JPH08108510A - Decorative sheet and manufacture thereof - Google Patents

Abstract

PURPOSE: To provide a decorative sheet having high design properties in which an uneven pattern tuned with a design is formed even on the other surface without reducing concave upward feeling by inner fine uneven pattern and a method for manufacturing the same. CONSTITUTION: A lustrous layer 3, a design layer 4 and a transparent thermoplastic resin film 6 are laminated on an opaque thermoplastic resin film 2, and a groovelike uneven pattern 5 made of a linear grouplike pattern having a depth of 3-30μm and an interval of convex and concave of 1-1000μm is formed on the upper boundary of the lustrous layer. Further, an ultraviolet cure suppressed design layer 7 is laminated on the transparent thermoplastic resin film, and a transparent resin layer 8 of ionizing radiation curable resin cured by ultraviolet rays and electron beam to cover the entire surface of the film having an uneven pattern 9 tuned with the design layer is laminated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet having an uneven pattern on both the inside and the surface thereof, which is excellent in the design expression of depth and three-dimensional effect, and particularly suitable for the expression of wood grain, and its manufacturing method.

[0002]

2. Description of the Related Art Conventionally, in a woodgrain decorative sheet, various measures have been taken in order to more realistically express the texture of natural wood, in addition to the plan print pattern. One is the representation of conduits that appear three-dimensionally as grooves on the surface.
For example, it has been practiced to print a conduit pattern with a matte ink, which is actually flat, but gives a pseudo three-dimensional effect due to the matte effect. Furthermore, by actually forming a groove on the surface by embossing and filling the groove with ink by wiping, it has become possible to express a more realistic conduit by synchronizing the surface irregularity pattern and the conduit pattern. Specifically, for example, a transparent vinyl chloride film is laminated and embossed at the same time by doubling embossing on the printed surface of a colored vinyl chloride film on which a wood grain pattern is printed, and ink is filled by wiping the groove made by embossing. To do.

One of the different texture expressions of natural wood is the unique feeling of light and the feeling of movement of natural wood (hereinafter, both are referred to as "shining feeling" unless it is necessary to use them properly).
Is an expression of. The shiny feeling is a result of the light that has penetrated into the interior of wood being reflected by the internal tissue having a certain regularity of wood fibers and reaching the surface again to be emitted. Therefore, in order to mimic the reflection of light by the internal tissue, various attempts have been made to form a reflecting layer having fine irregularities capable of reflecting light with a certain regularity inside the decorative sheet. For example, in Japanese Utility Model Application Laid-Open No. 5-35394, a pattern layer is provided on the surface of an opaque thermoplastic resin film having luster on the surface, and then a groove-like concavo-convex pattern composed of a specific line group pattern is formed on the pattern layer. Disclosed is a decorative sheet in which a transparent resin layer is formed on the surface of a groove-shaped uneven pattern and a transparent resin layer is provided so that the transparent resin layer is thicker than the depth of the unevenness, and the transparent sheet is attached to a decorative base material with an adhesive. .

[0004]

However, if both the expression of a feeling of light due to the uneven pattern inside the decorative sheet and the conduit expression in synchronism with the surface uneven pattern can be produced, a more realistic expression of the texture of natural wood can be achieved. A sheet should be obtained, but no one with a convincing design has yet been obtained. For example, Japanese Examined Patent Publication No. 63-24470 discloses a method of forming a concavo-convex pattern on the surface while maintaining the concavo-convex pattern as the internal structure of the decorative sheet by devising the processing conditions of the doubling embossing. However, this method has a problem in that the sharpness of the fine irregularities of the groove-like irregularity pattern suitable for expressing a feeling of gloss is reduced by heat and the effect is reduced, so that it cannot be applied.

Further, in Japanese Patent Publication No. 4-64443,
Disclosed is a method of dry laminating a thermoplastic resin film as a transparent resin layer on a groove-like concavo-convex pattern, and a method of expressing a conduit pattern on the surface of the transparent resin layer with a matte ink. However, with this method, the sharpness of the groove-shaped uneven pattern is still reduced due to the residual solvent in the adhesive during dry lamination, and the unevenness of the conduit is also poor, so compared to the combination of embossing and wiping described above, Is a plane, so there is a marked difference. Further, as described above, when the conduit is formed by embossing on the surface of the transparent resin layer formed by dry lamination later, the groove-shaped uneven pattern inside is dull due to heat during processing, and the feeling of shiny is reduced, and further, It may disappear.

In view of the above, the present invention provides a decorative sheet excellent in designability that can realistically express both the luster and the three-dimensional conduit of natural wood due to the unevenness on both the inside and the surface, and a method for producing the same. The purpose is to do.

[0007]

Therefore, in order to solve the above-mentioned problems in the decorative sheet of the present invention, at least a glitter layer and a pattern layer are laminated in this order on an opaque thermoplastic resin film, and further thereon. Is laminated with a transparent thermoplastic resin film and has a depth of 3 to 3 at the upper interface of the glitter layer.
A groove-like concavo-convex pattern having a line group pattern of 0 μm and a distance between the convex portions of 1 to 1000 μm is formed, and an ultraviolet curing suppressing pattern layer is further formed on the transparent thermoplastic resin film. Laminated and further covered with an ultraviolet ray and an electron beam, which has a concave-convex pattern in which a concave portion is formed in synchronization with the ultraviolet ray curing suppression pattern layer portion and covers the entire surface of the transparent thermoplastic resin film. A transparent resin layer made of an ionizing radiation curable resin is laminated.
Further, the pattern of the above-mentioned pattern layer and the pattern for suppressing ultraviolet ray curing may be synchronized with each other.

Further, the method for producing a decorative sheet of the present invention comprises the following steps (A) to (E). (A) A glitter layer on one side of an opaque thermoplastic resin film,
Step of forming a pattern layer. (B) a transparent thermoplastic resin film is laminated by doubling embossing on the layer forming surface side of the opaque thermoplastic resin film on which each of the above layers is formed, and at the same time, the transparent thermoplastic resin film side or the opaque thermoplastic resin Due to the embossing from the film side, the depth at the interface on the upper layer side of the glitter layer is 3 to 30 μm, and the interval between the convex portions is 1 to 10.
A step of forming a groove-shaped concavo-convex pattern having a line-group-shaped pattern of 00 μm. (C) A step of forming an ultraviolet curing suppression pattern layer on the surface of the transparent thermoplastic resin film. (D) The entire surface of the transparent thermoplastic resin film on which the ultraviolet curing suppression pattern layer is formed is coated with an ionizing radiation curable resin liquid that is cured by ultraviolet rays, and then cured by irradiation with ultraviolet rays, and the ultraviolet curing A step of forming a concavo-convex pattern in which the suppression pattern layer portion becomes a recess. (E) A step of irradiating the ionizing radiation curable resin with an electron beam to completely cure the resin, thereby forming a transparent resin layer having a concavo-convex pattern in synchronization with the ultraviolet curing suppression pattern layer.

The method for producing a decorative sheet of the present invention is
It is also configured by the following steps (A) to (D). (A) A step of forming a pattern layer and a glitter layer on the back surface of a transparent thermoplastic resin film, and an ultraviolet curing suppression pattern layer on the surface thereof. (B) The transparent thermoplastic resin film on which each of the layers is formed on the back side is laminated by doubling embossing on the opaque thermoplastic resin film, and at the same time, the transparent thermoplastic resin film side or the opaque thermoplastic resin film side. By the embossing, the depth at the interface on the upper layer side of the glitter layer is 3 to 30 μm and the interval between the convex portions is 1 to 1000.
A step of forming a groove-shaped concavo-convex pattern composed of a line group-shaped pattern of μm. (C) The entire surface of the transparent thermoplastic resin film on which the UV-curing suppression pattern layer is formed is coated with an ionizing radiation-curable resin liquid that cures with UV light, and then cured by irradiation with UV light, and the UV cure A step of forming a concavo-convex pattern in which the suppression pattern layer portion becomes a recess. (D) A step of irradiating the ionizing radiation-curable resin with an electron beam to completely cure the resin, thereby forming a transparent resin layer having a concavo-convex pattern in synchronism with the ultraviolet curing suppression pattern layer.

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. In the decorative sheet 1 of the present invention shown in the figure, a glitter layer 3 and a pattern layer 4 are provided on an opaque thermoplastic resin film 2, and a transparent thermoplastic resin film 6 is doubled on the obtained film. It is laminated by ring embossing. At that time, embossing is performed so that the groove-shaped concavo-convex pattern 5 can be formed on the upper interface of the glitter layer 3 from the upper side transparent thermoplastic resin film 6 side. Further, thereafter, the ultraviolet curing suppressing pattern layer 7 is provided on the surface of the transparent thermoplastic resin film. Then, an ionizing radiation curing cured by ultraviolet rays and electron beams, which has an uneven pattern 9 which becomes a recess in synchronization with the portion of the ultraviolet curing suppressing pattern layer 7 and covers the entire surface of the transparent thermoplastic resin film 6. Transparent resin layer 8 made of resin
Is formed. Incidentally, there are various modes at the time of forming the glitter layer, the pattern layer, the target film for forming the ultraviolet curing suppression pattern layer, and the ultraviolet curing suppression pattern layer, which will be described later.

FIG. 2 is a vertical sectional view showing another embodiment of the decorative sheet of the present invention. The decorative sheet 1 of the present invention in FIG. 2 is a film obtained by first providing an ultraviolet curing suppressing pattern layer 7 on the upper side of a transparent thermoplastic resin film, and providing a pattern layer 4 and a glitter layer 3 on the lower side. Is laminated with the opaque thermoplastic resin film 2 by the dove ring embossing.
At that time, embossing is performed from the lower opaque thermoplastic resin film 2 side so that the groove-shaped concavo-convex pattern 5 can be formed at the upper interface of the glitter layer 3. Further, after that, the entire surface of the transparent thermoplastic resin film 6 provided with the ultraviolet curing suppression pattern layer 7 is covered, and the ultraviolet curing suppression pattern layer 7 is formed.
A transparent resin layer 8 is formed in which a portion forms a concave portion, and the concave portion has an uneven pattern 9 that is in synchronization with the ultraviolet curing suppression pattern layer 7. Incidentally, there are various modes at the time of forming the glitter layer, the pattern layer, the target film for forming the ultraviolet curing suppression pattern layer, and the ultraviolet curing suppression pattern layer, which will be described later.

FIG. 3 is a vertical sectional view showing another embodiment of the decorative sheet of the present invention. The decorative sheet 1 of the present invention in FIG. 3 is provided with a glitter layer 3 and a pattern layer 4 on an opaque thermoplastic resin film 2, and groove-like irregularities are formed by embossing the surface provided with these layers. A pattern 5 is formed. Further, after that, the ultraviolet curing suppressing pattern layer 7 is provided on the opaque thermoplastic resin film 2 on the side where the groove-shaped concavo-convex pattern 5 is formed. Then, the entire surface of the opaque thermoplastic resin film 2 provided with the glittering layer 3, the pattern layer 4 and the ultraviolet curing suppressing pattern layer 7 is covered, and the ultraviolet curing suppressing pattern layer 7 part forms a concave part, and the concave part is formed. The transparent resin layer 8 has a concavo-convex pattern 9 aligned with the ultraviolet curing suppression pattern layer 7.
Is formed.

First, the opaque thermoplastic resin film 2 constituting the decorative sheet of the present invention will be described. As the opaque thermoplastic resin film 2, an opaque, colored or non-colored one is used in order to conceal the base material to which the decorative sheet is attached. As such a film, a film of a colored vinyl chloride resin is usually used, but in addition to this, for example, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate-vinyl chloride Polymers, polyvinyl butyral, polyvinyl fluoride, polyvinylidene fluoride, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers and other vinyl resins, polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymers, polybutylene terephthalate, etc. Acrylic resin such as polyester resin, methyl polymethacrylate, methyl polyacrylate, ethyl polymethacrylate, polyacrylonitrile, polystyrene, acrylonitrile-
Butadiene-styrene resin (ABS), styrene resin such as acrylonitrile-styrene copolymer, polyolefin resin such as polyethylene, polypropylene, polymethylpentene, cellulose derivative such as cellulose acetate and nitrocellulose, nylon 6, nylon 66 A known film made of a resin such as polyamide resin, polyvinyl alcohol, or polycarbonate may be used. In order to make the film opaque, pigments such as titanium dioxide, carbon black, and rouge are mixed and mixed. The thickness of the film is about 0.01 to 5 mm, usually about 0.02 to 1 mm. As shown in FIG. 2, when a groove-like uneven pattern is formed on the internal interlayer interface by doubling embossing from the opaque thermoplastic resin film side, if the film is too thick, the embossing does not reach the inside sufficiently. Therefore, the thickness is preferably 0.1 mm or less, though it depends on the plate depth of the embossing plate.

Further, the transparent thermoplastic resin film 6 used in the construction illustrated in FIGS. 1 and 2 is for arranging a UV-curing-inhibiting pattern layer at a distance in the vertical direction from the lower pattern layer. Therefore, as a transparent thermoplastic resin film, the thickness that can secure a vertical distance enough to express a sense of depth, and the lower pattern layer can be seen through, and the light reaching the glitter layer can be seen. It is sufficient that it is at least transparent enough to reflect and return to the surface. Further, if it is transparent, it may be colored or may be semi-transparent. As the transparent thermoplastic resin film, a known film made of a resin that can be used for the above opaque thermoplastic resin film can be used. The thickness of the film is
Usually, it is about 10 to 200 μm, but if it is too thin, the distance between the pattern layer and the ultraviolet curing suppression pattern layer is too close to give a sense of depth. Is preferred. If it is too thick, the depth will increase, but the cost will increase. On the other hand, when forming a groove-like concavo-convex pattern by embossing on the internal interlayer interface by doubling embossing from the transparent thermoplastic resin film side, depending on the plate depth of the embossing plate, if the film is too thick, the embossing will reach the inside. Since it does not reach sufficiently, the thickness is preferably 100 μm or less.

The glitter layer 3 reflects light inside the decorative sheet in order to express a feeling of shine, and it is sufficient that it has light reflectivity, and a metal layer or a printing layer of ink containing a glitter pigment is used. Is formed on the entire surface or in the form of a pattern. When it is formed as a metal layer, a metal or alloy such as aluminum, chromium, copper, iron and nickel is vacuum deposited,
It is provided by a known method such as sputtering or electroless plating. In this case, the thickness of the glitter layer is usually 4 to 1000Å
The degree is preferred. When forming as a printing layer,
The glitter ink having the glitter pigment is provided by a known printing means such as gravure printing, flexographic printing, silk screen printing. Examples of bright pigments include metal powders such as gold powder, silver powder, aluminum powder, copper powder, brass powder, and metal flakes, or metallic luster pigments having metallic luster such as cut pieces of metal-deposited synthetic resin film, and titanium dioxide coating. Known bright pigments such as pearl pigments having pearl luster or interference luster such as mica, fish scales, bismuth chloride and the like can be used, but titanium dioxide-coated mica is preferable. A mixture of these glitter pigments with a known vehicle is used as a glitter ink. The vehicle is vinyl type, acrylic type,
Amino resins, amino alkyd resins, polyurethane resins, cellulose resins, butyral resins, etc. are used. in this case,
The thickness of the glitter layer is usually preferably about 1 to 10 μm.
Further, the glitter layer may be formed not by the ink but by adjusting as a coating liquid and coating. The glitter layer is prepared by kneading a glitter pigment in an opaque thermoplastic resin,
It can also be integrated with an opaque thermoplastic resin.

For the pattern layer 4, various patterns such as a wood grain pattern of natural wood, a stone pattern pattern of marble, granite, etc., a cloth pattern pattern, or an abstract pattern pattern such as a figure and a symbol are appropriately used depending on the purpose of the decorative sheet. The decorative sheet of the present invention is particularly suitable for reproducing the grain pattern of natural wood. The pattern layer is a vehicle using a vinyl resin, an acrylic resin, a cellulose resin, an aminoalkyd resin, a butyral resin, or the like, and if necessary, a pigment, a coloring agent such as a dye, an extender pigment, a stabilizer, a plasticizer, etc. Known printing ink mixed with, gravure printing,
It is formed by a known printing means such as flexographic printing and silk screen printing.

The UV-cure suppressing pattern layer 7 is a layer used for expressing a conduit pattern in the expression of a wood grain pattern of natural wood, and is made of an ionizing radiation-curable resin which is cured by ultraviolet rays and is coated thereon. It is also a pattern layer having the function of suppressing the curing reaction and forming recesses in the ionizing radiation curable resin there to form an uneven pattern on the surface of the decorative sheet. The ultraviolet curing inhibition pattern layer is a known vehicle that can be used for the pattern layer,
Gravure printing, flexographic printing, silk screen printing, etc., using a printing ink prepared by adding an ultraviolet curing inhibitor that suppresses the curing of ionizing radiation curable resin with ultraviolet rays in addition to colorants and other additives. It is formed by a known printing means. As the ultraviolet curing inhibitor, in the mechanism of the curing reaction of the ionizing radiation-curable resin with ultraviolet rays, it deactivates radicals to suppress curing,
In the mechanism of the curing reaction by electron beam, a known radical deactivator which is a substance that does not inhibit the curing due to the competition of the deactivation of the radical and the radical polymerization reaction is used. For example, the nitroso compound is N-nitroso. Phenylhydroxylamine ammonium salt, aluminum-N
-Nitrosophenylhydroxylamine and the like,
Aluminum-N-nitrosophenylhydroxylamine is particularly preferable. The total amount of ink resin is 100
It is about 1 to 20 parts by weight with respect to parts by weight. If it is too small, the effect of suppressing curing will be small and the unevenness of the surface unevenness pattern will be too shallow, and if it is too large, the sharpness of the unevenness will be lost, so
Not preferred.

In the structures illustrated in FIG. 1 and FIG. 2, the objects for forming the glitter layer, the pattern layer and the ultraviolet curing suppressing pattern layer may be any layer structure of the intended decorative sheet as a result. There are various modes. For example, the glitter layer 3 and the pattern layer 4 are formed on the opaque thermoplastic resin film 2, and the transparent thermoplastic resin film 6 is laminated on the opaque thermoplastic resin film 2 after forming these layers. After that, there is a method of forming an ultraviolet curing suppression pattern layer on the laminated transparent thermoplastic resin film. Further, an ultraviolet curing suppression pattern layer is formed on the front surface side of the transparent thermoplastic resin film 6, and a pattern layer and a glitter layer are sequentially formed on the back surface side of the transparent thermoplastic resin film 6 after forming these layers. Thermoplastic resin film 2 opaque to the back surface
And the like. In this method, it is also possible to form the ultraviolet curing suppression pattern layer and the pattern layer in synchronization with each other (for example, as in Japanese Patent Application No. 5-286243, the film is inverted using a turn bar to simultaneously print on the front and back sides inline. Yes, the design feeling is further enhanced.

The groove-shaped concavo-convex pattern 5 controls the reflection direction of the light reflected by the glitter layer 3 and expresses a design feeling due to internal light reflection such as a shiny feeling of natural wood. FIG. 4 is an enlarged view of a cross section of a groove-like concavo-convex pattern, which is a so-called parallel line pattern and is a line-group-shaped pattern composed of a large number of line groups. As shown in the figure, the groove-shaped uneven pattern has a groove depth of 3 to 30 μm and an interval between the protrusions of 1 to 100.
It has a shape of 0 μ, and the interval between the convex portions is more preferably about 1 to 100 μm for expressing the shiny feeling of natural wood. The depth and the interval between the convex portions do not have to be constant in the line group, and in the case of having a partition as shown in FIG. 5D described later, the value may be changed for each partition, or a little between adjacent lines. You may change it one by one. By changing the shape in this way, the light reflection effect can be changed slightly depending on the place.

FIG. 5 is a plan view showing various aspects of the groove-shaped concavo-convex pattern formed by the above-mentioned line pattern. Figure 5
5A is a parallel line pattern composed of a wave-shaped parallel curve group 10, FIG. 5B is a parallel line pattern composed of a plurality of straight line groups having different directions in a plurality of sections, and FIG. 5C is a parallel curve. A parallel line pattern in which the group 10 and the parallel straight line group 11 are combined, FIG. 5D shows a parallel line pattern formed by the parallel curve group 10 of closed curves, and FIG. 5E shows parallel lines having different directions in a plurality of sections. A line pattern consisting of a group of curves, FIG.
The parallel line pattern which consists of the non-parallel curve group 12 which changes the function parameter of a function curve and the space | interval between each curve changes in a line direction is shown. Further, a line pattern or the like composed of a measurement curve group 13 using a measurement waveform obtained by observing voice with an oscilloscope as shown in FIG. 5G may be used. The function curve includes, for example, a sine wave curve, a cycloid curve, an elliptic function curve, a Bessel function curve, and the like. Various measurement waveforms such as a waveform measured by measuring the surface roughness of an object and output by a pen recorder can be used. In this way, in the line group-like pattern forming the groove-shaped uneven pattern, the unevenness of adjacent lines is
A group of lines that change the depth and the unevenness interval to be the same or subtly.
Further, by dividing these line groups and combining them, a light reflection pattern is produced.

Since the groove-shaped uneven pattern as described above is intended to cause reflection of light entering the interior of the decorative sheet by the uneven surface of the groove-shaped uneven pattern, the glitter layer which is a light-reflecting functional layer. Is formed on at least the interface on the upper surface side.

The groove-like concavo-convex pattern is formed by embossing of a flat pressure type or a circular pressure type. There are two types of forming methods depending on the position of the groove-shaped concavo-convex pattern. The first method is a method of forming an opaque thermoplastic resin film and a transparent thermoplastic resin film by laminating by a doubling embossing process as illustrated in FIGS. 1 and 2.

In the doubling embossing method,
At least the pattern layer and the glitter layer are the lower opaque thermoplastic resin film 2 side or the transparent thermoplastic resin film 6 side, or the glitter layer is the opaque thermoplastic resin film 2 side and the pattern layer is transparent. The thermoplastic resin film 6 side, etc., and the two films are laminated at the same time so as to have a layered structure interposed therebetween. In the usual doubling embossing, the shaping is intended for the surface, but in the decorative sheet and the manufacturing method thereof of the present invention, for the purpose of internal shaping, the surface unevenness obtained on the surface where the embossing plate is pressed is the result. It is nothing more than what you get. Since the target shaping surface is the internal interface,
There are two types of embossing methods, from the front surface side (transparent thermoplastic resin film side) and the back surface side (opaque thermoplastic resin film side), depending on the surface of the embossing plate that is brought into pressure contact.

On the other hand, in the film to be used, the film on the pressure contact surface side of the embossing plate can form a groove-like uneven pattern deeper if it is made thinner depending on the balance with the plate depth of the embossing plate. In addition to this, if the thickness of the thermoplastic resin film on the side opposite to the pressure contact surface side of the embossing plate is made thinner on the pressure contact surface side than the opposite surface side, it is The uneven pattern can be sufficiently shaped. Further, in order to fully express the sense of depth due to the pattern layer and the ultraviolet curing suppression pattern layer, it is preferable that the transparent thermoplastic resin film is thick, and in this respect, the pressure contact surface of the embossing plate is opaque on the lower side. The thermoplastic resin film side is preferable. However, depending on the sense of depth to be expressed, the upper transparent thermoplastic resin film may be used.

It is to be noted that a thinner film on the embossing plate pressure contact surface side is advantageous in terms of forming groove-like irregularities, but if the film does not have moderate heat resistance, the film will be stretched by the heat of drying during printing, and a multicolor film will be formed. The printing accuracy such as register accuracy in printing and machine suitability is deteriorated. For this reason, when using a film having poor heat resistance, such as a vinyl chloride film, to thin the film, it is only possible to perform printing on the entire surface without register accuracy. On the other hand, in terms of depth, it was preferable that the transparent thermoplastic resin film be thick. Therefore, in order to balance the three points of depth, formation of groove-like unevenness, and printability, a groove-like uneven pattern is formed by embossing from the thinned opaque thermoplastic resin film side, and thickened transparent thermoplastic resin. It is sufficient to print all of the pattern layer, the glitter layer, and the ultraviolet curing suppression pattern layer on the film. Moreover, in this way, synchronous printing of the pattern layer and the ultraviolet curing suppression pattern layer is also possible.

The step of providing the ultraviolet curing suppressing pattern layer may be any step before or after the doubling embossing. Therefore, the ultraviolet curing suppressing pattern layer may have been already formed at the time of doubling embossing, or may be before being formed. The resulting layer structure is the same. However, when the ultraviolet suppressor contained in the ultraviolet curing suppressing pattern layer is thermally deteriorated by heat during embossing, it is after embossing. On the other hand, in order to synchronize the pattern layer and the UV-curing suppression pattern layer, it is better to have those layers on the same film, and the film size changes slightly due to the heat history due to doubling embossing. It is better to install it before doing. In this respect, the pattern layer and the ultraviolet curing suppression pattern layer may be synchronously printed on both sides of the transparent thermoplastic resin film before embossing, and if the glitter layer is also printed at the same time, separate films can be obtained. Since the number of steps is smaller than that of printing on, it is also advantageous in terms of manufacturing cost.

The second method for forming the groove-shaped uneven pattern is shown in FIG.
As illustrated in FIG. 3, a method of embossing an uneven pattern on the surface of the opaque thermoplastic resin film 2 without providing a transparent thermoplastic resin film. That is, on one surface of an opaque thermoplastic resin film, usually a glitter layer is provided on the entire surface, and further, a picture layer formed as a pattern so that a part of the glitter layer is usually exposed is provided thereon. The resulting surface, that is, the layer exposed on the surface,
A pattern layer and a glittering layer exposed from a part of the pattern of the pattern layer, and an embossing plate is directly pressed onto the surface under heating to form a groove-shaped uneven pattern by embossing.

The transparent resin layer 8 is formed by applying a transparent ionizing radiation-curable resin liquid curable with ultraviolet rays on the surface and then curing it. The transparent resin layer may be colored as long as it is transparent, or may be semitransparent.
When ionizing radiation curable resin is used for the transparent resin layer, the ionizing radiation curable resin does not require heat for curing, so it is possible to prevent the minute groove-like uneven pattern from becoming dull due to the heat during curing, unlike thermosetting resin. it can. Further, since it is liquid and can be solvent-free, there is an advantage that it is possible to prevent the solvent from deforming the groove-shaped concavo-convex pattern even when directly contacting the groove-shaped concavities and convexities. Conventionally, a concavo-convex pattern on the surface that is synchronized with the conduit pattern is formed by using an ink to which a thermosetting inhibitor that suppresses thermosetting of the thermosetting resin is added, and the thermosetting resin is applied onto it. There is also a method of forming a concavo-convex pattern by curing by curing with this method, but in this method, the sharpness of the internal fine groove-shaped concavo-convex pattern is deteriorated by the heat during thermosetting.

As the ionizing radiation curable resin forming the transparent resin layer, a known ultraviolet curable resin can be used. As such an ionizing radiation curable resin, for example, a (meth) acryloyl group in the molecule [(meth) in "(meth) acryloyl" means acryloyl or methacryloyl). The same applies hereinafter. ] An oligomer having two or more photopolymerizable functional groups such as ethylenically unsaturated groups and epoxy groups, and / or monofunctional and polyfunctional monomers are appropriately mixed. Examples of the oligomer include urethane (meth) acrylate and epoxy (meth)
Examples thereof include (meth) acrylates such as acrylates, polyester (meth) acrylates, silicone (meth) acrylates, melamine (meth) acrylates, unsaturated polyesters, epoxy resins, and polyenes / polythiols.

As the monofunctional or polyfunctional monomer,
For example, styrene, styrene-based monomers such as α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate. , (Meta)
2-ethylhexyl acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate,
(Meth) acrylic acid esters such as methoxybutyl (meth) acrylate, phenyl (meth) acrylate, and lauryl (meth) methacrylate, (meth) acrylic acid-2-
Substituted amino alcohol esters of unsaturated acids such as (N, N-diethylamino) ethyl and (meth) acrylic acid-2- (N, N-dibenzylamino) ethyl, and unsaturated carboxylic acid amides such as acrylamide and methacrylamide. , Monofunctional monomers such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Polyfunctional monomer having a plurality of (meth) acryloyl groups such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or a molecule 2 or more in Polythiol compounds having a thiol group, for example, trimethylolpropane trithioglycolate, trimethylolpropane tri thio propylate, pentaerythritol thioglycolate, and the like.

In addition to the above-mentioned components, known photopolymerization initiators such as benzophenones, acetophenones, and thioxanthones, and n-butylamine, triethylamine, etc., in order to be curable by ultraviolet rays as ionizing radiation. Known amines, known photosensitizers such as tri-n-butylphosphine, etc. are added.

A non-ionizing radiation curable resin may be used in combination with the ionizing radiation curable resin. Examples of the non-ionizing radiation curable resin include urethane resins, cellulose resins, polyester resins, acrylic resins, vinyl acetate resins, vinyl chloride resins, polyvinyl acetal resins such as polyvinyl butyral, and vinyl chloride-acetic acid. Examples thereof include vinyl copolymers. The amount of the non-ionizing radiation curable resin used is usually in the range of 1 to 70% by weight, preferably 5 to 50% by weight. By using a non-ionizing radiation curable resin together, the coating suitability is adjusted by controlling the viscosity of the ionizing radiation curable resin liquid, and the desired physical properties are especially achieved by balancing the hardness and flexibility of the cured product. You can

A composition comprising the above-mentioned ionizing radiation-curable resin and a non-ionizing radiation-curable resin used as appropriate is used as an ionizing-radiation-curable resin liquid. Additives such as a colorant, a filler, a matting agent, a stabilizer, and a thermal polymerization inhibitor may be blended in a range that does not hinder the curing by an electron beam or the like. Further, the ionizing radiation curable resin liquid is preferably a liquid itself at room temperature. In the case of a solid, it can be liquefied by adding a solvent, but in the embodiment in which the transparent resin layer is provided in contact with the groove-shaped uneven pattern, the glitter layer or the pattern layer may be dissolved by the solvent to dull the groove-shaped uneven pattern. Yes, it is not preferable.

The ionizing radiation includes visible rays, ultraviolet rays, electromagnetic waves such as X-rays, and particle beams such as electron beams. Ultraviolet rays are used in the first curing step and electron beams are used in the final complete curing step. .

The liquid transparent ionizing radiation curable resin described above is applied to a gravure coat, a comma coat, a flow coat,
A transparent resin layer is obtained by applying a known coating method such as roll coating, spray coating, or brush coating, and then curing it by irradiation with ultraviolet rays and then with an electron beam. The thickness of the transparent resin layer is usually about 0.1 to 100 μm.

The concavo-convex pattern 9 formed on the surface of the transparent resin layer 8 reproduces a three-dimensional pattern on the outer surface of the decorative sheet, and a wood-grained decorative sheet expresses a recessed conduit pattern. . The uneven pattern is formed by skillfully utilizing the effect of suppressing the curing of the ionizing radiation curable resin by the ultraviolet rays by the ultraviolet ray curing suppression pattern layer. Initially, the ionizing radiation curable resin liquid applied on the transparent thermoplastic resin film has a uniform thickness including the portion on the ultraviolet curing suppression pattern layer, but the curing reaction proceeds by irradiating ultraviolet rays. As the volume shrinks, the thickness becomes thinner. However, since the part on the ultraviolet curing suppression pattern layer does not cure, it is thicker than the surrounding thickness with the original thickness, and as a result, a difference in thickness occurs, and the resin liquid flows from the high-thickness portion to the low-thickness portion. ,
The thickness changes in the direction of homogenization. That is, the ionizing radiation-curable resin on the ultraviolet-curing-inhibited pattern layer moves to the surrounding area where there is no ultraviolet-ray inhibitor. Next, by irradiating with an electron beam to completely cure the applied resin liquid including the part on the ultraviolet curing suppression pattern layer, the resin liquid on the part on the ultraviolet curing suppression pattern layer is uncured and before volume shrinkage occurs. However, the surrounding area has already been hardened and volume contraction has already occurred. Therefore, the volume on the portion on the ultraviolet-curing-inhibited pattern layer has a larger volume shrinkage than that of the surrounding area, so that a concave portion is formed. At this time, if a solvent is added to the ionizing radiation curable resin liquid,
The effect of forming the recesses is further increased. In this manner, the formation of the transparent resin layer 8 having the concavo-convex pattern 9 synchronized with the ultraviolet curing suppression pattern layer is completed by selectively using the ultraviolet curing suppression pattern layer and curing by ultraviolet rays and electron beams.

Thus, the decorative sheet of the present invention and the method for producing the same can provide a decorative sheet having excellent designability. Further, the decorative sheet of the present invention is particularly suitable for the expression of wood grain, but in addition, it is also used for various design expressions such as stone, cloth, or abstract pattern by taking advantage of its excellent depth, three-dimensional effect, and shiny feeling. can do.

[0038]

In the decorative sheet of the present invention, since the light-reflecting surface of the inner glittering layer has the groove-like concavo-convex pattern, the feeling of luster and the depth due to the inner picture layer and the glittering layer are expressed. In addition, a real three-dimensional effect is expressed by the uneven pattern on the surface that is synchronized with the ultraviolet curing suppression pattern layer. As a result, the luster of the natural wood and the texture of the conduit are realistically expressed. Further, a richer sense of depth is expressed by the two picture layers including the ultraviolet curing suppression picture layer on the picture pattern inside. Moreover, by synchronizing the pattern layer and the ultraviolet curing suppression pattern layer, a pattern in which the three of the surface unevenness pattern are synchronized is formed,
A more realistic depth and design feeling is expressed.

In the method for producing a decorative sheet of the present invention, after the groove-like uneven pattern to be the internal unevenness is provided, the uneven pattern on the surface of the decorative sheet is formed by the ionizing radiation curable resin which does not require heat, so that it is fine. Does not reduce the sharpness of the groove-like uneven pattern. Furthermore, when two pattern layers, a pattern layer and an ultraviolet curing suppression pattern layer, are formed on the front and back of the transparent thermoplastic resin film, they can be synchronized.

[0040]

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

Example 1 On one side of a colored opaque vinyl chloride film (thickness 0.1 mm, plasticizer 20 phr), a glitter layer was formed on the entire surface with a pearl ink of vinyl chloride-vinyl acetate resin, and further thereon. A woodgrain pattern layer was formed by gravure printing using a vinyl chloride-vinyl acetate resin ink. Next, by circular pressure type doubling embossing,
An upper surface on which the glitter layer of the film obtained above is formed,
Transparent vinyl chloride film (thickness 0.03 mm, plasticizer 20
phr), and embossed from the side of the transparent vinyl chloride film by using an embossing roll having a groove-like concavo-convex pattern with a line pattern consisting of parallel curved lines in a sinusoidal shape with a depth of 20 μm and a convex interval of 70 μm. Was carried out to obtain an intermediate sheet. Embossing conditions are heating drum temperature 16
The temperature was 5 ° C., the plate surface temperature was 70 ° C., the embossing pressure was 4 MPa, and the run speed was 10 m / min.

Then, on the surface of the transparent vinyl chloride film of the intermediate sheet, a vinyl chloride-vinyl acetate resin in which 7% by weight of aluminum-N-nitrosophenylhydroxylamine as an ultraviolet curing inhibitor is added to the total amount of the ink resin content. A conduit pattern was formed by gravure printing with the above ink to form an ultraviolet curing suppression pattern layer. Then, an ionizing radiation curable resin liquid having the following composition was applied to the upper surface of the transparent thermoplastic resin film, on which the ultraviolet curing suppression pattern layer was formed, by a gravure reverse method to a film thickness of 40 μm and irradiated with ultraviolet rays. After the first step of curing, the composition is completely cured by irradiation with an electron beam to form a transparent resin layer having an uneven pattern on the surface of the ultraviolet curing suppression pattern layer to obtain a decorative sheet of the present invention. It was The irradiation condition of ultraviolet rays is 160 W / cm
Line speed is 20m / min with 2 x lamps, electron beam irradiation conditions are 175keV, 3Mrad, and line speed is 3
It was set to 0 m / min. Ionizing radiation curable resin liquid oligomer component Urethane acrylate oligomer 29 parts by weight Monomer component 2-ethylhexyl acrylate 7 parts by weight Ethyl carbitol acrylate 8 parts by weight Polyethylene glycol 200 diacrylate 6 parts by weight Matting agent Polycarbonate beads 4 parts by weight Solvent (toluene, Xylene, cyclohexanone) 46 parts by weight Sensitizer (Ciba Geigy, Irgacure 184) 2 parts by weight Slip agent (methacryl-modified silicone) 0.5 parts by weight

Example 2 A transparent vinyl chloride film (thickness 0.10 mm, plasticizer 20 phr) was provided on the surface with a conduit pattern UV-curing-inhibiting pattern layer, and on the back side was a wood grain pattern layer and the overall glitter layer. Formed by printing. The ink used for each layer is the same as in Example 1. Next, by circular pressure type doubling embossing, the back side of the film obtained above on which the glitter layer is formed and a colored opaque vinyl chloride film (thickness 0.03 mm, plasticizer 20 phr) are attached, and the emboss is colored. An intermediate sheet was obtained in the same manner as in Example 1 except that the opaque vinyl chloride film was used. Then, a transparent resin layer having an uneven pattern was formed on the above intermediate sheet by using an ionizing radiation curable resin in the same manner as in Example 1 to obtain a decorative sheet of the present invention.

[0044]

As described in detail above, according to the decorative sheet of the present invention, it is possible to express excellent depth, depth, shine and surface stereoscopic effect. In particular, since it is possible to express both the shiny feeling of wood grain and the expression of a three-dimensional conduit pattern on the surface, it is possible to express an extremely realistic texture of natural wood. Further, according to the method for producing a decorative sheet of the present invention, the concavo-convex pattern used for expressing the conduit groove and the like is used as the conduit pattern without reducing the sharpness of the internal groove-like concavo-convex pattern used for expressing the feeling of shinyness. It can be formed on the surface of the sheet in synchronization.

[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 vertical sectional view showing another embodiment of the decorative sheet of the present invention.

FIG. 3 is a longitudinal sectional view showing another embodiment of the decorative sheet of the present invention.

FIG. 4 is an enlarged cross-sectional view of a groove-shaped concavo-convex pattern used in the decorative sheet of the present invention.

FIG. 5 is a plan view showing various examples of groove-shaped uneven patterns used for the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Opaque thermoplastic resin film 3 Glittering layer 4 Picture layer 5 Groove-like concavo-convex pattern 6 Transparent thermoplastic resin film 7 UV curing suppression picture layer 8 Transparent resin layer 9 Concavo-convex pattern 10 Parallel curve group 11 Parallel straight line group 12 Non-parallel curve group 13 Measurement curve group

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location B32B 31/00 9349-4F

Claims (4)

[Claims] 1. An opaque thermoplastic resin film, on which at least a glitter layer and a picture layer are laminated in this order, and a transparent thermoplastic resin film is further laminated thereon, and a deep interface is formed at the upper interface of the glitter layer. Of 3 to 30 μm and the interval between the protrusions is 1 to 1000 μm, and a groove-like concavo-convex pattern composed of a line-group-like pattern is formed on the transparent thermoplastic resin film. An ultraviolet ray and an electron beam are provided on which a suppression pattern layer is laminated, and which has an uneven pattern in which concave portions are formed in synchronization with the ultraviolet curing suppression pattern layer portion and which covers the entire surface of the transparent thermoplastic resin film. A decorative sheet comprising a transparent resin layer formed by laminating an ionizing radiation curable resin cured in step 1. 2. The decorative sheet according to claim 1, wherein the pattern of the pattern layer and the pattern of the ultraviolet curing suppression pattern are aligned with each other. 3. A method for producing a decorative sheet, comprising the following steps (A) to (E): (A) A glitter layer on one side of an opaque thermoplastic resin film,
Step of forming a pattern layer. (B) a transparent thermoplastic resin film is laminated by doubling embossing on the layer forming surface side of the opaque thermoplastic resin film on which each of the above layers is formed, and at the same time, the transparent thermoplastic resin film side or the opaque thermoplastic resin Due to the embossing from the film side, the depth at the interface on the upper layer side of the glitter layer is 3 to 30 μm, and the interval between the convex portions is 1 to 10.
A step of forming a groove-shaped concavo-convex pattern having a line-group-shaped pattern of 00 μm. (C) A step of forming an ultraviolet curing suppression pattern layer on the surface of the transparent thermoplastic resin film. (D) The entire surface of the transparent thermoplastic resin film on which the ultraviolet curing suppression pattern layer is formed is coated with an ionizing radiation curable resin liquid that is cured by ultraviolet rays, and then cured by irradiation with ultraviolet rays, and the ultraviolet curing A step of forming a concavo-convex pattern in which the suppression pattern layer portion becomes a recess. (E) A step of irradiating the ionizing radiation curable resin with an electron beam to completely cure the resin, thereby forming a transparent resin layer having a concavo-convex pattern in synchronization with the ultraviolet curing suppression pattern layer. 4. A method of manufacturing a decorative sheet, comprising the following steps (A) to (D): (A) A step of forming a pattern layer and a glitter layer on the back surface of a transparent thermoplastic resin film, and an ultraviolet curing suppression pattern layer on the surface thereof. (B) The transparent thermoplastic resin film on which each of the layers is formed on the back side is laminated by doubling embossing on the opaque thermoplastic resin film, and at the same time, the transparent thermoplastic resin film side or the opaque thermoplastic resin film side. By the embossing, the depth at the interface on the upper layer side of the glitter layer is 3 to 30 μm and the interval between the convex portions is 1 to 1000.
A step of forming a groove-shaped concavo-convex pattern composed of a line group-shaped pattern of μm. (C) The entire surface of the transparent thermoplastic resin film on which the UV-curing suppression pattern layer is formed is coated with an ionizing radiation-curable resin liquid that cures with UV light, and then cured by irradiation with UV light, and the UV cure A step of forming a concavo-convex pattern in which the suppression pattern layer portion becomes a recess. (D) A step of irradiating the ionizing radiation-curable resin with an electron beam to completely cure the resin, thereby forming a transparent resin layer having a concavo-convex pattern in synchronism with the ultraviolet curing suppression pattern layer.