JP2000211090A - Production of decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a decorative sheet by forming a pattern to the rear surface of a transparent base sheet having an embossed pattern formed on the surface thereof with good dimensional accuracy. SOLUTION: By a transfer method adapting a transfer sheet 5 consisting of a support sheet 6 and a transfer layer 7 and having a printing ink layer 8 having a pattern on the transfer layer to the surface of a transfer sheet 5, which has an embossed pattern 2 formed on the surface thereof and based on a thermoplastic resin, on the side opposite to the embossed surface while the base sheet is allowed to run as a long strip like sheet, the printing ink layer is transferred and formed to the base sheet to produce a decorative sheet S. The base sheet may be more enhanced in dimensional stability by applying curable resin paint to the surface on the side of the embossed pattern of the base sheet before the printing ink layer is formed to crosslink and cure the same to form a hard coating film layer 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative sheet having a transparent base sheet having an uneven pattern on the surface and a pattern on the back. This decorative sheet is used for various uses such as flooring (floor).

[0002]

2. Description of the Related Art Conventionally, a decorative sheet having a structure in which an uneven pattern is formed on the front side of a transparent base sheet and a printing ink layer having a picture is formed by printing on the back side of the sheet is, for example,
It was manufactured as follows. That is, the molten transparent resin sheet is extruded from a T-die, brought into contact with an embossing / cooling roller, solidified by cooling, and then peeled off from the roller to form an uneven pattern on the surface. A pattern layer and a solid color layer as a printing ink layer are printed on the back surface of the substrate (see JP-A-9-24585). That is, it is a method of forming a printing ink layer after shaping of a concavo-convex pattern.

[0003]

However, the method for producing a decorative sheet as described above has the following problems. That is, when a pattern or the like is printed on a long strip-shaped base sheet on which a concavo-convex pattern is formed, for example, by gravure rotary printing, the sheet passes through a drying device that dries the ink, and the sheet is heated. Will be. In the drying step at the time of printing a plastic film, it is rare to heat the film so as to cause deformation. Moreover, at this time, since tension is applied to the sheet, dimensional change occurs if the dimensional stability during heating of the base sheet is insufficient. Therefore, problems such as lack of dimensional stability of the pattern, misregistration of each color in the pattern of multicolor printing, or inability to match the pattern of the already formed concavo-convex pattern with the pattern pattern occur. There was something.

[0004] Incidentally, a method of shaping the concavo-convex pattern after forming the printing ink layer by reversing the order of printing and shaping of the concavo-convex pattern can be considered. However, in this case, after the printed sheet is heated to a semi-molten state, it is pressed with an embossing roll to form an uneven pattern, and in some cases, deformation by applying tension or stress relaxation of the sheet itself. And the like, and the dimensional stability of the printed pattern is further deteriorated, so that it is not practical. Moreover, since the base sheet to be used needs to have a property of softening by heating such that a concavo-convex pattern can be formed by embossing by hot pressure,
The dimensional stability is inevitably lower than that of a sheet that does not require embossing. Therefore, as a practical method of shaping a concavo-convex pattern after printing, a first transparent base material sheet made of a thermoplastic resin on which a printing ink layer has been formed is used as a second transparent base material made of a thermoplastic resin. This is performed by a so-called doubling embossing method or the like in which a sheet (top sheet) is laminated and at the same time an uneven pattern is formed on the second transparent base material sheet (see Japanese Patent Application Laid-Open No. 54-62255). However, in such a method in which two base sheets are laminated and used, the printing formation of the entire solid colored layer by the colored base sheet can be omitted, but the cost increases. Also, since the thickness of the colored base sheet is added to the decorative sheet, the whitening occurs in the decorative sheet, especially when the decorative sheet is attached to a wooden board or the like in the winter or the like and then V-cut. There are things. Further, since the colored base sheet and the transparent base sheet are each laminated by heat and pressure as solid sheets, the adhesion between the two sheets may be reduced by heat, moisture, light or the like.

[0005] As described above, if the register accuracy between the concavo-convex pattern and the picture pattern is poor, the design property is deteriorated, and the dimensional stability of the picture pattern (actually, the entire picture pattern including the concavo-convex pattern) is reduced. If it is not good, problems may occur in floor materials, window frame applications, and the like. For example, there is a floor material laminated with a decorative sheet instead of laminating a sliced veneer on MDF (medium density fiberboard) or plywood. In this case, the pattern of the decorative sheet is
As a pattern in which the veneers are bonded side by side, a grooving process is performed to make the joint portion between the adjacent veneers even more realistic. However, if the dimensional stability of the pattern on the decorative sheet is poor, the seam portion of the veneer on the pattern will be misaligned, and the actual groove position and the seam portion will not be aligned, resulting in unsightly flooring .

[0006] Accordingly, an object of the present invention is to provide a base material sheet having two
An object of the present invention is to provide a method of manufacturing a decorative sheet having a concave-convex pattern having a configuration using one base sheet, which can provide a pattern pattern with good dimensional stability on the back surface side without bonding. Another object of the present invention is to provide a manufacturing method capable of registering the picture pattern with the uneven pattern on the front side.

[0007]

In order to solve the above-mentioned problems, a method for producing a decorative sheet according to the present invention uses a transparent base sheet mainly made of a thermoplastic resin having an irregular pattern formed on its surface. , While running as a long strip-shaped sheet,
On the surface of the substrate sheet opposite to the uneven pattern, the printing ink layer is transferred by a transfer method using a transfer sheet comprising a support sheet and a transfer layer and having a printing ink layer having a picture as the transfer layer. The decorative sheet was transferred and formed. As a result, when a pattern is formed on the substrate sheet on which the concavo-convex pattern is formed, the printing ink layer does not contain a volatile solvent component such as, for example, gravure printing. The sheet is not heated by the drying device, and the dimensional accuracy of the pattern at the time of transfer formation of the printing ink layer can be reproduced as it is, and the dimensional stability of the pattern can be secured. In addition, even when a multicolor printing pattern is formed, it can be formed by transferring a transfer layer formed in advance by multicolor printing, and the color shift at the time of manufacturing a transfer sheet is about the same as the color shift of a normal print with respect to a sheet having good dimensional stability. Large color misalignment does not occur because the accuracy is within. This is because, in the transfer sheet, the support sheet does not need embossing properties for forming a concavo-convex pattern, and it is not necessary to use a sheet that is easily softened by heating, and a sheet having good dimensional stability can be used. In addition, since the dimensional stability of the picture pattern is good, registration of the picture pattern and the uneven pattern can be performed if necessary. For this reason, even when the decorative sheet obtained by the present invention is used for flooring or the like, the pattern does not look unsightly at the seam and does not shift. Further, since the decorative sheet obtained by the present invention has only one base sheet, the thickness of the decorative sheet can be reduced correspondingly, so that the sheet is whitened at the time of sheet bending such as V-cut processing. Nor.

[0008] The method for producing a decorative sheet according to the present invention comprises:
In addition to the above method, before transferring and forming the printing ink layer as a transfer layer on the substrate sheet, a transparent curable resin coating material is applied to the surface of the substrate sheet on the side of the uneven pattern and crosslinked and cured. To form a hard coating layer. By the hard coating layer, the base sheet further increases the dimensional stability, the dimensional stability of the picture pattern is further improved, and if necessary, the register between the picture pattern and the uneven pattern can be more accurately matched. .

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a method for manufacturing a decorative sheet according to the present invention will be described with reference to the drawings.

FIG. 1 is a conceptual diagram for explaining a method for producing a decorative sheet according to the present invention. FIG. 2 is a schematic view showing a method of forming a concave and convex pattern on a substrate sheet used in the present invention. FIG. 3 is a conceptual view illustrating the method, FIG. 3 is a conceptual view illustrating another method for forming a base sheet by similarly forming an uneven pattern, and FIG. 4 is an example of a layer configuration of the base sheet obtained by the method of FIG. FIG. 5 is a cross-sectional view schematically showing a base sheet provided with a hard coating layer, FIG. 6 is a cross-sectional view of an example of a transfer sheet used in the present invention, and FIG. 7 is obtained in the present invention. It is sectional drawing which illustrates some of decorative sheets.

[Base Sheet] The base sheet 1 is a sheet mainly composed of a thermoplastic resin, and is not particularly limited as long as it is a transparent sheet having at least one surface formed with a concavo-convex pattern. The simplest configuration is a sheet in which the entire thickness of the base sheet is made of a thermoplastic resin, but a sheet in which a majority of the entire thickness is made of a thermoplastic resin, that is, a sheet mainly containing a thermoplastic resin. Good. For example, a base sheet or the like in which a layer made of a substance other than the thermoplastic resin, such as a hard coating layer made of a curable resin described later, is laminated on a layer made of a thermoplastic resin (see FIG. 5). In addition, the transparency of the base sheet only needs to be such that the pattern of the printing ink layer formed on the back side of the decorative sheet when the decorative sheet is formed is transparent to the extent that it is visible or more. Further, the term “transparent” may be colorless and transparent in addition to non-colored and transparent. The thickness of the base sheet depends on the depth of the concavo-convex pattern to be formed.
About 200 μm.

Examples of the thermoplastic resin include, for example, polyolefin resin, vinyl resin such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate. Polyester resin such as isophthalate copolymer, acrylic resin such as polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, cellophane, It is a resin such as polycarbonate.

The above-mentioned polyolefin resin includes highly crystalline non-crystalline resins such as polyethylene (low density or high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer and propylene-butene copolymer. Elastomer polyolefin resins or various olefin thermoplastic elastomers can be used. As the olefin-based thermoplastic elastomer, for example, the following can be used.

In Japanese Patent Publication No. Hei 6-23278,
(A) As a soft segment, the number average molecular weight Mn is 2
An atactic polypropylene soluble in boiling heptane having a weight average molecular weight Mw of not less than 5,000 and a ratio of weight average molecular weight Mw to number average molecular weight Mn of 7 to 10 to 90% by weight;
As a hard segment, the melt index is 0.1
Soft polypropylene consisting of a mixture of ４4 g / 10 min boiling heptane-insoluble isotactic polypropylene 90-10 wt%. Among this kind of olefin-based thermoplastic elastomers, so-called "necking" is unlikely to occur, and when molded into various shapes by heating and pressing, as a material having good suitability, a mixture of isotactic polypropylene and atactic polypropylene is used. In the above, the mixing ratio of the isotactic polypropylene and the atactic polypropylene is 5% by weight or more and 50% by weight or less in weight ratio of the atactic polypropylene.

[0015] The polypropylene-based olefin-based thermoplastic elastomer itself is already known, but when it is used in a conventionally known application such as a packaging container, the weight of the atactic polypropylene as a soft segment is emphasized in order to emphasize strength. Those with a ratio of less than 5% by weight were exclusively used. However, when forming into a three-dimensional shape or a concavo-convex shape, necking occurs as described above, and good processing is impossible. Therefore, contrary to the conventional composition design, the V-cut processing, the three-dimensional shape, or the uneven shape, in which the weight ratio of the atactic polypropylene is 5% by weight or more in the polypropylene-based olefin-based thermoplastic elastomer. Non-uniform sheet deformation due to necking when forming into the article surface shape, and the resulting wrinkles,
Defects such as pattern distortion can be eliminated. Particularly, the case where the weight ratio of the atactic polypropylene is 20% by weight or more is preferable. On the other hand, if the weight ratio of the atactic polypropylene increases too much, the sheet itself tends to deform,
Further, it is not preferable because it is easily broken during molding. The upper limit of the weight ratio of the atactic polypropylene is 50% by weight or less, and more preferably 4% or less, when vacuum forming, V-cutting, and simultaneous lamination of injection molding are employed.
0% by weight or less.

A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer resin. Here, as the butene, 1-butene, 2-butene and isobutylene are used.
Any of the structural isomers can be used. The copolymer is a random copolymer and partially includes an amorphous portion. Preferred specific examples of the ethylene-propylene-butene copolymer include the following (i) to (iii). (i) Those described in JP-A-9-111055. It is a random copolymer of a terpolymer of ethylene, propylene and butene. The weight ratio of the monomer components is 90% by weight or more of propylene. The melt flow rate is preferably 1 to 50 g / 10 minutes at 230 ° C. and 2.16 kg. And, for 100 parts by weight of such a ternary random copolymer, 0.01 to 50 parts by weight of a transparent nucleating agent containing a phosphate aryl ester compound as a main component,
It is obtained by melting and kneading 0.003 to 0.3 parts by weight of a fatty acid amide having 12 to 22 carbon atoms. (ii) Those described in JP-A-5-77371. this is,
80 to 0% by weight of crystalline polypropylene is added to 20 to 100% by weight of an amorphous polymer having a propylene content of 50% by weight or more, which is a terpolymer of ethylene, propylene and 1-butene. It is. (iii) Those described in JP-A-7-316358. This is a terpolymer of ethylene, propylene, and 1-butene, and the content of propylene and / or 1-butene is 50% by weight or more and 20 to 100% by weight of the low crystalline polymer. 0.5% by weight of an oil gelling agent such as N-acylamino acid amine salt or N-acylamino acid ester is added to a composition containing 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. It becomes.

The ethylene-propylene-butene copolymer resin may be used alone, or may be used in the above (i) to (iii).
If necessary, another polyolefin-based resin may be mixed and used.

As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partially crosslinked ethylene- Propylene copolymer rubber, unsaturated ethylene-propylene-
An olefin-based elastomer obtained by using a monoolefin copolymer rubber such as a non-conjugated diene terpolymer rubber as a soft segment, and uniformly mixing and mixing these. Incidentally, monoolefin rubber / olefin polymer = 50/50 to 90
/ 10 (weight ratio).

As described in JP-B-53-34210 and the like, (B) an uncrosslinked monoolefin copolymer rubber (soft segment) and (A) an olefin copolymer (crystalline, hard segment) are crosslinked. An olefin-based elastomer obtained by mixing with an agent, heating and applying shear stress to dynamically partially cross-link. (B) Monoolefin rubber / (A)
Olefin copolymer = 60/40 to 80/20 (weight ratio).

As described in JP-B-56-15741, (A) mixing with a peroxide such as isotactic polypropylene, propylene-ethylene copolymer or propylene-butene-1 copolymer and heating reduces the molecular weight. Mixing and heating with a peroxide-decomposable olefin polymer (hard segment) that increases fluidity and (B) a peroxide such as ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene terpolymer rubber, etc. Mixes with peroxides such as peroxide-crosslinked monoolefin copolymer rubber (soft segment), which crosslinks and reduces fluidity, (C) polyisobutylene, butyl rubber, etc.
Peroxide non-crosslinked hydrocarbon rubber (soft segment and fluidity-modifying component) that does not crosslink even when heated and does not change fluidity, and (D) mineral oils such as paraffinic, naphthenic, and aromatic An olefin-based elastomer obtained by mixing a softener and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 10 to 60 parts by weight.
(A) + (B) = 100 parts by weight,
(C) and / or (D) have a compounding ratio of 5 to 100 parts by weight.

An olefin thermoplastic elastomer comprising an ethylene-styrene-butylene copolymer as described in JP-A-2-139232.

The above olefinic thermoplastic elastomer having a hydroxyl group and / or a carboxyl group as a polar group. For example, an olefin-based thermoplastic elastomer having a hydroxyl group introduced by graft polymerization of an ethylene-vinyl alcohol copolymer or the like and a carboxyl group introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like is used. Either of these hydroxyl groups and carboxyl groups,
Alternatively, both polar groups may be used in combination, and these polar groups have an effect of improving the adhesion to other layers such as a printing ink layer and an adhesive layer.

The base sheet may optionally have
Various additives are added. Examples of the additives include fillers such as inorganic powders such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, foaming agents, lubricants, ultraviolet absorbers, and light stabilizers. In particular, in applications where improved weather (light) resistance is required, one or both of an ultraviolet absorber such as a benzotriazole type and a light stabilizer such as a hindered amine type radical scavenger are added as a weathering agent, and the It is preferable to improve the light) property. The amount of addition is usually 0.1.
It is in the range of 1 to 5% by weight. In the case where the base sheet is colored and transparent, a known colorant, such as those listed in a printing ink layer described later, may be kneaded into the resin.

(Shaping of a concavo-convex pattern) In order to make a base sheet having a concavo-convex pattern, a known method may be used.
The concavo-convex pattern may be formed simultaneously with the formation of the base sheet (see FIG. 2), or the base sheet may be formed by forming the concavo-convex pattern on a material sheet having no concavo-convex pattern (for example, FIG.
Or a method of heating and pressing with an embossing roller).

For example, a method of shaping a concavo-convex pattern simultaneously with the formation of a substrate sheet is described in the conceptual diagram of FIG.
When the resin in a molten state is extruded from the die 21 and solidified by cooling with a cooling roller, the substrate sheet 1 is formed simultaneously with the film formation by using an embossing / cooling roller 22 having a concave and convex pattern on the cooling surface when forming the film. Any method is acceptable. In particular, this method is preferable from the viewpoint of productivity because the film formation of the sheet and the embossing pattern shaping can be performed at the same time as compared with the method of shaping the embossing pattern on the material sheet later.

That is, as shown in FIG. 2, a molten sheet 11 made of a heated and melted transparent thermoplastic resin extruded from a T-die 21 is rotated by a rotating embossing / cooling roller 22 having a desired uneven pattern on its surface and a pressing roller 23. And the molten sheet is cooled and solidified on the embossing / cooling roller, and the concavo-convex pattern on the roller is shaped into the cooled and solidified molten sheet, and the transparent base having the concavo-convex pattern 2 is formed. After forming the material sheet 1, the base sheet is appropriately separated from the peeling roller 24.
When the film is peeled off from the roller using, for example, an uneven pattern is formed on the surface, the transparent base sheet 1 mainly composed of a thermoplastic resin is used.
Is obtained. The embossing / cooling roller 22 is a cylindrical rotating roller whose roller surface is an embossing / cooling surface. For example, a copper layer is formed on the surface of a hollow cylindrical iron roller by plating, and the copper layer surface is photo-etched,
A roller having a desired uneven pattern formed by a method such as a mill engraving method can be used. The molten sheet is cooled by passing a cooling medium such as water into the hollow of the cylinder.

In the method of forming a base material sheet by forming an uneven pattern on a material sheet later, it is common to use a thermoplastic resin sheet for the material sheet and form the material sheet by heat and pressure using a known embossing roller. It is a target. Alternatively, as illustrated in FIG. 3, a method may be used in which an uneven pattern is formed on a material sheet as a cured product of an ionizing radiation curable resin to form a base sheet. FIG. 4 shows a substrate sheet 1 obtained by this method, on which a concavo-convex pattern 2 is formed as a concavo-convex pattern layer 13 which is a cured product on a material sheet 12. The concavo-convex pattern layer 13 may be a continuous layer continuous on the surface of the material sheet, or may be a discontinuous layer in which some or all of the projections are separated and independent.
This method is particularly suitable for forming a sharp shape. The method of forming the concavo-convex pattern is described in JP-A-57-87318, JP-B-57-22755, JP-B-63-50066, and JP-A-7-324.
No. 76, etc., which is a method capable of faithfully shaping the uneven shape of a shaping die (roll intaglio) into an uneven pattern on a substrate sheet. This method basically includes the following steps (see FIG. 3).

A cylindrical plate cylinder (roll intaglio) 50 having a concave / convex pattern (concavo-convex pattern) 40 having the same shape as the target concavo-convex pattern and a reverse concavo-convex pattern on the surface is prepared. Rotate around. The long strip-shaped material sheet 12 is supplied at the same speed as the peripheral speed of the roll intaglio. The material sheet 12 and the roll intaglio 50 are overlapped with each other via an uncured liquid composition 70 of an ionizing radiation-curable resin therebetween, and the liquid composition completely fills at least the concave portions of the roll intaglio. I will do it. In that state, the liquid composition is irradiated with ionizing radiation R from the ionizing radiation irradiation device 80 to crosslink and cure the liquid composition. Thereafter, the material sheet 12 is peeled off from the roll intaglio together with the concave / convex pattern 2 composed of the concave / convex pattern layer 13 of the cured product of the ionizing radiation-curable resin in which the concave / convex shape 40 on the roll intaglio is adhered thereto. I do. As a result, as illustrated in FIG. 4, the base sheet 1 is obtained in a configuration in which the concavo-convex pattern 2 is formed by bonding the concavo-convex pattern layer 13 to the material sheet 12.

In the above method, the roll intaglio 50 (shaping mold) is basically a known intaglio, gravure, or embossing plate, and is basically made of the same material, the same structure, and the same manufacturing method. You can use it. As a material for roll intaglio,
Usually, metals such as iron and copper are used. However, when irradiating ultraviolet light or visible light from inside the roll intaglio, a transparent material such as glass or quartz is used. The rotary drive about the axis of the intaglio roll may be performed by using the same mechanism and method as those of a normal transfer type gravure printing machine, rotary embossing machine, or the like. In order to adhere the material sheet to the roll intaglio, the material sheet is pressed by a roller (pressure roller) 90 made of rubber, metal, or the like. Also, when the base sheet is peeled from the roll intaglio, the base sheet is peeled by pressing with a roller (peeling roller) 100 made of rubber, metal or the like. In addition, a long sheet-shaped material sheet is used. Such a material sheet is unwound from an unwinding roll (supply roll), and is wound up by a winding roll (discharge roll) after shaping of the uneven pattern.

The following modes (1) to (3) are used to superimpose the material sheet and the roll intaglio on each other with the uncured liquid composition of the ionizing radiation-curable resin therebetween. (1) First, a liquid composition is applied onto a material sheet, and then the material sheet is superimposed on the roll intaglio such that the applied surface faces the surface of the roll intaglio. (2) As shown in FIG. 3, first, the liquid composition 70 is applied to the roll intaglio 50 using a coating liquid supply device 200 such as a T-die, and then the material sheet 12 is superimposed on the application surface on the roll intaglio. (3) First, the liquid composition is applied to each of the roll intaglio and the material sheet, and then the material sheet and the roll intaglio are overlapped such that the respective application surfaces face each other.

The mode of irradiation of the uncured liquid composition between the intaglio roll and the material sheet with ionizing radiation is as follows. Since a material sheet made of a thermoplastic resin such as a polypropylene sheet is transparent to ionizing radiation, it is irradiated from the material sheet side as shown in FIG. A roll intaglio that is transparent to ionizing radiation is selected (for example, a quartz roll intaglio is selected for ultraviolet rays) and irradiated from inside the roll intaglio.

The material of the material sheet 12 is typically a resin sheet which can be irradiated with ionizing radiation in the above-described manner. That is, in the present invention, as the material of the material sheet, thermoplastic polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and olefin-based thermoplastic elastomer, and the like are listed as the thermoplastic resins used for the base sheet described above. Use resin sheets made of various resins. The thickness of the material sheet is usually about 10 to 200 μm.

The ionizing radiation-curable resin may be appropriately selected from resins known as resins curable by ionizing radiation. For example, (meth) acryloyl groups,
A polymerizable unsaturated bond such as a (meth) acryloyloxy group,
Alternatively, a composition comprising a prepolymer, a monomer, or a polymer having a cationically polymerizable functional group such as an epoxy group, or a polythiol compound, and one or a mixture of two or more of these compounds is used. The composition used is a liquid when uncured.

For example, examples of the prepolymer having a polymerizable unsaturated bond in the molecule include unsaturated polyesters such as a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol;
Polyester (meth) acrylate, urethane (meth)
There are (meth) acrylates such as acrylate, epoxy (meth) acrylate, and melamine (meth) acrylate [In the present specification, (meth) acrylate is used to mean acrylate or methacrylate. The same applies hereinafter. Examples of the monomer include various (meth) acrylates such as methyl (meth) acrylate, trimethylpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The ionizing radiation for curing the ionizing radiation-curable resin is described later in the hard coating layer, but usually uses ultraviolet rays or electron beams. When curing with ultraviolet rays, a photopolymerization initiator is further added to the ionizing radiation-curable resin. The type and the amount of the photopolymerization initiator may be the same as the compounds and the amount of the hard coat layer described later.

To apply the above uncured liquid composition of the ionizing radiation-curable resin composition to a roll intaglio or a material sheet, various known methods, for example, roll coating, curtain coating, T-die coating (FIG. 3) And so on. Especially in the case of roll intaglio coating, the liquid composition in the ink pan,
A method of immersing a rotating roll intaglio (so-called dip immersion)
Is also possible.

(Concavo-convex pattern) The concavo-convex pattern 2 is not particularly limited. Any suitable for the purpose of the decorative sheet may be used. The uneven pattern is, for example, a grain surface, a satin surface, a hairline, a linear groove, a stone surface unevenness such as a cleavage plane of granite, a wood grain conduit groove, a wood grain annual ring unevenness, a floating annual ring unevenness, a wood grain unevenness, a cloth texture surface texture, a skin squeezing. , Characters, geometric patterns, etc. In addition, a linear groove is described in, for example, Japanese Patent Publication No.
An aggregate of a concave portion and a convex portion formed by grooves of a parallel curve group or a straight line group, as disclosed in JP-A-106625, JP-A-4-125199, and the like. The curve group is, for example, a line group such as a sine wave, a cycloid curve, an arc, and other curves. The depth of the concave portion and the width of the concave portion and the convex portion are, for example, 0.1.
It is about 1 to 100 μm. As will be described later in connection with the printing ink layer, a concavo-convex pattern that is in register with the pattern is also suitable in the present invention because the pattern can be formed with high dimensional accuracy.

[Easy Adhesion Treatment to Base Sheet] When forming other layers such as a printing ink layer, a hard coating layer, an adhesive layer, and a colored portion, which will be described later, on the base sheet, these layers are used as a base. In order to improve the adhesion to the material sheet, it is preferable to appropriately perform an easy adhesion treatment as needed. The conceptual diagram of the production of the base sheet illustrated in FIG. 2 is an example in which the corona discharge treatment is performed by the corona discharge treatment device 25 as the easy adhesion treatment to the base sheet. In addition, in addition to the above, a plasma treatment, formation of an easy-adhesion layer by coating or printing, and the like are appropriately used for the easy-adhesion treatment. The easy-adhesion layer may be appropriately selected from known anchor agents and the like according to the base material sheet and the resin material of the layer formed thereon. The easy-adhesion layer may be, for example, a layer formed of a two-component curable urethane resin such as a thermosetting resin by a coating method or a printing method.

[Hard coating layer] Dimensional stability of base sheet (and dimensional stability of pattern on decorative sheet)
In order to further improve this as needed, as shown in FIG. 5, before the transfer ink layer is formed on the base sheet, the surface of the base sheet 1 on the side of the concavo-convex pattern 2 is transparent. It is preferable to form a hard coating layer (hard coat layer) 3 by applying a curable resin paint and crosslinking and curing. As a result, it is possible to register the concavo-convex pattern and the picture pattern with higher accuracy. The hard coating layer is formed by roll coating,
A conventionally known coating method such as flow coating may be used.

The resin of the curable resin paint is not particularly limited as long as it is basically a curable resin. However, in the case of a resin that requires heating for curing, the heat tends to cause the base sheet to easily stretch and impair dimensional stability. For this reason, a resin that cures by means other than heat is preferred. For example, an ionizing radiation-curable resin that is cured by ionizing radiation such as ultraviolet light or an electron beam is preferable. The thickness of the hard coating layer may be usually about 2 to 25 μm. If it is too thin, the effect of stabilizing the dimensions cannot be obtained, and if it is too thick, the flexibility of the transparent base material sheet will decrease or the cost will increase. In addition, the hard coating layer, in addition to the purpose of dimensional stabilization, if necessary, may be appropriately adjusted for gloss, imparting design properties such as a feeling of painting, and improving the surface properties such as scratch resistance. .

The ionizing radiation-curable resin is a composition curable by ionizing radiation, and specifically, a prepolymer (so-called prepolymer) having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in a molecule. Oligomers)
A composition which is curable by ionizing radiation and / or is appropriately mixed with a monomer is preferably used. These prepolymers or monomers are used alone or as a mixture of two or more.

The above prepolymer or monomer specifically has a radical polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, a cationic polymerizable functional group such as an epoxy group in the molecule. Consisting of a compound having Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferably used. In addition, for example, a (meth) acryloyl group is
It means an acryloyl group or a methacryloyl group. Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. The molecular weight is usually 250
Approximately 100,000 are used.

Examples of monomers having a radical polymerizable unsaturated group include monofunctional monomers such as methyl (meth)
There are acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.
Also, as polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylpropane tri (meth)
There are also acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. Examples of prepolymers having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those obtained by adding allyl alcohol to both ends of a polyurethane made of a diol and a diisocyanate.

The ionizing radiation-curable resin may further contain various additives as required. These additives include, for example, vinyl chloride-vinyl acetate copolymers, polyvinyl acetates, acrylic resins, thermoplastic resins such as cellulose resins, and fine powders such as calcium carbonate, barium sulfate, silica, and alumina. Extender (filler) and the like.

In the case of curing with ultraviolet light or visible light, a photopolymerization initiator is further added to the ionizing radiation-curable resin. In the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers 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 metallocene compound, a benzoinsulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. In addition,
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.

As the ionizing radiation, an electromagnetic wave or a charged particle having an energy capable of crosslinking the molecules in the adhesive is used. Usually, ultraviolet rays or electron beams are used, but it is also possible to use visible rays, X-rays, ion beams or the like. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp is used. As a wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm is usually mainly used. As the electron beam source, various electron beam accelerators such as Cockcroft-Walton type, Van degraft type, resonance transformer type, insulating core transformer type, or linear type, dynamitron type, high frequency type, etc.
One that irradiates electrons with energy of 1000 keV, preferably 100 to 300 keV is used.

In the case where a colored portion is formed in the concavo-convex pattern by wiping or the like to be described later, the hard coating layer may be formed afterwards. FIG. 7B shows an example of the decorative sheet S in which the hard coating layer 3 is formed after forming the colored portion 4 in the uneven pattern 2. That is, the decorative sheet S in FIG. 7 (B) has the colored portion 4 in the concave portion of the concave-convex pattern 2 of the base sheet 1, and the hard coating layer 3 is formed on the entire surface on the concave-convex pattern side, The decorative sheet is a decorative sheet having a configuration in which a printing ink layer 8 composed of a pattern layer 8a and an entire solid color layer 8b is formed in this order on the surface of the base sheet opposite to the uneven pattern.

[Formation of Colored Part in Uneven Pattern] FIG. 7 (B)
As illustrated in (1), a colored portion 4 may be formed in the concavo-convex pattern 2 of the base sheet 1 as necessary. In order to form the colored portion 4 in the concave portion of the concavo-convex pattern 2, the concave portion may be filled with a coloring ink by a known wiping method (see Japanese Patent Publication No. 58-14312, etc.) to form the colored portion 4. As the coloring ink, those similar to the above-described inks for the printing ink layer can be used. However, in terms of abrasion resistance, it is preferable to use a two-component curable urethane resin as a binder resin.

[Transfer Sheet] The transfer sheet 5 is shown in FIG.
As shown in (A), the transfer layer 7 includes at least a transfer layer 7 including a printing ink layer 8 and a support sheet 6 having a release property from the transfer layer. Normally, as in the transfer sheet 5 illustrated in FIG. 6B, the printing ink layer 8 has a pattern layer 8a and a solid color layer 8b on the entire surface. The full solid color layer is usually opaque. Further, as shown in FIG. 6 (B), the transfer layer 7 may have a release layer 9 as a component as necessary.
And the like.

(Support Sheet) As the support sheet,
For example, polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate-isophthalate copolymer, polyester resin such as polyarylate, polyethylene, polypropylene, polymethylpentene, polyolefin resin such as olefin thermoplastic elastomer, nylon 6, nylon 66, etc. Polyamide, polyvinyl chloride, ethylene-vinyl acetate copolymer, ethylene-
Vinyl alcohol copolymers, polyvinyl alcohols, vinyl polymers such as vinylon, cellulose resins such as cellulose triacetate and cellophane, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate A resin film (sheet) of a resin or the like, or a single-layer body or a plurality of laminates of paper such as high-quality paper, thin paper, glassine paper, parchment paper, or the like is used.
The thickness of the support sheet is usually from 5 to 200 μm. Among them, the support sheet of the transfer sheet used in the present invention is preferably a sheet having good dimensional stability, for example, a heat-resistant resin film such as polyethylene terephthalate, or paper as a support base material. A support sheet or the like having a configuration in which a release layer made of a polyolefin resin, a silicone resin, or the like is provided on the substrate is preferred. For example, FIG.
The support sheet 6 in the transfer sheet 5 exemplified in (1) has a configuration in which a release layer 6b is laminated on a support base material 6a.

The support sheet may be provided, if necessary, with a release layer on the transfer layer side as a component of the support sheet in order to improve the releasability from the transfer layer [FIG. 6 (B). )reference〕. The release layer is removed from the transfer layer as a part of the support sheet when the support sheet is released. As the release layer, for example, a simple substance such as a silicone resin, a melamine resin, a polyamide resin, a urethane resin, a polyolefin resin, a wax, or a mixture containing these is used. Further, in order to adjust the releasability, the surface of the support sheet on the transfer layer side may be subjected to corona discharge treatment, ozone treatment or the like.

(Printing Ink Layer of Transfer Layer) The transfer layer has at least a printing ink layer having a pattern. The printing ink layer has at least a pattern layer expressing a pattern by single color printing or multicolor printing. In addition to the pattern layer, the printing ink layer has a solid color layer on the entire surface for expressing the base color and for covering the color of the adherend to which the decorative sheet is to be attached and unnecessary patterns on the surface thereof. It may be provided on the support sheet side of the pattern layer (that is, on the outer side of the pattern layer in the decorative sheet). The printing ink layer may be formed by a conventionally known printing method and material such as gravure printing, silk screen printing, offset printing, or transfer printing. It is to be noted that, in addition to the printing method, a coating method such as roll coating can be used for the entire solid color layer. However, the term "printing ink layer" used in the present invention means that the entire surface solid color layer formed by using the coating liquid by such a coating method is included in the printing ink layer.

In particular, the method of manufacturing the decorative sheet of the present invention, in which the effect of the dimensional stability of the picture pattern in the composition of the printing ink layer is emphasized, is that the picture pattern layer of multicolor printing or the entire surface is solid-colored. This is the case where the layer is formed as a printing ink layer. Among them, a practical form is a case where the printing ink layer has a pattern layer and a solid color layer on the entire surface. The pattern layer may be printed in a single color, but is usually printed in a multicolor. In such a case, the reason why the present invention is particularly effective is that when these layers are formed directly on the base sheet by a direct printing method requiring solvent drying by gravure printing or the like instead of transfer printing, This is because the material sheet receives a large amount of heat particularly during drying of the solvent, and is likely to undergo dimensional changes. That is, in multicolor printing, the base sheet is heated each time after passing through the drying device for the number of colors, so that the dimensional change is likely to occur. In addition, since the solid color layer on the entire surface is heated at a higher temperature for a longer time (longer drying pass) than the pattern layer because of a large amount of the dry solvent, the dimensional change is also likely to occur. However, when the printing ink layer is formed by transfer printing as in the present invention, the substrate sheet does not receive heat for drying the solvent of the printing ink layer. The heat is applied to the support sheet (of the transfer sheet) for which it is not necessary to consider the embossing suitability or the like for the shaping of the concavo-convex pattern, and the support sheet can be a sheet emphasizing dimensional stability. It is.

The pattern of the picture pattern and the color tone of the entire solid colored layer may be determined according to the intended use. For example, the pattern patterns include a wood pattern, a stone pattern, a grain pattern, a cloth pattern, a squeezed pattern, a geometric figure, a character, and a symbol. In particular, since the picture pattern can be formed with good dimensional stability in the method for producing a decorative sheet of the present invention, the picture pattern can be formed in register with the concavo-convex pattern. As a preferable combination of the picture pattern and the concavo-convex pattern, for example, when the concavo-convex pattern is a wood-grain conduit groove, a floating ring-shaped concavo-convex pattern, or a wood-bump pattern, the wood pattern is preferably a wood-grain pattern. Further, in the case where the uneven pattern is a grain pattern, the unevenness of a cleavage plane of granite, or the like, the picture pattern is preferably a stone pattern or a grain pattern. In addition, it is not always necessary to match each of the concavo-convex pattern and the picture pattern, that is, it is not necessary to match the positions of the respective patterns as the same pattern. The solid color layer on the entire surface is preferably transparently colored when utilizing the color tone of the surface of the adherend when the decorative sheet is attached to the adherend. However, in the case of hiding without utilizing the color tone of the surface of the adherend, opaque coloring, that is, concealing coloring is preferable. In the method for producing a decorative sheet according to the present invention, such an entire solid color layer can be formed simultaneously with the pattern layer, so that a colored base sheet is prepared as in the case of the so-called doubling embossing method described in the section of the prior art. It is not necessary to laminate two base sheets. Therefore, the colored base sheet can be omitted by the solid color layer on the entire surface, and the thickness of the decorative sheet can be reduced accordingly, so that when the obtained decorative sheet is bent by V-cut processing or the like,
The sheet is hard to whiten.

The ink used for the printing ink layer may be appropriately selected from known ones according to the use of the decorative sheet, the material of the base sheet to be formed, and the like. For example, as the resin of the binder used in the vehicle of the ink, chlorinated polyethylene, chlorinated polyolefin such as chlorinated polypropylene, polyester resin, urethane resin, acrylic resin,
A known resin such as a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, or a cellulose resin is used alone or in combination of two or more. Examples of coloring agents such as pigments and dyes include, for example, inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, and carbon black.
Isoindolinone, Hansa Yellow A, quinacridone,
Pearls made of organic pigments (or dyes) such as Permanent Red 4R, Phthalocyanine Blue, Indaslen Blue RS, and Aniline Black, metal pigments such as aluminum and brass, titanium dioxide-coated mica, and foil powders such as basic lead carbonate A gloss (pearl) pigment or the like is used.

As the printing ink layer of the transfer layer, a release layer may be provided if necessary. The release layer is a component of the transfer layer, and is a layer that remains on the object to be transferred (substrate sheet) and transfers and transfers when the support sheet is separated. The release layer is usually used for adjusting the releasability from the support sheet. After the transfer, the release layer is the outermost layer on the side of the printing ink layer formed on the base sheet, and when the decorative sheet is adhered to the adherend with an adhesive on the printing ink layer side. In addition, it is a layer that affects the adhesiveness. Therefore, it can be used to improve the adhesiveness of the decorative sheet. The release layer may be formed by printing with an ink using a suitable resin from among the binder resins used for the ink of the above-described pattern pattern layer, similarly to the pattern pattern layer and the entire solid color layer.

[Adhesive for Transfer] In order to transfer and bond at least the transfer layer consisting of the printing ink layer to the base sheet, when the printing ink layer alone cannot be used for bonding, the adhesive layer constituting the transfer layer of the transfer sheet The adhesive is used as an adhesive layer on the base sheet side or as an adhesive layer on both the transfer sheet side and the base sheet side. The formation of these adhesive layers is performed when or before the transfer sheet is laminated.
Apply to objects inline or offline. Of course, when the printing ink layer itself provided as the outermost layer in the transfer sheet has sufficient adhesiveness, the adhesive layer may be omitted. The adhesive may be selected from known adhesives such as a heat-sensitive adhesive or a curable adhesive such as an ionizing radiation-curable adhesive or a thermosetting adhesive, depending on the application. In addition, as long as the adhesive is applied immediately before lamination of the transfer sheet, the adhesive may be selected from known adhesives according to the intended use. The embodiment of the method for manufacturing a decorative sheet of the present invention illustrated in FIG. 1 is an example in which the adhesive A is applied only to the base sheet 1 side by the adhesive coating device 33 to form the adhesive layer 10. Normally, the adhesive needs to be dried by heating a volatile solvent. When an adhesive layer is formed on the base sheet side as shown in FIG. 1, the base sheet is heated before the transfer sheet is laminated. Nevertheless, the degree of heat received by the base sheet is smaller than that of directly forming a pattern pattern layer for multicolor printing and a solid color layer on the entire surface, which are the most common printing ink layer configurations. The effect is obtained. Of course, it is more preferable to apply the adhesive on the transfer sheet side, not on the base sheet side, from the viewpoint of dimensional stability of the base sheet because the base sheet does not receive such heat.
However, in some cases, such as when the material of the base sheet is poor in adhesiveness, it may be better to apply an adhesive to the base sheet side in terms of the adhesiveness of the adhesive layer itself to the base sheet. The object to which the adhesive is to be applied is determined.

The adhesive used is, for example, in the case of a heat-sensitive adhesive, a styrene resin such as polystyrene and poly-α-methylstyrene or a styrene copolymer, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and the like.
Acrylic resins such as polybutyl acrylate; vinyl polymers such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer and polyvinyl butyral; rubber resins such as polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber , Or a mixture of two or more resins such as polyamide resins. As the thermosetting adhesive, a phenol resin, a urea resin, a diallyl phthalate resin, a thermosetting urethane resin, an epoxy resin, or the like is used. It is easy to apply the thermosetting adhesive immediately before the transfer. The adhesive is applied to a transfer sheet or a base sheet by a conventionally known solution coating means such as a gravure roll coat, a spray coat, and a curtain flow coat. The thickness of the adhesive layer is usually about 5 to 100 μm.

[Adhesive for sticking the decorative sheet to the adherend] The decorative sheet obtained as described above may be further provided with an adhesive on its sticking surface as necessary. Further, an adhesive layer for attaching the decorative sheet to the adherend may be provided. As the adhesive, a known adhesive, for example, the adhesive listed in the above-mentioned adhesive layer for transfer may be used depending on the application. For example, a conventionally known adhesive such as a thermosetting resin such as a thermoplastic resin such as polyamide and a thermosetting resin such as urethane resin may be used.

[Transfer Method of Printing Ink Layer by Transfer Sheet] While a long strip-shaped base sheet is running, a printing ink layer or the like is transferred and formed as a transfer layer on the base sheet by the long strip-shaped transfer sheet. There is no particular limitation on the transfer method used for the above. For example, a general roller transfer method using a transfer roller may be used. However, since the object to be transferred is different from a rigid plate-like object and is a long strip-like sheet usually having flexibility like the transfer sheet, as shown in FIG. It is preferable to press the base sheet 1 and the transfer sheet 5 so as to sandwich the base sheet 1 and the transfer sheet 5. Of course, at this time, the transfer sheet is formed such that the transfer layer 7 faces the base sheet side, and the base sheet faces the transfer sheet side on the side opposite to the surface on the uneven pattern side. Then, the base sheet is supplied between the two transfer rollers. After the transfer sheet is laminated on the base sheet in this manner, the timing of peeling the support sheet of the transfer sheet is performed immediately after the transfer sheet passes through the transfer roller 31 using the above-described transfer roller 31 as a peeling roller. After the transfer sheet passes through the transfer roller 31 as shown in FIG.
May be used for peeling. Of course, when peeling off the support sheet, it is necessary that only the support sheet is peeled off and the transfer layer is adhered to such an extent that the transfer layer remains on the base sheet side. In this case, when a curable adhesive is used as the adhesive, the curing is performed in such a manner that the adhesive sheet satisfies such adhesiveness at the time of peeling the support sheet, and the completion of the curing is performed after the peeling of the support sheet. But it is good.

[Applied Body of Decorative Sheet] The application of the decorative sheet obtained in the present invention is not particularly limited, and the decorative sheet is laminated on the surface of various adherends and used for decorative application of the surface. The adherend is a plate material such as a flat plate or a curved plate of various materials, a three-dimensional article, a sheet (or film), or the like. For example, wood veneer,
Wood board material such as wood plywood, particle board, wood fiber board such as MDF (medium density fiber board), wood board material used as three-dimensional article, plate material such as iron and aluminum, metal used as three-dimensional article or sheet Materials, glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates, ceramic materials used as three-dimensional articles, acrylic resin, Polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin,
Cellulosic resin, plate materials such as rubber, resin materials used as three-dimensional articles or sheets, or high-quality paper used exclusively as sheets, paper such as Japanese paper, carbon, asbestos,
Nonwoven fabrics or woven fabrics made of fibers such as glass and synthetic resin can be used.

[Laminating method of decorative sheet on adherend] As a method of laminating the decorative sheet on these various adherends, for example, pressure is applied to a plate-like substrate with a pressure roller via an adhesive. As described in JP-B-50-19132, JP-B-43-27488, etc., after the decorative sheet is placed between the male and female molds for injection molding, the molten resin is placed in the mold. A so-called simultaneous injection molding lamination method in which injection molding is performed and a decorative sheet is adhered and laminated on the surface of the resin molded article simultaneously with the molding thereof, as described in JP-B-56-45768 and JP-B-60-58014. , A decorative sheet is opposed to or placed on the surface of a three-dimensional article such as a molded article with an adhesive therebetween, and the decorative sheet is laminated on the surface of the three-dimensional article by a pressure difference due to vacuum suction from the three-dimensional article side. So-called vacuum Laminating method, as described in JP-B-61-5895, JP-B-3-2666, etc., an adhesive is provided between a decorative sheet and a columnar substrate such as a column or a polygonal column in the long axis direction. While feeding through
There is a so-called lapping method in which decorative sheets are successively pressed and laminated on a plurality of side surfaces constituting a columnar substrate by a plurality of rollers having different directions.

Further, as a further processing method for a product in which decorative sheets are laminated to form a decorative board, Japanese Utility Model 15-311
No. 22, JP-A-48-47972, a decorative sheet is first laminated on a plate-like base material with an adhesive therebetween to form a decorative sheet, and the surface opposite to the decorative sheet is used. To
Cut a V-shaped or U-shaped groove reaching the interface between the decorative sheet and the plate-shaped substrate, and then apply an adhesive in the groove and bend the groove to form a box or column. Is a so-called V-cut or U-cut processing method.

[Use of decorative sheet and laminate thereof] The decorative sheet obtained in the present invention is laminated on various adherends, and if necessary, subjected to a predetermined molding process and used for various purposes.
For example, interior decoration of buildings such as walls, ceilings, floors, window frames, doors, surface decoration of fittings such as handrails, surface decoration of furniture or cabinets of light electric / OA equipment, vehicle interiors such as automobiles, trains, aircraft, ships, Window glass makeup. In particular, the decorative sheet obtained by the production method of the present invention has good dimensional stability,
It is suitable for applications requiring dimensional stability such as floors and window frames.

[0065]

EXAMPLES The method for producing a decorative sheet according to the present invention will be further described below with reference to examples.

Example 1 A decorative sheet was produced by a method as shown in FIG. First, FIG. 6 for forming a printing ink layer
A transfer sheet 5 as shown in (B) was prepared as follows. First, a support sheet 6 having a 16 μm-thick polyester film as a support substrate 6a and a release layer 6b made of an acrylic melamine resin formed on one surface thereof was prepared. Then, on the release layer side surface of the support sheet, a release layer 9 made of acrylic vinyl chloride resin, a three-color printing made of a solid colored layer 8b made of thermoplastic acrylic urethane resin, and a thermoplastic acrylic urethane resin. And a printing ink layer 8 composed of a wood pattern pattern layer 8a by gravure printing in this order to prepare a transfer sheet. For the solid color layer and the picture pattern layer, red iron oxide, titanium white, carbon black, and yellow color were used as color pigments, and the solid color layer was formed as an opaque concealing layer.

On the other hand, the base sheet 1 is made of a transparent polyolefin made of a polypropylene-based olefin thermoplastic elastomer having a weight ratio of isotactic polypropylene to atactic polypropylene of 80:20 by the method shown in FIG. The system resin was extruded from the T-die 21 while being hung as a molten sheet 11 and supplied between the embossing / cooling roller 22 and the pressing roller 23. As the embossing / cooling roller, a roller having a concavo-convex pattern for cooling the roller to form a wood grain conduit groove was used. Then, the substrate sheet 1 was peeled off from the embossing / cooling roller 22 by the peeling roller 24 to produce the transparent substrate sheet 1 having a thickness of 100 μm in which the concavo-convex pattern 2 was formed on one side.
At this time, corona discharge treatment was performed on both the front and back surfaces of the obtained base sheet in-line by the corona discharge treatment device 25.

Next, the entire surface on the side of the concavo-convex pattern has the following composition [contains a urethane acrylate prepolymer, but the main component is epoxy acrylate, and it can be said that epoxy acrylate or a mixture thereof is used. ] After applying an electron beam curable resin coating material to the entire front and side surfaces by a roll coating method, a 175 keV electron beam is irradiated with 5 Mrad using a scanning type electron beam irradiation device to crosslink and cure the coating material so that the uneven pattern is filled. A hard coating layer 3 having a thickness of 10 μm was formed.

Composition of electron beam-curable resin coating composition Bifunctional bisphenol A epoxy acrylate prepolymer 20 parts by weight Bifunctional phenolic epoxy acrylate prepolymer 20 parts by weight Trimethylolpropane triacrylate 20 parts by weight Urethane acrylate (molecular weight 1700) [* 1] 20 parts by weight Silicone acrylate 0.8 parts by weight Spherical α-alumina particles (average particle size 25 μm) 15 parts by weight

* 1: The composition of the urethane acrylate is shown below. Polytetramethylene glycol (molecular weight 1000) 1000 parts by weight Isophorone diisocyanate 444 parts by weight 2-hydroxyethyl acrylate 232 parts by weight

Next, a two-component curable urethane resin composed of polyester polyol and tolylene diisocyanate is adhered to the entire surface of the long strip-shaped base sheet on which the hard coating layer is formed and opposite to the uneven pattern. The agent was gravure coated to form an adhesive layer, and then the printing ink layer was further transferred to the substrate sheet by the adhesive layer using the transfer sheet prepared above. In the transfer method, transfer pressure was applied using two transfer rollers 31 as shown in FIG. The transfer roller 31 used was a rubber roller in which the surface of the iron core was covered with silicone rubber and heated. Further, the support sheet of the transfer sheet was peeled off by a peeling roller 32.

The decorative sheet obtained was a method for producing a decorative sheet having good dimensional accuracy of the pattern of the printing ink layer and good dimensional stability.

[0073]

According to the method for producing a decorative sheet of the present invention, since a pattern is formed by a transfer method when a pattern is formed on a substrate sheet on which a concavo-convex pattern is formed, printing having a pattern to be transferred as a transfer layer is performed. The ink layer does not contain a volatile solvent as in, for example, gravure printing, and therefore, the sheet is not heated by a drying device for drying the volatile solvent, and the pattern at the time of transferring the printing ink layer is formed. Dimensional accuracy can be reproduced as it is, and dimensional stability of the picture pattern can be secured. In addition, even if the printing ink layer is a multicolor printing pattern, it can be formed by transferring a transfer layer formed in advance by multicolor printing, and color misregistration at the time of manufacturing a transfer sheet can be achieved by ordinary printing on a sheet having good dimensional stability. Since the accuracy within the color misregistration can be obtained, no large color misregistration occurs. This is because, in the transfer sheet, the support sheet does not need embossing properties for forming a concavo-convex pattern, and it is not necessary to use a sheet that is easily softened by heating, and a sheet having good dimensional stability can be used. In addition, since the dimensional stability of the picture pattern is good, registration of the picture pattern and the uneven pattern can be performed if necessary. For this reason, even when the decorative sheet obtained by the present invention is used for flooring or the like, the pattern does not look unsightly at the seam and does not shift. Further, the decorative sheet obtained in the present invention, the base sheet is one sheet without stacking a plurality of sheets,
As a result, the thickness of the decorative sheet can be reduced, so that the sheet does not whiten when the sheet is bent at the time of V-cut processing or the like. Further, before the transfer ink layer is formed as a transfer layer on the substrate sheet, a transparent curable resin paint is applied to the surface of the substrate sheet on the side of the concavo-convex pattern and crosslinked and cured to form a hard coating layer. If it is a method such as to keep, the base sheet further increases the dimensional stability by the hard coating layer, the dimensional stability of the picture pattern is further improved, and if necessary, the register between the picture pattern and the uneven pattern is more improved. It can be adjusted to high precision.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram illustrating a method for manufacturing a decorative sheet according to the present invention.

FIG. 2 is a conceptual diagram illustrating one method of shaping a concavo-convex pattern into a base sheet.

FIG. 3 is a conceptual diagram illustrating another method of forming a substrate sheet by shaping a concavo-convex pattern.

FIG. 4 is a cross-sectional view of an example of a base sheet used in the present invention, obtained by the method of FIG.

FIG. 5 is a cross-sectional view of an example having a hard coating layer as a base sheet used in the present invention.

FIG. 6 is a cross-sectional view of an example of a transfer sheet used in the present invention.

FIG. 7 is a cross-sectional view illustrating some of the decorative sheets obtained by the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Rough pattern 3 Hard coating layer 4 Colored part 5 Transfer sheet 6 Support sheet 6a Support base material 6b Release layer 7 Transfer layer 8 Printing ink layer 8a Picture pattern layer 8b Solid color layer 9 Release layer DESCRIPTION OF SYMBOLS 10 Adhesive layer 11 Melt sheet 12 Material sheet 13 Concavo-convex pattern layer 21 T-die 22 Embossing and cooling roller 23 Press roller 24 Peeling roller 25 Corona discharge treatment device 31 Transfer roller 32 Peeling roller 33 Adhesive coating device 40 Uneven shape 50 roll Intaglio 60 Shaft core 70 Liquid composition 80 Ionizing radiation irradiation device 90 Compression roller 100 Peeling roller 200 Coating liquid supply device A Adhesive R Ionizing radiation S Cosmetic sheet

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 23:00 F term (Reference) 4F100 AA19C AK01A AK01C AK07A AK25B AK25C AK51B AK51C AK51G AK52C AK53C AL05A BA02 BA03 BA07 BA10B BA10C CA13B CB00 CC00B CC00C DD01A EA021 EC042 EH171 EH461 EJ051 EJ081 EJ40A EJ531 EJ551 GB08 HB00B HB01B HB31B JA11A JA12A JB12C JB14C JB16A JB16B JK12C JL02 JL04 JL10B JN01A JN01C 4F209 AA11 AC03 AD05 AD08 AD27 AF01 AF08 AG01 AG03 AG05 AH48 PA04 PB02 PG12 PQ09 PW43

Claims (2)

[Claims] 1. A surface of a base sheet opposite to the uneven pattern while a transparent base sheet mainly formed of a thermoplastic resin having an uneven pattern formed thereon is run as a long strip-shaped sheet. A method for producing a decorative sheet, wherein the printing ink layer is transferred and formed by a transfer method using a transfer sheet comprising a support sheet and a transfer layer and having a printing ink layer having a pattern as the transfer layer. 2. Before transferring and forming a printing ink layer as a transfer layer on a base material sheet, a transparent curable resin coating material is applied to the surface of the base material sheet on the side of the concavo-convex pattern and crosslinked and hardened. The method for producing a decorative sheet according to claim 1, wherein the decorative sheet is formed as a coating layer.