern 33 and the surface protection layer 3
The thickness of the surface protective layer 3 after curing is preferably at least 5 μm, and most preferably in the range of 10 to 30 μm in order to form a sufficient step between the surface protective layer 3 and the surface protective layer 3.

In the above method, in order to secure the solvent resistance and the surface hardness of the liquid repellent pattern 33, it is desirable that the liquid repellent pattern 33 be formed from a composition mainly composed of a curable resin. The liquid-repellent pattern 33 may be formed from a composition mainly composed of a thermosetting resin such as a urethane-based resin or an aminoalkyd-based resin. The surface protective layer 3 can be cured simultaneously with the curing of the surface protective layer 3 by an ionizing radiation irradiation step after the coating of the layer 3 is formed. Also, there is an advantage that excellent adhesion can be obtained by the conversion.

In addition to the above-mentioned methods for forming the tuning concavo-convex pattern on the surface protective layer 3, (1) a porous material such as porous silica is contained in a portion of the surface of the thermoplastic sheet 1 where a concave portion is to be formed. A resin-absorptive pattern made of the composition is formed, and thereafter, an ionizing radiation-curable coating liquid is applied to the entire surface of the thermoplastic sheet 1 including the resin-absorptive pattern. A method of forming a concave portion by absorbing an ionizing radiation-curable coating liquid into a resin absorbent pattern,
(2) A foamed resin pattern is formed on the surface of the thermoplastic sheet 1 where a concave portion is to be formed, and an ionizing radiation-curable coating liquid is applied to the entire surface of the thermoplastic sheet 1 including the foamed resin pattern. Then, after or before curing, a method of forming a concave portion by depressing the foamed resin pattern portion by a method such as heating, action of a solvent, or mechanical grinding, and (3) forming a concave portion on the surface of the thermoplastic sheet 1 A reactive pattern containing a chemical substance that chemically reacts with a component in the ionizing radiation-curable coating liquid to generate a gas is formed at a desired position, and the thermoplastic sheet 1 containing the reactive pattern is formed. Ionizing radiation-curable coating liquid is applied over the entire surface, and the ionizing radiation-curable coating liquid on the reactive pattern is foamed by reacting with the chemical substance in the reactive pattern. After or before curing the coating liquid, heat, Alternatively, a method in which the foamed portion is depressed by a method such as mechanical grinding to form a concave portion, and (4) a curing suppression pattern containing an ionizing radiation curing inhibitor is formed in a portion of the surface of the thermoplastic sheet 1 where a concave portion is to be formed. Aside
An ionizing radiation-curable coating liquid is applied to the entire surface of the thermoplastic sheet 1 including the curing-suppressing pattern, and the coating liquid is irradiated with ionizing radiation to apply the ionizing radiation-curable coating liquid to portions other than on the curing-suppressing pattern. Utilizes the phenomenon of curing and shrinking faster than on the cure-inhibiting pattern to form recesses on the curing-inhibiting pattern, or an uncured ionizing radiation-curable type that remains on the curing-inhibiting pattern after irradiation with ionizing radiation A method for washing and removing the coating liquid,
Any method selected from the above can be adopted. In any case, if the resin absorbent pattern, the foamed resin pattern, the reactive pattern, the curing control pattern, and the like are colored in an appropriate color, a concave portion that perfectly matches (tunes) with the color pattern is formed on the surface. (These are not particularly shown, but in FIG. 3, the lyophobic pattern 33 is a resin absorbent pattern,
This is a form read as a foamed resin pattern, a reactive pattern, a curing suppression pattern, or the like).

An excellent three-dimensional design feeling can be achieved by providing the unevenness 34 on the surface of the surface protection layer 3 instead of providing the synchronized unevenness pattern on the surface protection layer 3 as described above. be able to. This method can be roughly classified into the following two methods. The first method is a method in which the unevenness 34 is formed on the surface of the thermoplastic sheet 1 in advance, and the surface protective layer 3 is formed thereon while holding the unevenness 34 (FIG. 4). The second approach is
This is a method of forming the surface protective layer 3 having the unevenness 34 on the surface of the thermoplastic sheet 1 having a smooth surface (FIG. 5). Of course, it is technically possible to use both together.

In the first method, the method of forming the irregularities 34 on the surface of the thermoplastic sheet 1 includes, for example, (1) the irregularities 34 to be formed on the surface of the thermoplastic sheet 1. An embossing plate, embossing roll or shaping film made of a hard and heat-resistant material such as a metal or a heat-resistant resin having a concavo-convex shape inverted on the surface is prepared in advance, and this is heated and softened. A method of transferring and forming the uneven shape 34 on the surface of the thermoplastic sheet by pressing the surface of the sheet 1; (2) simultaneously extruding the heated and melted thermoplastic resin into a film or sheet, and embossing the same as the above. A method of laminating in a molten state on a surface of a plate, an embossing roll, a shaping film, or the like, and separating from the surface of the embossing plate or the like after cooling and solidifying; (3) the surface of the thermoplastic sheet 1 A method of performing a stencil printing with an appropriate resin composition on a surface of a portion to be a convex portion by a method such as a gravure printing method or a screen printing method, and (4) a portion to be a convex portion on the surface of the thermoplastic sheet 1. Forming a resist pattern made of a chemical resistant material, and dissolving or decomposing and removing a surface portion of the thermoplastic sheet 1 in a portion where the resist pattern is not provided with an appropriate solvent or chemical to form a concave portion; Thereafter, an appropriate method selected from a method of removing the resist pattern and the like can be adopted.

On the other hand, in the second method, the method for forming the surface protective layer 3 having the irregularities 34 on the surface of the thermoplastic sheet 1 is specifically exemplified by (1) Thermoplastic sheet An ionizing radiation curable coating liquid is applied to a uniform thickness on the surface of No. 1 and the same embossing plate, embossing roll or shaping film as described above is pressed onto the surface to transfer and form the uneven shape 34. A method of curing by irradiating with ionizing radiation before or after separating it from the embossing plate or the like, (2) ionizing radiation curable coating on the surface of the same embossing plate, embossing roll or molding film as described above A liquid is applied, and the thermoplastic sheet 1 is pressed against the coated surface to laminate an ionizing radiation-curable coating liquid on the thermoplastic sheet 1, and before or after the ionizing radiation is released from the embossing plate or the like, Irradiated and cured That method, (3) a thermoplastic sheet 1
Is uniformly coated with an ionizing radiation-curable coating liquid, and the coated surface is exposed through an ionizing radiation shielding pattern such as a photomask or a plate making film, or formed by a method such as a beam scanning method. Irradiation is performed at different exposure doses depending on the height of the uneven shape 34 to be formed, and the uneven shape 34 is formed by utilizing a difference in shrinkage due to a difference in curing speed, or curing after irradiation with ionizing radiation is performed. A method of forming an uneven shape 34 by washing and removing an uncured ionizing radiation-curable coating liquid by utilizing a difference in state, (4) an ionizing radiation curing accelerator or a curing inhibitor in advance on the thermoplastic sheet 1 Is formed, and the unevenness 34 is formed using the difference in shrinkage due to the difference in curing speed, or the uncured ionizing radiation is used using the difference in the curing state after irradiation with ionizing radiation. Curable coating (5) a method of uniformly forming an ionizing radiation-curable coating solution on the surface of the thermoplastic sheet 1 by coating the surface of the thermoplastic sheet 1 with an ionizing radiation-curable coating liquid; Irradiating with ionizing radiation in a state in which the pattern surface of the pattern film on which the curing control pattern containing the curing accelerator or the curing inhibitor has been formed is pressed, and using the difference in shrinkage due to the difference in curing speed to form the uneven shape 34 Or, using the difference in curing state after irradiation with ionizing radiation,
Uncured ionizing radiation-curable coating liquid is removed to remove unevenness 3
(6) Ionizing radiation is applied to the thermoplastic sheet 1 by an appropriate method such as a gravure printing method or a screen printing method, depending on the height of the concave / convex shape 34 to be formed. An appropriate method selected from a method of applying a curable coating liquid and curing the liquid can be adopted.

As described above, even when the unevenness 34 is provided on the surface protective layer 3, if the colored ink 35 is applied to the concave portion of the unevenness 34, the surface of the surface becomes similar to the case of the above-mentioned synchronous unevenness pattern. Having a color pattern synchronized with the uneven shape 34,
A decorative sheet excellent in a three-dimensional design feeling can be obtained. The coloring ink 35 is selectively applied only to the concave portions of the concave / convex shape 34 by a method such as a wiping method in which unnecessary ink on the convex portions is scraped off with a doctor or a cloth or the like after the ink is applied to the entire surface. Can be.

When the irregularities 34 are formed on the surface protective layer 34 itself without being provided on the thermoplastic sheet 1, the place where the colored ink 35 is applied is necessarily on the surface protective layer 3 (FIG. 6). However, when the uneven shape 34 is provided on the surface of the thermoplastic sheet 1, the location where the colored ink 35 is applied may be on the surface protective layer 3 (FIG. 7), or the thermoplastic sheet may be used. 1 and the surface protective layer 3 (FIG. 8). When the irregularities 34 are provided on the surface of the thermoplastic sheet 1, the coloring ink 35 is preferably provided between the thermoplastic sheet 1 and the surface protective layer 3 by using a normal ink as the coloring ink 35. Even so, the protection by the surface protective layer 3 is advantageous because problems such as solvent resistance and abrasion resistance do not occur.

On the other hand, when the colored ink 35 is provided on the surface protective layer 3, in consideration of solvent resistance, abrasion resistance, etc., an ink using a curable resin as a vehicle is used as the colored ink 35. In particular, it is most preferable to use an ink using an ionizing radiation-curable resin as a vehicle. Further, since the completely cured ionizing radiation-curable resin generally has poor adhesiveness, if the colored ink 35 is provided after the surface protective layer 3 is completely cured, the adhesion between the surface protective layer 3 and the colored ink 35 tends to be insufficient. . Therefore,
The colored ink 35 is applied in an incompletely cured state in which the surface protective layer 3 has been cured to such an extent that the colored ink 35 can be applied or wiped, and then the surface protective layer 3 is completely cured by irradiating ionizing radiation again. Is good. Specifically, the incompletely cured state is about 50 to 99%, more preferably 70 to 95%, of the radically polymerizable double bonds of the ionizing radiation-curable resin composition forming the surface protective layer 3. It is desirable that the degree is consumed by the polymerization reaction. When the coloring ink 35 uses an ionizing radiation curable resin as a vehicle, the radical polymerizable double bond contained in the coloring ink 35 and the radicals remaining in the incompletely cured surface protective layer 3 are formed. There is an advantage that excellent adhesion between the surface protective layer 3 and the coloring ink 35 can be obtained by chemically and strongly bonding the two by a polymerization crosslinking reaction with the polymerizable double bond. .

As the thermoplastic sheet 1 as the base sheet of the decorative sheet of the present invention, any known film or sheet made of a thermoplastic resin which has been generally used as a constituent material of the decorative sheet is conventionally used. Can be used. Specifically, for example, polyethylene, polypropylene, polybutene, polyolefins such as polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene- Vinyl alcohol such as vinyl alcohol copolymer, vinylon, etc., polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate-isophthalate copolymer, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polyacryl Acrylics such as butyl acid, polyamides such as nylon 6 and nylon 66, cellulose triacetate, cellulosic such as cellophane,
Examples include a single layer or a laminate of a synthetic resin film or sheet of polystyrene, polycarbonate, polyarylate, polyimide and the like. The thickness of the thermoplastic sheet 1 is not particularly limited, but is generally selected from a range of about 20 to 500 μm, and most preferably a range of about 50 to 250 μm.

Further, the thermoplastic sheet 1 may be provided with a picture layer 2 expressing a desired and appropriate picture pattern. The formation position of the picture layer 2 may be on the front surface of the thermoplastic sheet 1 (FIGS. 1 to 8), or when the thermoplastic sheet 1 is transparent or translucent, on the back surface of the thermoplastic sheet 1. (Fig. 9). When the thermoplastic sheet 1 is a laminate of a plurality of thermoplastic resin layers, as long as the thermoplastic resin layer on the surface side of the picture layer 2 is transparent or translucent, the plurality of thermoplastic resin layers Any layer may be used. For example, when the thermoplastic sheet 1 is composed of two layers, a base thermoplastic sheet 11 on the back side and a transparent thermoplastic sheet 12 on the front side, the picture layer 2 is formed of the base thermoplastic sheet 11 and the transparent thermoplastic sheet. 12 (FIG. 10). Further, the formation position of the picture layer 2 is not limited to one place, but by providing it at a plurality of places with the transparent layer interposed, it is possible to express a complicated design that changes depending on the viewing angle.

As described above, even when the picture layer 2 is provided on the back surface or between layers of the thermoplastic sheet 1 or on a plurality of locations selected from the front surface, the back surface and the interlayer, the surface protective layer 3 has a pattern having a gloss difference. Of course, it is also possible to provide a tuned uneven pattern or uneven shape, or to provide a colored ink in a concave portion of the uneven shape.

When the pattern layer 2 is provided on the surface of the thermoplastic sheet 1, that is, between the surface protective layer 3 and the pattern layer 2,
The ink used for printing preferably has good adhesion to both the thermoplastic sheet 1 and the ionizing radiation-curable resin composition constituting the surface protective layer 3, and may be appropriately selected according to the respective materials. . The method of forming the picture layer 2 is not particularly limited, and a suitable resin is used as a vehicle, and a printing ink or a paint which is colored with a suitable coloring agent such as a dye or a pigment is used. It can be formed by any conventionally known printing method such as a printing method, a gravure offset printing method, a flexographic printing method, a dry offset printing method, a screen printing method, and an inkjet printing method.

In general, decorative sheets often require a concealing property for concealing undesired colors, color unevenness, defects and the like on the surface of the base material for decorative materials. Thermoplastic sheet 1
And when the pattern layer 2 does not achieve a sufficient concealing property, the same as the case of the pattern layer 2 except that the opaque layer contains a concealing pigment such as an inorganic pigment and has a concealing property. 21 can be provided (FIG. 11).
As a method for forming the concealing layer 21, various printing methods similar to those for the picture layer 2, such as a gravure coating method, a die coating method, a lip coating method, a knife coating method, an air knife coating method, a spray coating method, and a flow coating method Method, a roll coating method, a dip coating method, and other various coating methods can be appropriately selected and applied.

If the adhesiveness between the thermoplastic sheet 1 and / or the picture layer 2 and the surface protective layer 3 is insufficient, an ionizing radiation-curable coating liquid for forming the surface protective layer 3 is applied. Before the coating, a primer layer 4 for improving the adhesion with the ionizing radiation-curable coating liquid can be provided on the thermoplastic sheet 1 with or without the picture layer 2 (FIG. 1).
2). Examples of the primer layer 4 include acrylic resins, urethane resins, carboxylic acid-modified olefin resins, chlorinated olefin resins, ethylene-vinyl acetate resins, vinyl chloride-vinyl acetate resins, polyester resins, and polyamide resins. An easy-adhesive resin composition comprising an epoxy resin, a cellulose derivative and the like can be used. Among them, it is most preferable to use an acrylic resin or a urethane resin from the viewpoint of adhesion to various thermoplastic resins and ionizing radiation-curable resins and weather resistance.

The easily adhesive resin composition constituting the primer layer 4 may be of a one-pack type or a two-pack type.
In particular, when a two-pack type resin composition containing an isocyanate compound is used, the thermoplastic sheet 1 is a resin having poor adhesion due to the high reaction activity of the isocyanate compound, such as an olefin resin. Also,
There is an advantage that excellent adhesion can be achieved. Of course, the present invention can be applied to the thermoplastic sheet 1 made of a general thermoplastic resin other than the olefin resin. Specifically, as a resin composition containing such an isocyanate compound,
For example, acrylic polyol, polyester polyol,
Resin compositions in which polyol compounds such as polyurethane polyols and polyether polyols are mixed with polyisocyanate compounds such as tolylene diisocyanate, mesitylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate can be exemplified.

In particular, when a resin composition containing at least a compound containing a radical polymerizable double bond is used as the primer layer 4, the primer layer 4 may be in contact with the ionizing radiation-curable resin composition forming the surface protective layer 3. Has the advantage that it can be chemically bonded strongly by a radical polymerization reaction to achieve excellent adhesion. Examples of the compound containing a radical polymerizable double bond include, for example, various prepolymers, oligomers, and monomers described as the constituents of the ionizing radiation-curable resin composition for forming the surface protective layer 3 described above. Can be. When such a resin composition is employed, before the radical polymerizable double bond in the primer layer 4 is consumed by the crosslinking reaction, an ionizing radiation-curable coating liquid for forming the surface protective layer 3 is applied. Work,
It is needless to say that it is desirable to irradiate this with ionizing radiation to simultaneously cross-link and cure the two.

The decorative sheet of the present invention is used by sticking to the surface of various types of decorative material base materials as in the case of the conventional decorative sheet. In some cases, adhesion to a general-purpose adhesive used for adhesion to a substrate is poor. In such a case, for example, an acrylic resin, a urethane-based resin, a polyester-based resin, an ethylene-vinyl acetate-based resin, a vinyl chloride-vinyl acetate-based resin, or the like, is mainly provided on the back surface of the thermoplastic sheet 1. By providing the easy-adhesive back coat layer 5 described above, the adhesiveness with various adhesives can be improved (FIG. 13). The easily adhesive back coat layer 5
In addition, for example, when a powdery substance such as silica is added, the surface becomes a mat-like, and it is effective in preventing blocking during winding and storage, and further improving the adhesiveness by utilizing an anchoring effect. is there.

The decorative sheet 93 of the present invention described above
For example, wood-based materials such as plywood, particle board, medium density fiber board, and inorganic materials such as gypsum board, calcium silicate board, asbestos cement board, wood wool cement board, glass fiber reinforced concrete board, lightweight cellular concrete board, etc. Base material, AB
An optional adhesive 92 may be applied to the surface of any cosmetic material base material 91 selected from a synthetic resin base material such as S resin and a metal base material such as iron, brass, stainless steel, and aluminum, if necessary. The laminated decorative material 9 can be used for interior and exterior of buildings and vehicles, and for surface decoration of furniture and fixtures, home appliances, and the like.

The decorative sheet 93 of the present invention is attached to one side of a flat base material 91 for decorative material,
1, on the surface on which the decorative sheet 93 is not attached,
For example, V-shaped, U-shaped or comb-shaped grooves are formed and bent, and formed into a three-dimensional shape to form a decorative material 9 (V-cut processing) (FIG. 14), or for a decorative material having a three-dimensional shape On the surface of the base material 91, for example, a method of applying heat or pressure using an elastic plate or an elastic roll made of rubber or the like, for example, a lapping laminating method, a vacuum forming laminating method (including a pressurized air laminating method and a vacuum pressurizing laminating method), By means, the decorative sheet 93 is formed in accordance with the three-dimensional shape of the surface of the decorative material base material 91 and laminated to form the decorative material 9 (three-dimensional molding laminate) (FIG. 15). be able to. That is, the decorative sheet 93 of the present invention is excellent in bending workability and three-dimensional forming workability by using the thermoplastic sheet 1 as a base sheet, and can be three-dimensionally processed without fear of forming defects such as breakage, The surface is provided with a surface protective layer made of ionizing radiation curable resin, so it has excellent surface hardness, scratch resistance, abrasion resistance, solvent resistance, etc. This is because the feeling can be easily given.

[0050]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples of the decorative sheet of the present invention.

Example 1 A corona treatment was applied to the surface of a 90 μm-thick colored random-polymerized polypropylene resin film, and the grain pattern was formed by a gravure printing method using a urethane gravure printing ink (“Lamistar” manufactured by Toyo Ink Mfg. Co., Ltd.). Is applied, and a primer containing an isocyanate compound and a urethane acrylate compound ("Primer X" manufactured by Dainichi Seika Co., Ltd./"Ebecryl 1290 "manufactured by Daicel UCB) is dried and coated on the printed surface. An amount of 1 g / m ² to form a primer layer, and thereafter, an ionizing radiation-curable coating solution (“EB-230” manufactured by Daicel UCB Co., Ltd./1,6-hexanediol diacrylate / Daicel U CB Co., Ltd. “Evecryl 350”, viscosity adjusted to 300 cps) by gravure coating method To a coating amount of 8 g / m ^2, and irradiate an electron beam with an electron beam irradiation device at an accelerating voltage of 200 kV and an irradiation dose of 5 Mrad / cm ² to form a surface protective layer, and finally a corona treatment on the back surface Thereafter, a urethane-based easily-adhesive backcoat layer containing silica powder was applied to a coating amount of 1 g / m ² after drying to prepare a decorative sheet of the present invention.

<Example 2> The surface of a colored random polymerization polypropylene resin film having a thickness of 90 μm was subjected to a corona treatment, and a wood pattern was formed by a gravure printing method using a urethane gravure printing ink (“Lamistar” manufactured by Toyo Ink Mfg. Co., Ltd.). Is applied, and a primer containing an isocyanate compound and a urethane acrylate compound ("Primer X" manufactured by Dainichi Seika Co., Ltd./"Ebecryl 1290 "manufactured by Daicel UCB) is dried and coated on the printed surface. An amount of 1 g / m ² was applied to form a primer layer, and thereafter, 10% by weight of a silica-based matting agent and a photoradical polymerization initiator (“Darocur 1173” manufactured by Merck)
Ionizing radiation-curable coating liquid containing 3% by weight (“EB-230” / 1,6-hexanediol diacrylate manufactured by Daicel UCB / Evecryl 350 ”manufactured by Daicel UCB, adjusted to a viscosity of 300 cps ) Was applied to a coating amount of 4 g / m ² by a gravure coating method to form a low-gloss surface protective layer. Using the same ionizing radiation-curable coating liquid to which the above-mentioned radical polymerization initiator is not added, and applying a gravure printing method to a portion other than the wood grain conduit portion to a coating amount of 6 g / m ² to obtain a high gloss surface A protective layer is formed, and thereafter, an acceleration voltage of 200 kV and an irradiation dose of 5 Mrad / cm by an electron beam irradiation device.
Irradiation of the electron beam of ² to cure to form a surface protective layer, and finally apply a urethane-based easy-adhesion back coat layer containing silica powder after corona treatment on the back surface to a coating amount of 1 g / m ² after drying, A decorative sheet of the present invention was produced.

<Example 3> The surface of a colored random polymerization polypropylene resin film having a thickness of 90 µm was subjected to a corona treatment, and the grain pattern was formed by a gravure printing method using a urethane-based gravure printing ink (“Lamistar” manufactured by Toyo Ink Mfg. Co., Ltd.). Is applied, and a primer containing an isocyanate compound and a urethane acrylate compound ("Primer X" manufactured by Dainichi Seika Co., Ltd./"Ebecryl 1290 "manufactured by Daicel UCB) is dried and coated on the printed surface. An amount of 1 g / m ² was applied to form a primer layer, and a liquid-repellent ionizing radiation-curable ink containing 5% by weight of silicone oil (“EB-810 manufactured by Daicel UCB Co., Ltd.”) was formed on the primer layer. / Trimethylolpropane triacrylate / color pigment) by gravure printing After that, an ionizing radiation-curable coating liquid (“EB-230” manufactured by Daicel UCB Co., Ltd./1,6-hexanediol diacrylate / “Ebecryl 350 manufactured by Daicel UCB Co., Ltd.”) ”, Adjusted to a viscosity of 300 cps) by a gravure coating method at an application amount of 8 g / m ^2, and repelled on the lyophobic pattern to form a concave portion. A surface protection layer is formed by irradiating with 5 Mrad / cm ^{2 of} an electron beam to form a surface protective layer. Finally, a urethane-based easy-adhesion back coat layer containing silica powder after corona treatment is applied to the back surface to a coating amount of 1 g / m ² after drying. Give
A decorative sheet of the present invention was produced.

Example 4 A corona treatment was applied to the surface of a 90 μm-thick colored random-polymerized polypropylene resin film, and the grain pattern was formed by a gravure printing method using a urethane gravure printing ink (“Lamister” manufactured by Toyo Ink Mfg. Co., Ltd.). Is applied, and a primer containing an isocyanate compound and a urethane acrylate compound ("Primer X" manufactured by Dainichi Seika Co., Ltd./"Ebecryl 1290 "manufactured by Daicel UCB) is dried and coated on the printed surface. An amount of 1 g / m ² was applied to form a primer layer, and an ionizing radiation-curable ink (“EB-810” manufactured by Daicel UCB Co., Ltd.) Resin absorption of conduit pattern by gravure printing method with methylol propane triacrylate / colored pigment) After that, an ionizing radiation curable coating liquid (“EB-230” manufactured by Daicel UCB Co., Ltd./1,6-hexanediol diacrylate / “Evecryl 350” manufactured by Daicel UCB Co., Ltd.) (Adjusted to a viscosity of 300 cps) by a gravure coating method to a coating amount of 8 g / m ² , absorb the coating liquid on the resin-formed pattern into a resin-absorptive pattern to form a concave portion, and then apply it to an electron beam irradiation device. The surface protective layer was formed by irradiating an electron beam with an acceleration voltage of 200 kV and an irradiation dose of 5 Mrad / cm ² to form a surface protective layer. Finally, the back surface of the urethane-based easy-adhesive back coat layer containing silica powder after corona treatment was dried. The decorative sheet was applied at an application amount of 1 g / m ² to prepare a decorative sheet of the present invention.

Example 5 A corona treatment was applied to the surface of a 90 μm-thick colored random polymerization polypropylene resin film, and a wood pattern was formed by a gravure printing method using a urethane-based gravure printing ink (“Lamistar” manufactured by Toyo Ink Mfg. Co., Ltd.). Is printed, and a two-liquid urethane-based primer agent (“Adcoat AD-
502 ”) after coating and drying to a coating amount of 1 g / m ² after drying.
A 20 μm thick heat-adhesive resin (maleic acid-modified ethylene-ethyl acrylate copolymer) and a 60 μm thick transparent olefin resin (random polymerized polypropylene /
Low-density polyethylene), and simultaneously melt-extruding the heat-adhesive resin surface and laminating the printed surface of the film,
Simultaneously with the lamination, emboss the conduit pattern on the transparent olefin resin surface using an emboss roll, and after corona treatment,
The concave portion of the emboss is filled with a urethane-based ink ("Ramister" manufactured by Toyo Ink Manufacturing Co., Ltd.) by a wiping method, and a primer containing an isocyanate compound and a urethane acrylate compound over the entire surface (manufactured by Dainichi Seika Co., Ltd.) Primer X "/" Evecryl 1290 "manufactured by Daicel UCB Co., Ltd.)
The primer layer is formed by coating the m ^2, thereafter, the ionizing radiation-curable coating liquid (Daicel UCB Co., Ltd. "EB-230" / 1,6 / Daicel UCB Co., Ltd. "Evecryl 350", adjusted to a viscosity of 300 cps) by a gravure coating method at an application amount of 8 g / m ² , and is cured by irradiating an electron beam with an acceleration voltage of 200 kV and an irradiation dose of 5 Mrad / cm ² by an electron beam irradiation device. To form a surface protective layer. Finally, the back surface layer was subjected to corona treatment, and a urethane-based easy-adhesion back coat layer containing silica powder was applied to the applied amount of 1 g / m ² after drying to produce a decorative sheet of the present invention. .

Example 6 A surface of a colored random polymerization polypropylene resin film having a thickness of 90 μm was subjected to a corona treatment, and a wood pattern was formed by a gravure printing method using a urethane gravure printing ink (“Lamistar” manufactured by Toyo Ink Mfg. Co., Ltd.). Is applied, and a primer containing an isocyanate compound and a urethane acrylate compound ("Primer X" manufactured by Dainichi Seika Co., Ltd./"Ebecryl 1290 "manufactured by Daicel UCB) is dried and coated on the printed surface. An amount of 1 g / m ² to form a primer layer, and thereafter, an ionizing radiation-curable coating liquid (Daicel UCB) to which 3% by weight of a photoradical polymerization initiator (“Darocur 1173” manufactured by Merck) was added. "EB"
-230 "/ 1,6-hexanediol diacrylate /" Evecryl 35 manufactured by Daicel UCB Co., Ltd.
0 ", adjusted to a viscosity of 300 cps) to a coating amount of 20 g / m ² by a gravure coating method.
After pressing a molding film formed by embossing and printing a conduit pattern with a silicone ink on a biaxially stretched polyethylene terephthalate film of μm in pressure, it was irradiated with ultraviolet light from an ultra-high pressure mercury lamp to obtain an incompletely cured state. The mold film is peeled off to form a surface protective layer in which the irregular shape of the conduit pattern is formed, and ionizing radiation-curable coloring ink (“EB-81” manufactured by Daicel UCB Co., Ltd.) is formed in the concave portion of the irregular shape.
0 "/ trimethylolpropane triacrylate / colored pigment) by a wiping method, and then irradiating an electron beam with an electron beam irradiation device at an acceleration voltage of 200 kV and an irradiation dose of 3 Mrad / cm ² to color the surface protective layer and the concave portions. The ink was completely cured, and finally, the back surface was subjected to corona treatment, and a urethane-based easy-adhesion back coat layer containing silica powder was applied to a dry coating amount of 1 g / m ² to prepare a decorative sheet of the present invention.

Using the six types of decorative sheets of Examples 1 to 6, an aqueous two-liquid urethane resin-based adhesive was previously applied to the surface to a coating amount of 10 g / m ² after drying, and dried. When three-dimensionally formed and laminated on the surface of a wooden base material having a three-dimensional three-dimensional shape of 5R by a vacuum forming method, any three-dimensionally formed decorative material can be obtained without any forming defects such as sheet breakage. I was able to. In addition, when these decorative sheets were attached to the surface of a plywood having a thickness of 3 mm, and the back surface of the plywood was subjected to V-cut processing and bent, any of the sheets was bent and formed without any forming defects such as sheet breakage. The obtained decorative material was obtained. In addition, these decorative materials have a surface hardness of 2H or more in pencil hardness, have scratch resistance and interlayer adhesion that do not hinder practical use, and, in addition to having a clear pattern by printing, of course, particularly in the working examples. Those using the decorative sheets Nos. 2 to 6 each had an excellent three-dimensional design feeling due to a difference in gloss and unevenness, and were full of luxury.

[0058]

As described in detail above, the decorative sheet of the present invention is characterized in that, in a decorative sheet provided with a surface protective layer on a thermoplastic sheet, an ionizing radiation-curable resin is used for the surface protective layer. Since the base sheet is a thermoplastic sheet, it is excellent in bending workability such as V-cut processing, lapping processing, vacuum forming processing and three-dimensional forming workability, and can perform three-dimensional processing without worrying about molding defects such as breakage,
The surface is provided with a surface protective layer using ionizing radiation-curable resin, so it has excellent surface hardness, scratch resistance, abrasion resistance, solvent resistance, etc., and the heat resistance of the base sheet Without limitation, excellent three-dimensional design feeling can be easily provided by a gloss difference pattern, a synchronous uneven pattern, an uneven shape, or the like. And the cosmetic material of the present invention,
By using such a decorative sheet of the present invention, a decorative material having a complex three-dimensional shape having both surface physical properties such as surface hardness and scratch resistance and a three-dimensional design feeling due to a difference in gloss and unevenness. Can be easily realized.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view showing an example of an embodiment of the decorative sheet of the present invention.

FIG. 3 is a schematic sectional view showing an example of an embodiment of the decorative sheet of the present invention.

FIG. 4 is a schematic sectional view showing an example of an embodiment of the decorative sheet of the present invention.

FIG. 5 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 6 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 7 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 8 is a schematic sectional view showing an example of an embodiment of the decorative sheet of the present invention.

FIG. 9 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 10 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 11 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 12 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 13 is a schematic sectional view showing an example of an embodiment of a decorative sheet of the present invention.

FIG. 14 is a schematic sectional view showing an example of an embodiment of a cosmetic material of the present invention.

FIG. 15 is a schematic cross-sectional view showing an example of an embodiment of the cosmetic material of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 thermoplastic sheet 11 base thermoplastic sheet 12 transparent thermoplastic sheet 2 picture layer 21 concealing layer 3 surface protective layer 31 low gloss surface protective layer 32 high gloss surface protective layer 33 liquid repellent pattern 34 uneven shape 35 colorant 4 primer layer 5 Easy-adhesive back coat layer 9 Make-up material 91 Make-up material base material 92 Adhesive 93 Make-up sheet

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK01A AK01B AK07 AS00B AT00C BA02 BA03 BA07 BA10B BA10C CC00B DD01B DD05C DD07B DD09B EH462 EJ283 EJ39B EJ532 EJ551 EJ651 GB07 GB08 GB81 HB00J HB31 JB14B JB14B

Claims (8)

[Claims] 1. A decorative sheet comprising a thermoplastic sheet provided with a surface protective layer, wherein the surface protective layer comprises an ionizing radiation-curable resin. 2. The decorative sheet according to claim 1, wherein a pattern having a difference in gloss is provided on the surface protective layer. 3. The decorative sheet according to claim 1, wherein said surface protective layer is provided with a synchronous uneven pattern. 4. The decorative sheet according to claim 1, wherein the surface protective layer has an uneven shape. 5. The decorative sheet according to claim 4, wherein a colored ink is applied to the concave and convex portions. 6. The decorative sheet according to claim 1, wherein a primer layer is provided between said thermoplastic sheet and said surface protective layer. 7. The decorative sheet according to any one of claims 1 to 6, which is attached to one side of a flat base material for decorative material, and the side of the base material for decorative material on which the decorative sheet is not attached. A decorative material characterized by being formed into a three-dimensional shape by subjecting a surface to a groove processing and bending. 8. A decorative material obtained by subjecting the decorative sheet according to any one of claims 1 to 6 to three-dimensional molding and laminating on the surface of a decorative material substrate having a three-dimensional shape.