JPH0852849A - Decorative sheet and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a decorative sheet, which has excellent three-dimensional sense of particle such as profoundness, depth and the like and a design expression of brightness feeling of a crystal particle, and a manufacturing method thereof. CONSTITUTION:A particle pattern layer 3, and a transparent or semi-transparent resin layer 4, which covers the entire surface of the particle pattern layer, are sequentially laminated on a thermoplastic resin base material 2. A groove-shaped irregular pattern 5 comprising a line-group-shaped pattern, which is partitioned with closed regions, has the different aligning pattern in the neighboring closed region, has the depth of the groove of 3-100mum and has an interval between a protruding part and the adjoining protruding part of 1-1000mum, is provided at the interface of the grain pattern layer and the resin layer. The manufacturing method is as follows. An ionizing- radiation hardening resin liquid is provided between a roll concave plate, which has the groove-shaped irregular pattern and the inverted concave part, and a film base material, which is hardened with the ionizing radiation and tightly fixed to the film base material. Thus, the groove-shaped irregular pattern layer is formed. Then, the film base material is peeled from the roll concave part, and the irregular sheet is obtained. This sheet is laminated on a thermoplastic resin base material, wherein the grain pattern layer is formed, by thermal compression.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a three-dimensional effect such as a unique depth and depth due to the unevenness inside, and is particularly suitable for expressing the brilliance of crystal grains in a stone pattern. And a manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, various methods have been tried for expressing a three-dimensional effect such as depth and depth in a decorative sheet having a stone pattern used for interior materials such as flooring materials and wall covering materials, and furniture. Came. For example, a transparent thermoplastic resin sheet is laminated on a thermoplastic resin sheet printed with a stone pattern by doubling embossing, and at the same time, unevenness similar to the cleavage surface of a stone plate is formed on the upper surface of the transparent thermoplastic resin sheet. In addition, there was a decorative sheet on which a clear layer was provided with a urethane resin-based paint. In this, unevenness was formed on the outer surface of the decorative sheet to express the three-dimensional effect of the surface of the stone. Further, for example, Japanese Patent Laid-Open No. 6-
In Japanese Patent No. 64131, a thermoplastic resin layer having a glittering property is used as a decorative sheet expressing the surface glossiness of a stone plate, in which a line-shaped groove-shaped uneven pattern, which is a groove-shaped uneven pattern, is formed inside the decorative sheet. It is disclosed that a combination of a stone pattern pattern layer formed on the above and a line-shaped uneven pattern having a spiral curve in a region defined by a closed curve is suitable. Further, in the same publication, when a liquid-repellent pattern layer is formed on the surface of a line-shaped uneven pattern, and when the transparent resin layer is formed, the transparent resin layer on the part where the liquid-repellent pattern layer is formed is repelled. As a result, it is not formed, and as a result, the surface three-dimensional effect due to the surface unevenness pattern can be expressed.

[0003]

However, in the above decorative sheet by doubling embossing, a surface three-dimensional effect can be expressed by the surface unevenness pattern formed on the surface, but each crystal grain which is often seen in stone is usually observed. It was not possible to express even the unique shining sensation of the stone pattern, which shines differently depending on the viewing angle. Further, the surface unevenness pattern and the stone pattern were not on the same level plane, and the harmony of both patterns was insufficient. Therefore, design expression has a certain limit. Moreover, since the surface has an uneven pattern, it has a drawback that it is easily scratched and dust is easily attached. In addition, JP-A-6-64
In the decorative sheet according to Japanese Patent No. 131, since the internal ruggedness pattern is exposed at the portion repelled by the liquid-repellent pattern layer, no depth or depth feeling can be obtained, and the same Japanese Patent Laid-Open No. The line-shaped concavo-convex pattern divided by the closed curve disclosed in 1) was not necessarily optimal for the stone expression. In addition, since there is a pattern layer formed by printing on the upper side of the glitter layer, sufficient glitter feeling cannot be expressed. The present invention has been made to solve such drawbacks, and is suitable for expression peculiar to a stone pattern, and has an excellent three-dimensional effect such as depth and depth,
The present invention provides a decorative sheet capable of expressing the glittering feeling of crystal grains of a stone pattern and capable of more excellent design expression, and a manufacturing method thereof.

[0004]

In order to solve the above problems in the present invention, therefore, in the decorative sheet of the present invention, the entire surface of the stone pattern layer, and further the entire surface of the stone pattern layer, on the thermoplastic resin substrate. A transparent or semi-transparent resin layer is sequentially laminated so as to cover the surface of the stone pattern, and the interface between the stone pattern layer and the resin layer is divided by a closed region, and the direction in which the adjacent closed regions are lined up is different. Is 3 to 100 μm and the interval between the convex portions is 1 to 1000 μm
And a groove-shaped uneven pattern formed of a line group pattern. Further, the decorative sheet may have a matte pattern on the surface of the resin layer. In the above decorative sheet, the resin layer is
It is also configured such that it is composed of a transparent or semitransparent concavo-convex sheet composed of a film substrate and a groove-shaped concavo-convex pattern layer made of a curable resin from the front side.

On the other hand, in the method for producing a decorative sheet of the present invention, the step of producing a transparent or translucent concavo-convex sheet comprising a film substrate and a groove-like concavo-convex pattern layer has the same shape as that of the concavo-convex pattern in the groove-like concavo-convex layer. Adhesion of a groove-shaped uneven pattern layer obtained by irradiating and curing ionizing radiation with an ionizing radiation-curable resin liquid interposed between a roll intaglio having a concave and convex relationship with the film substrate After that, the film base material is peeled off together with the groove-shaped uneven pattern layer from the roll intaglio plate to obtain an uneven sheet composed of the film base material and the groove-shaped uneven pattern layer. Then, as a laminating step, the groove-shaped uneven pattern layer of the uneven sheet is formed. The side facing the stone pattern layer of the thermoplastic resin base material on which the stone pattern layer is formed is laminated by heating and pressurizing the convex portions of the groove-like uneven pattern layer to enter the stone pattern layer. Transparent consisting of a mesh pattern layer and an uneven sheet The interface between the translucent resin layer is partitioned by the closed region, the direction aligned between closed regions adjacent different depth interval of the convex portion and the convex portion is 3 to 100 m 1 to 1
The groove-shaped concavo-convex pattern having a line-group-like pattern of 000 μm is formed.

The present invention will be described in detail below with reference to the drawings. FIG. 1 is a longitudinal sectional view showing an embodiment of the decorative sheet of the present invention. The decorative sheet 1 of the present invention has a layer structure in which a transparent or semitransparent resin layer 4 is laminated on the entire surface of the stone pattern layer 3 and the stone pattern layer 3 on a thermoplastic resin substrate 2. A specific groove-shaped concavo-convex pattern 5 is provided at the interface between the handle layer 3 and the resin layer 4. The groove-shaped concavo-convex pattern 5 is divided into closed regions, and the directions in which adjacent closed regions are lined up are different from each other, and the depth is 3 to 100 μm, and the interval between the protrusions is 1 to 1000 μm. It is an uneven pattern. In the figure, the resin layer 4 is an example of a configuration including a transparent or semi-transparent film base material 41 and a groove-shaped uneven pattern layer 42 made of a curable resin. 2 is a perspective view of the decorative sheet 1 of FIG. 1 in which a thermoplastic resin substrate 2 having a stone pattern layer 3 and a transparent resin layer 4 are virtually disassembled into upper and lower two layers. Is. On the upper side surface of the thermoplastic resin base material 2, a stone pattern layer 3 is formed. In this figure, the surface of the stone pattern layer 3 is a plane and is in a state before the groove-shaped concavo-convex pattern 5 is formed. 3 is a perspective view showing the groove-shaped uneven pattern 5 when the resin layer 4 of FIG. 2 is viewed from the groove-shaped uneven pattern layer 42 side.

An outline of an example of the method for producing a decorative sheet having such a structure is as follows:
A transparent or semi-transparent concavo-convex sheet 4 in which a groove-like concavo-convex pattern layer 42 made of an ionizing radiation curable resin is formed on one surface of a transparent or semi-transparent film substrate 41 is once created, and the groove of the concavo-convex sheet 4 is formed. The uneven pattern layer 42 is laminated by heat and pressure so as to face the stone pattern layer of the thermoplastic resin substrate 2 on which the stone pattern layer 3 is formed by printing, and the groove-like uneven pattern layer 42 is formed.
When it is made to enter inside, it becomes a decorative sheet having a groove-shaped uneven pattern 5 as internal unevenness at the interface between the both.

The thermoplastic resin substrate 2 may be a continuous belt-shaped film or sheet made of a known thermoplastic resin, or a plate-shaped sheet. When such a thermoplastic resin base material is usually a continuous strip having a thickness of about 25 to 200 μm, printing and forming a stone pattern layer and a step of laminating with a continuous strip-shaped concavo-convex sheet which will be described later. Can be continuously performed to efficiently produce a decorative sheet. However, even if it is a plate-shaped sheet rather than a continuous strip, especially for a thick thermoplastic resin substrate having a thickness of about 1 to 10 mm, for example, each sheet is subjected to a heat press by a hot press to produce an uneven sheet. It can also be laminated.

Examples of the resin used for the thermoplastic resin substrate 2 include polyolefin resins such as polyethylene, polypropylene and polymethylpentene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyvinyl chloride and vinyl chloride. Vinyl acetate copolymer, polyvinylidene chloride, vinyl-based polymer such as ethylene-vinyl acetate copolymer, polystyrene, styrene-based resin such as acrylonitrile-styrene copolymer, polymethyl methacrylate, polymethyl acrylate, polymethacryl Examples thereof include acrylic resins such as ethyl acidate, polyamide resins such as nylon 6 and nylon 66, polycarbonates, and cellulose derivatives such as cellulose acetate and cellophane. Among them, polyvinyl chloride has heat resistance, processability,
It is preferable in terms of economy.

The thermoplastic resin base material 2 may have a color concealing property. The coloring may be white, but if the hiding property is provided, when the decorative sheet is applied to the surface of the decorative base material, the decorative sheet itself is not affected by the color and color unevenness of the base decorative base material. You can express the color and design.
Also, if colored, a part of the pattern of the stone pattern layer on the thermoplastic resin substrate is carried by the thermoplastic resin substrate, and the stone pattern layer is printed with a reduced number of colors. Can also be simplified. However, the thermoplastic resin substrate used in the present invention is not limited to those having a color hiding property. For example, if it is transparent or semi-transparent even in coloring, depending on the base, it is possible to make a design expression that makes use of the hue and pattern, and if the decorative base material on which the decorative sheet is applied is transparent like glass, it will be transparent. This is because it is possible to express the design of a unique stone pattern that has From this point of view, the thermoplastic resin substrate may be colorless transparent or semi-transparent.

As one of various embodiments of the thermoplastic resin base material as described above, a thermoplastic resin base material in which a bright pigment is kneaded and mixed, or a thermoplastic resin base material on which a stone pattern layer is formed is formed. A thermoplastic resin base material having a glittering property can also be used, such as a thermoplastic resin base material having a glittering layer formed on the entire surface by printing or coating with a glittering ink or paint. The thermoplastic resin base material having a glittering property is not limited to an opaque one as described in the description of the colored and transparent above, and the amount of the glittering pigment is such that the decorative base material can be seen through. It does not matter even if the number is reduced. In this case, the stone pattern layer is at least transparent to the surface so that the effect of the glittering effect of the thermoplastic resin base material of the lower layer is effective,
It goes without saying that it is necessary to be formed partially or to be formed from a transparent handle. Further, as the thermoplastic resin base material, it is possible to simultaneously use the retention of glitter and the coloring. In this way, it is possible to help the design expression of various natural stone patterns or abstract stone patterns even on the thermoplastic resin substrate side.

The stone pattern layer 3 is prepared by a gravure printing method using a conventionally known ink in which a coloring agent such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer and the like are appropriately mixed and adjusted in a vehicle. A stone pattern of granite (granite), marble (travertine, onyx, marble, etc.) is formed by a known printing method such as a flexographic printing method or a silk screen printing method. The vehicle may be, for example, cellulose resin such as nitrocellulose, styrene resin, acrylic resin, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl resin such as polyvinyl butyral, rosin. A natural or synthetic thermoplastic resin such as a system resin can be used.

Further, when at least one color of a glittering ink containing a glittering pigment is used for forming the stone pattern layer,
It is preferable for expressing the glittering feeling of crystal grains that is unique to the stone pattern. However,
As described above, if the lower thermoplastic resin base material has glitter, it may be omitted in some cases.
When the color tone of the glittering feeling is different depending on each crystal grain of the stone pattern, it is possible to perform various expressions with a multicolor printing of the glittering ink of a plurality of shades that is colored by using together with a coloring agent. In addition,
When the lower layer thermoplastic resin base material has glitter,
As described above, in order to make the glittering effect effective, the stone pattern layer has a partial opening, and the thermoplastic resin base material of the lower layer can be seen from there, or the stone pattern layer itself has a dye. It is advisable to use a transparent colorant of the system, or to reduce the addition amount of the pigment system so that the lower layer can be seen. Further, when the stone pattern layer is printed in multiple colors, or when the color of the colored layer below the layer formed by the glitter ink is used as the coloring thermoplastic resin substrate, the layer formed by the glitter ink is a layer of the glitter pigment. The blending amount,
It is better to suppress the bottom of the glitter layer so that it can be seen through.

FIG. 2 shows an example of the pattern of the stone pattern layer 3, but each region represents a different crystal grain. It is not always necessary that all of these areas be formed by the glitter ink. Also, due to the difference in the refractive index between the stone pattern layer and the resin layer that is an upper layer, light is reflected at the interface between these layers, and it is possible to produce a brilliant feeling although it is smaller than the brilliance of the brilliant pigment. is there.

The bright pigments used in the thermoplastic resin, in the bright layer formed on the thermoplastic resin, or in the stone pattern layer include metallic luster pigments and pearl pigments. Examples of the metallic luster pigment include metallic powders such as gold powder, silver powder, aluminum powder, copper powder, brass powder and the like, metallic flakes, and metal luster such as cut pieces of metal-deposited synthetic resin film. Examples of pearl pigments include pigments having pearly luster and interference luster, such as titanium dioxide-coated mica, fish scales, and bismuth chloride chloride. In particular, pearl pigments such as titanium dioxide-coated mica, fish scales, and bismuth chloride oxide are excellent in the design effect of luster. The blending amount of these pigments is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the thermoplastic resin or the resin content of the ink or the coating liquid. In particular, when the layer containing these glittering pigments is brought into contact with the groove-like uneven pattern serving as the internal unevenness, the design feeling of the stone pattern due to the unique glittering feeling is expressed. In addition, the glitter feeling due to the groove-shaped concavo-convex pattern and the layer having the bright pigment is due to the modulation effect of the reflection of light by the concavo-convex surface of the groove-shaped concavo-convex pattern. Although the amount of reflection is small, reflection occurs, and the glittering feeling is small but it is expressed.

A transparent or semi-transparent resin layer 4 is laminated on the stone pattern layer 3, and the interface between the stone pattern layer and the resin layer is divided into closed regions, and between adjacent closed regions. Different line-up directions, depth of 3 to 100 μm, and interval between convex parts is 1 to 1
The groove-like concavo-convex pattern 5 having a line group-like pattern of 000 μm is provided.

The formation of the groove-shaped uneven pattern 5 which becomes the internal unevenness
A transparent or semi-transparent resin sheet having a groove-like concavo-convex pattern, that is, a concavo-convex sheet 4 is applied to the thermoplastic resin base material 2 on which the stone pattern layer 3 is formed by applying heat and pressure to form grooves in the concavo-convex sheet. The protrusions of the textured pattern layer may be laminated so as to enter at least the stone pattern layer, and further to the thermoplastic resin substrate below the stone pattern layer. When this heat pressure is applied, the groove-like uneven pattern layer needs to be harder than the stone pattern layer and particularly the thermoplastic resin substrate.

As the concavo-convex sheet 4 used in this way,
A thermoplastic resin may be used as long as it has a higher heat distortion temperature and heat resistance than the thermoplastic resin base material used in combination, and a resin base material having a groove-shaped uneven pattern formed by embossing can be used. In this case, the obtained transparent or translucent resin layer 4 has a single layer structure.

However, in the two-layered concavo-convex sheet in which the groove-shaped concavo-convex pattern layer 42 made of a curable resin is formed on the film base material 41 by the method described below, the groove-shaped concavo-convex pattern layer 5 obtained is sharp. Moreover, since it can be made hard, it is suitable for obtaining a unique glittering feeling due to the groove-shaped concavo-convex pattern. The material, manufacturing method, and the like of the transparent or translucent concavo-convex sheet 4 having the two-layer structure will be described.

The uneven sheet 4 is formed by forming a groove-like uneven pattern layer 42 on one surface of a film base material 41. The film base material 41 is transparent or translucent so that the groove-like uneven pattern layer and the stone pattern layer on the lower side can be seen through, and has mechanical strength and heat resistance sufficient to withstand processing during manufacturing. I just need something. Specifically, for example, polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polyester resin such as polybutylene terephthalate, polyarylate resin, chlorinated resin such as polyvinyl chloride, polyvinylidene chloride, acrylic such as polymethylmethacrylate. Thickness of resin, polycarbonate, polyetheretherketone, polyimide, etc. 10 ~ 300μm
Degree, preferably about 25 to 100 μm, and particularly 2
Axial stretched polyethylene terephthalate film costs
Excellent in strength and transparency. Also, as will be described later,
In the case of a mode in which a surface that is the surface of a decorative sheet of an uneven sheet is embossed with an embossing plate to create a matte pattern on the surface, it becomes flexible under the heat and pressure conditions during embossing and the embossing suitability is An excellent film such as polyvinyl chloride is suitable. In addition, on the surface of the film substrate, in order to improve the adhesion with the groove-shaped uneven pattern layer or the stone pattern layer or the thermoplastic resin substrate, corona discharge treatment, plasma discharge treatment, primer coating treatment, etc. The easy adhesion treatment may be applied.

The groove-like uneven pattern layer 42 is formed of a curable resin, and as the curable resin, for example, a known ionizing radiation curable resin, a known thermosetting resin, or the like can be used. The groove-shaped uneven pattern layer is provided on one side of the film base material, and when the thermoplastic resin base material having the stone pattern layer is laminated and adhered by heat and pressure, the uneven shape of the groove-shaped uneven pattern layer is maintained as much as possible. The convex-concave portion is at least in the stone pattern layer, and in the thermoplastic resin substrate that is the lower layer of the stone pattern layer when the stone pattern layer is thinner than the concave-convex pattern of the groove-shaped pattern. It is sufficient if it has enough heat resistance and hardness that it can enter. In addition, if the film base material that supports the groove-shaped uneven pattern layer from the upper side is too soft than the thermoplastic resin base material at the time of hot pressing, the groove-shaped uneven pattern layer may conversely enter the film base material side. , Not desirable.

As the ionizing radiation-curable resin component that can be used for forming the groove-shaped uneven pattern layer 42, a known ultraviolet-curable resin or electron beam-curable resin can be used. The ionizing radiation curable resin is, for example, a (meth) acryloyl group in the molecule [“(meth) acryloyl” means acryloyl or methacryloyl). The same applies below. ] A prepolymer having a plurality of photopolymerizable functional groups such as ethylenically unsaturated groups and epoxy groups, a monomer, or a mixture of a prepolymer and a monomer as a main component.

Examples of the prepolymer include (meth) acrylates such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, silicone (meth) acrylate, melamine (meth) acrylate, and unsaturated. Polyesters,
Examples thereof include epoxy resins and polyene / polythiols.

Examples of the monomer include styrene,
Styrene-based monomers such as α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Propyl acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate,
(Meth) acrylic acid esters such as butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, phenyl (meth) acrylate, and lauryl (meth) methacrylate, (meth) acrylic acid-2- (N, N-diethylamino) ethyl, (meth) acrylic acid-2- (N, N-
Substituted amino alcohol esters of unsaturated acids such as dibenzylamino) ethyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, diethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, And the like, a polyfunctional compound having an ethylenically unsaturated group having a plurality of (meth) acryloyl groups, or a polythiol compound having two or more thiol groups in the molecule, for example, trimethylo Le propane trithioglycolate, trimethylolpropane tri thio propylate,
Examples thereof include pentaerythritol tetrathioglycol. These monofunctional or polyfunctional monomers are appropriately mixed with the prepolymer to control the viscosity of the ionizing radiation-curable resin liquid to adjust the coating suitability, or to adjust the hardness of the cured product. It is preferable to balance the flexibility. Further, for the same purpose as above, a non-ionizing radiation curable resin such as a urethane resin or a cellulose resin may be appropriately added.

The ionizing radiation includes visible rays, ultraviolet rays, electromagnetic waves such as X-rays, and particle beams such as electron rays, and usually ultraviolet rays or electron rays are used. When ultraviolet rays are used, as the ionizing radiation curable resin, in addition to the above-mentioned components, known photopolymerization initiators, photosensitizers and the like are added. As the photopolymerization initiator, for example, benzophenones, acetophenones, benzoquinones, and thioxanthones are used, and as the photosensitizer, amines such as n-butylamine and triethylamine, tri-n-butylphosphine, and the like are used.

The composition containing the above components is liquid or solid at room temperature. Especially in the case of a solid, as the ionizing radiation curable resin liquid prepared by dissolving the composition in a known solvent,
It is used for forming groove-like uneven patterns by roll intaglio. Also,
Even a liquid composition may be appropriately diluted with a solvent to adjust the viscosity of the ionizing radiation curable resin solution. Further, the ionizing radiation-curable resin liquid containing the ionizing radiation-curable resin, as long as it does not hinder the curing by ultraviolet rays or electron beams, as other additives, dyes, colorants such as pigments, silica Further, an extender pigment such as calcium carbonate, clay, talc, and barium sulfate, a thermal polymerization inhibitor, etc. may be added. It should be noted that the uneven sheet 4 is finally the resin layer 4
Therefore, these additives are used within a range that does not impair the transparent or translucent property of the resin layer.

A preferred method of manufacturing an uneven sheet composed of the groove-like uneven pattern layer 42 and the film base material 41 will be described with reference to FIGS. 4 and 5.

FIG. 4 is a process drawing of an embodiment of the uneven sheet manufacturing process at the step of manufacturing the uneven sheet used for the decorative sheet of the present invention, and FIG. 5 is a view showing the manufacturing apparatus used in the same embodiment. Is. First, referring to the manufacturing apparatus of FIG. 5, in the figure, 41 is a transparent or translucent film base material, 71 is a roll intaglio plate provided with a groove-shaped uneven pattern layer 42 to be formed and a recess 72 having an inverse uneven shape. (However, in order to simplify the drawing, the concave portion is shown in a quadrangular cross section), 73 is an ionizing radiation-curable resin liquid, 74 is a pressing roll that abuts the roll intaglio plate and presses the film substrate 41 into the roll intaglio plate, 7
5 is a guide roll for supporting the traveling of the film base material 41, 7
6 is a peeling roll, 77a and 77b are ionizing radiation irradiation devices for curing the ionizing radiation curable resin liquid, and 42 is a film base material 41 as a cured product of the ionizing radiation curable resin liquid.
The groove-like uneven pattern layer 4 formed above, 4 is the groove-like uneven pattern layer 4
An uneven sheet having 2 on the film substrate 41, a coating device 78 for an ionizing radiation curable resin liquid, and a drying device 79 for drying the solvent when the ionizing radiation curable resin liquid contains a solvent component. Is.

The roll intaglio plate 71 is a cylindrical plate material, and in order to provide a recess 72 having a desired groove-shaped concavo-convex pattern and an inverse concavo-convex pattern, the cylindrical plate material is formed by direct lathe processing or electroforming. It is performed by a method of cutting by milling with a mill, an electroforming method, a photo etching method, or the like. As a material for the roll intaglio, a metal such as copper, chromium, or iron, a synthetic resin such as NBR, an epoxy resin, or ebonite, or a ceramic such as glass can be used. The size of the roll intaglio plate is not particularly limited. Although not shown, the roll intaglio plate is connected to a driving device and is rotationally driven in the direction of the arrow around the shaft center.

Using the apparatus as shown in FIG. 5, the steps of manufacturing the uneven sheet are as shown in FIG. 4, a filling step as step 1, a contact step as step 2, a hardening step as step 3, and a close contact as step 4. The process includes a peeling process as Step 5. The filling step as Step 1 is a step of rotating a roll intaglio having recesses corresponding to the irregularities of the groove-shaped irregular pattern layer and filling at least the recesses of the roll intaglio with an ionizing radiation curable resin liquid by a coating device. . In the contact step as the next step 2, the film base material running in synchronization with the rotation direction of the roll intaglio is contacted with the ionizing radiation curable resin liquid filled in at least the recess of the roll intaglio in the filling step. It is the process of making. In the curing step as the next step 3, the film substrate is brought into contact with the roll intaglio by the contact step,
Until peeling in the peeling step described below, the ionizing radiation curable resin liquid interposed between the film substrate and the roll intaglio is irradiated with ionizing radiation by an ionizing radiation irradiating device to cure. is there. The next adhesion step as step 4 is a step that normally proceeds simultaneously with the previous curing step.
In the curing step, a cured product formed by curing the ionizing radiation-curable resin liquid is brought into close contact with the film substrate as a groove-shaped uneven pattern layer. The peeling step as the final step 5 is a step of peeling the film base material on which the groove-shaped concave-convex pattern layer has been formed in close contact in the previous adhesion step to obtain an uneven sheet. Thus, it is possible to obtain an uneven sheet having a two-layer structure having a desired groove-like uneven pattern layer on the film substrate.

FIG. 6 is a view showing a manufacturing apparatus according to another embodiment of the uneven sheet manufacturing process. This manufacturing device is suitable for the case where the ionizing radiation-curable resin liquid contains a solvent component for adjusting the coating viscosity, etc., and when the solvent component is dried and then unevenness is formed by the roll intaglio. Is. According to the figure, the groove-like uneven pattern layer is formed on the film substrate as a coating step. The coating of the ionizing radiation curable resin liquid is not directly applied to the roll intaglio 71, but the coating shown on the left side is performed. The device 78 previously coats the film base material 41. A conventionally known coating means is used for such a coating device. Next, as a drying step, the ionizing radiation curable resin liquid applied to the film base material is dried by a drying device 79.
The solvent is dried by. If necessary, pre-curing may be performed by the ionizing radiation irradiation device 77a. This pre-curing is for viscosity adjustment. And
In the contact filling step, the film base material holding the coated ionizing radiation-curable resin liquid is run in synchronization with the rotation direction of the roll intaglio plate while the roll intaglio plate 7 is pressed by the pressing roll 74.
1 is pressed to fill the concave portion of the roll intaglio with the ionizing radiation curable resin liquid. Thereafter, similar to the steps already described with reference to FIG. 5, a curing step, a contacting step, and a peeling step are sequentially performed to obtain an uneven sheet having a desired groove-like uneven pattern layer formed on the film substrate. To be

In addition to the above-mentioned manufacturing method, the groove-shaped concavo-convex pattern layer can be formed by, for example, screen printing or other raised printing on a film substrate.
In this case, the shape is not sharp, and a smooth wavy cross-sectional shape cannot be formed. However, in the method for producing a decorative sheet of the present invention, when the ionizing radiation-curable resin liquid is interposed between the roll intaglio and the film substrate, the roll is indurated and can be faithfully reproduced to the micron order. Since the groove-shaped concavo-convex pattern formed by the method can be used, it is possible to express the design by sharply reproducing the shape. In such a case, the deformation resistance due to the material of the groove-shaped concavo-convex pattern layer is more important. .

In addition, the side surface of the groove-like concavo-convex pattern layer of the concavo-convex sheet thus obtained is in close contact with the stone pattern layer, the thermoplastic resin base material, or the glitter layer formed on the base material. In order to improve the property, known easy-adhesion treatment such as corona discharge treatment, plasma discharge treatment, and primer coating treatment may be performed.

Next, the concavo-convex sheet obtained as described above,
This is a laminating step in which the uneven sheet is used as a transparent or opaque resin layer by laminating with a thermoplastic resin substrate on which the stone pattern layer has been formed, by heat and pressure, to obtain a target decorative sheet. The concavo-convex sheet is formed into a continuous strip, and the thermoplastic resin substrate on which the stone pattern layer has been formed is also formed into a continuous strip, and thermal lamination is performed by continuously applying heat and pressure for lamination. At this time, an embossing plate having an embossed pattern whose surface is not smooth is used as a means for applying heat pressure, and a thermoplastic resin which is softened and deformed by heat pressure such as a vinyl chloride film on the film base material of the uneven sheet. By using, it is possible to form a matte pattern by embossing on the outer surface of the concavo-convex sheet serving as the surface layer of the decorative sheet simultaneously with lamination. When the thermoplastic resin substrate on which the uneven sheet and the stone pattern layer have been formed is to be formed into a single sheet, the single sheet is sequentially processed by a heat press device or the like. Note that the embossing during sheet-fed may be a pressure embossing. The heat and pressure conditions in the above laminating step may be appropriately selected depending on the presence or absence of embossing, the film base material and the thermoplastic resin base material, and the material of the uneven sheet that is the source of the groove-like uneven pattern. For example, when vinyl chloride resin is used for both of them, a temperature of about 120 to 170 ° C. is preferable in order that the concavo-convex pattern penetrates into the thermoplastic resin substrate having sufficient glitter.

Although it is not optimal for scratching the surface or adhering dust, in the case of wall surface applications where these are not a serious problem, after laminating as described above, matte ink is applied to the surface. If printed, the matte portion with a stone pattern as shown in FIG. 7 can be expressed. The matte portion on the surface is formed as shown in FIG. 8 even if embossing is performed at the same time when the above-mentioned concavo-convex sheet and the thermoplastic resin substrate on which the stone pattern is formed are laminated. You can express the matte part.

The groove-like concavo-convex pattern 5 formed at the interface between the stone pattern layer and the transparent resin layer is a line group pattern composed of a large number of line groups, which is a so-called line pattern. Since the line pattern used in the present invention expresses a stone pattern, a specific line pattern is suitable. That is, FIG.
As shown in the enlarged view of the cross section of the groove in FIG. 9, the groove-shaped unevenness pattern illustrated in FIG. 9 is a shape in which the depth of the groove is 3 to 100 μm and the interval between the convex portions is 1 to 1000 μm. The interval between the convex portions is more preferably 10 to 10 for expressing the glittering feeling of the pattern.
It is about 0 μm. The interval between the convex portions and the depth of the groove may not be constant. The depth of the groove-like concavo-convex pattern is usually several μm so that the concavo-convex pattern can sufficiently penetrate into the stone pattern layer. Is preferably smaller than the thickness of the base material so as to enter. The depth of the groove is more preferably about 5 to 10 μm, and the interval between the convex portions is more preferably about 40 to 80 μm in order to express the glittering feeling of the crystal grains of the stone pattern. If the depth of the groove is less than 3 μm, the glittering sensation due to the diffuse reflection of light is hardly visible, and if it exceeds 100 μm, the effect of expressing the glittering is saturated, so there is no advantage to intentionally exceed 100 μm. In addition, when the interval between the convex portions is less than 1 μm, the effect of glittering is insufficient, and the groove-shaped concave-convex pattern acts as a diffraction grating to generate a rainbow color due to the spectrum of reflected light. Also, 1
When it exceeds 000 μm, an uneven pattern is visible, which is not preferable.

As shown in various examples in FIG. 10, the group of lines forming the groove-shaped concavo-convex pattern is divided into closed regions, and the lines arranged in different directions between adjacent closed regions are suitable for the expression of the stone pattern. ing. 10 (a) and 10 (b) are preferred examples. 10 (c) and 10 (d) show the groove-like concavo-convex pattern disclosed in Japanese Patent Laid-Open No. 6-64131 as described in the description of the prior art as being suitable for a stone pattern. In (c), the line segment that divides the closed region is close to a circle,
It is not optimal because it has a feeling of discomfort because it is far from the jagged grain boundary shape of ordinary crystal grains. FIG.
The line segment that divides the closed region with the groove-like concavo-convex pattern of (d) has a fish scale-like shape, which is also far from the jagged grain boundary shape and is not optimal. In FIG. 10A and FIG. 10B, the line segment that defines the closed region is not a smooth curve but is jagged and the size of the closed region is not uniform, which is close to the actual grain boundary shape of the crystal grains, which is preferable. . Further, these are such that the array form of the line group in the closed region is parallel in each closed region in FIG. (A), and the angle of the parallel line is different between the adjacent closed regions. It is preferable to express the difference in brilliance for each crystal grain by. On the other hand, FIG.
In (b), since the closed region is complicatedly composed of circles and curves, and the arrangement of adjacent closed regions is different,
It is suitable for stone patterns that can produce complex changes in glitter within a single crystal grain and have various glitters for each grain. The groove-shaped concavo-convex patterns shown in FIGS. 10A and 10B may be used in combination.

It is to be noted that if the shape of the crystal grains by the stone pattern layer and the shape of the closed region of the groove-like concavo-convex pattern are the same shape, and the patterns are aligned and synchronized, a realistic stone is obtained. It is preferable because it can express the pattern, but even if the shapes are not always the same or the positions are not synchronized, the illusion causes the shine to be different in the part surrounded by the closed region,
By recognizing the shape of the crystal grains of the stone pattern, it is possible to give a feeling of brilliance due to the crystal grains of the stone pattern.

Thus, according to the present invention, it is possible to express a high design feeling, which has irregularities inside, has a peculiar three-dimensional effect such as depth and depth, and is particularly suitable for expressing the brilliance of crystal grains in a stone pattern. A decorative sheet can be obtained.

[0040]

In the decorative sheet of the present invention, as a result of having a groove-like uneven pattern composed of a line pattern surrounded by a specific closed area,
It is possible to express a design that has an unprecedented three-dimensional effect such as depth and depth, and a different glittering feeling due to the crystal grains that are unique to the stone pattern. In addition, the groove-shaped uneven pattern inside is adjacent to the uneven surface with the stone pattern layer, and is also adjacent to the part having the glitter pigment, so that the reflection of the light depending on the uneven pattern of the incoming light due to the glitter pigment etc. Modulation of 3D realizes a three-dimensional effect such as depth and a glittering effect of crystal grains. A matte pattern can be expressed on the outer surface by printing embossing or matte ink. In the method for producing a decorative sheet of the present invention, a resin layer constituting the decorative sheet is formed from a concavo-convex sheet, and the concavo-convex sheet is used as a production method for forming a groove-like concavo-convex pattern layer on a film substrate. The intaglio of the roll intaglio is precise because it is irradiated with ionizing radiation and cured to form an uneven pattern with the ionizing radiation-curable resin liquid interposed between the roll intaglio having a concave portion and the film base material that are in a reverse uneven relationship with the layer. Faithfully reproduces even minute shapes. As a result, a fine and sharp shape or a smooth wavy uneven shape can be formed inside, and a decorative sheet suitable for expressing the texture of the crystal grains with a bright feeling can be manufactured.

[0041]

EXAMPLES The decorative sheet of the present invention and the method for producing the same will be described below with reference to specific examples.

Manufacturing of Concavo- convex Sheet As a roll intaglio plate, it has a shape shown in FIG. 10 (a), the size of one side partitioning the closed region is distributed in the range of 2 to 10 mm, the groove depth is 10 μm, and the groove convex. A material having a groove-shaped concavo-convex pattern with an interval of 60 μm was prepared. The plate was formed on a copper cylinder surface by a photolithography method using photolithography. Next, using a production apparatus as illustrated in FIG. 5, a urethane acrylate-based prepolymer was added to a vinyl chloride film (GR, plasticizer 8 phr, 0.1 mm thick, manufactured by Riken Vinyl Co., Ltd.) as a transparent film substrate. An ionizing radiation curable resin composition prepared by diluting a polymer ionizing radiation curable resin composition with ethyl acetate as a solvent was used to produce a transparent uneven sheet using the roll intaglio plate. Ultraviolet rays are used as the ionizing radiation, and the irradiation conditions are 160 W / cm × 2 of a high pressure mercury lamp.
The lamp and line speed were set to 10 m / min.

Laminating step As a thermoplastic resin base material, a vinyl chloride resin sheet colored in white (manufactured by Riken Vinyl Co., Ltd., 12P, plasticizer 12)
phr, 0.1 mm thick), as a stone pattern, a granite pattern is printed in multicolor with vinyl chloride-vinyl acetate ink (however, there is no solid pattern), and a stone pattern layer as illustrated in FIG. Was formed. Of these, one color was printed with a red ink containing a titanium dioxide-coated mica pearl pigment as a bright pigment in order to express crystal grains having a high reflectance. Next, the decorative sheet of the present invention was obtained by performing thermal lamination on the stone pattern layer so that the groove-shaped irregular pattern layer side of the irregular sheet obtained above faced and pressure-laminated. The stacking condition is a temperature of 15
The line speed was 10 m / min at 0 to 160 ° C. The resulting decorative sheet, the unevenness of the groove-like uneven pattern layer of the uneven sheet enters the inside of the thermoplastic resin substrate through the stone pattern layer to form an internal groove-like uneven pattern, as a result,
It was a decorative sheet with a distinctive glittering texture of red granite stone grains and a deeper design expression.

[0044]

EFFECTS OF THE INVENTION According to the decorative sheet of the present invention, the three-dimensional effect such as depth and depth peculiar to the stone pattern, and especially the difference in each grain of the crystal grains, and the strength change depending on the light source direction and the line-of-sight direction. It has a glittering effect and can express a stone pattern with a high design that has never been seen before. Also, by providing fine irregularities on the outer surface with embossing or matte ink, it is possible to express matte patterns on stones. According to the manufacturing method of the present invention for such a decorative sheet, the thermoplastic resin substrate and the concave-convex sheet having the groove-shaped concave-convex pattern can be laminated easily by heat and with high productivity. In addition, since the uneven pattern is formed by using the roll intaglio and the ionizing radiation curable resin, a fine and sharp precise shape and a smooth uneven shape are also possible, and the texture of the crystal grains of the stone pattern is Design expression is also possible.

[Brief description of drawings]

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

FIG. 2 is a perspective view of the decorative sheet of FIG. 1 in which a thermoplastic resin substrate having a stone pattern and a transparent resin layer are virtually disassembled into two layers.

FIG. 3 is a perspective view showing a groove-shaped concavo-convex pattern of the transparent resin layer of FIG. 2 seen from the concavo-convex pattern layer side.

FIG. 4 is a process drawing of a step of manufacturing a concavo-convex sheet in the method for manufacturing a decorative sheet of the present invention.

FIG. 5 is a cross-sectional view showing an embodiment of a manufacturing apparatus for the uneven sheet manufacturing process.

FIG. 6 is a cross-sectional view showing another embodiment of the manufacturing apparatus in the uneven sheet manufacturing process.

FIG. 7 is a perspective view showing an example of a matte pattern formed on the surface of a decorative sheet with a matte ink.

FIG. 8 is a perspective view showing an example of a matte pattern formed by embossing on the surface of a decorative sheet.

FIG. 9 is an enlarged cross-sectional view of a groove-shaped concavo-convex pattern used in the decorative sheet of the present invention.

FIG. 10 is a plan view showing various examples of groove-shaped uneven patterns used in the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Thermoplastic resin base material 3 Stone pattern layer 4 Transparent resin layer, uneven sheet 5 Groove-like uneven pattern 6 Matte pattern 41 Transparent resin film 42 Groove-like uneven pattern layer 71 Roll intaglio 72 Recess 73 73 Ionizing radiation curability Resin liquid 74 Pressing roll 75 Guide roll 76 Peeling roll 77a, 77b Ionizing radiation irradiation device 78 Coating device 79 Drying device S1 Filling process S2 Contact process S3 Curing process S4 Adhesion process S5 Peeling process

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Claims (4)

[Claims] 1. A grain pattern layer and a transparent or semitransparent resin layer are sequentially laminated on a thermoplastic resin substrate so as to cover the entire surface of the grain pattern layer. The interface is divided by a closed region, and the direction in which adjacent closed regions are arranged is different,
The depth of the groove is 3 to 100 μm and the interval between the convex portions is 1 to 1
A decorative sheet having a groove-like concavo-convex pattern formed of a line group-like pattern having a thickness of 000 μm. 2. The decorative sheet according to claim 1, wherein the surface of the resin layer has a matte pattern. 3. The resin layer is composed of a transparent or semi-transparent concavo-convex sheet composed of a film base material and a groove-shaped concavo-convex pattern layer made of a curable resin from the front side. The decorative sheet according to 2. 4. A roll intaglio plate having a concave portion having the same inverse concavo-convex shape as the concavo-convex shape of the groove-shaped concavo-convex pattern layer in the manufacturing process of a transparent or semi-transparent concavo-convex sheet comprising a film substrate and a groove-shaped concavo-convex pattern layer. After the ionizing radiation-curable resin liquid is interposed between the film base material and the film base material, the groove-shaped uneven pattern layer obtained by irradiating and curing the ionizing radiation is adhered to the film base material, and then the film base material is groove-shaped A concavo-convex sheet consisting of a film base material and a groove-like concavo-convex pattern layer was peeled off together with the pattern layer to obtain a concavo-convex sheet, and then, as a laminating step, the groove-like concavo-convex pattern layer side of the concavo-convex sheet was heat-treated to form a stone pattern layer. It is composed of a stone pattern layer and a concave-convex sheet by facing the stone pattern layer of the plastic resin base material, heating and pressurizing and laminating the convex portion of the groove-like uneven pattern layer into the stone pattern layer. Partitioned in a closed area at the interface with the transparent or translucent resin layer , Adjacent closed regions are arranged in different directions, the depth is 3 to 100 μm, and the interval between the convex portions is 1
A method for producing a decorative sheet, which comprises forming a groove-shaped uneven pattern composed of a line group pattern having a size of ˜1000 μm.