JP2005125780A - Decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative material having a pattern formed on its surface, having a gloss difference which is visually recognized as a recessed part, corresponding to the pattern and having an uneven feeling on its surface. <P>SOLUTION: The decorative material has the low gloss pattern ink layer at least partially provided on a base material and the surface protective layer which is present on the low gloss pattern ink layer in a contact state to cover the whole surface containing a region where the low gloss pattern ink layer is formed and a region where the low gloss pattern ink layer is not formed of the base material. The surface protective layer is formed by crosslinking and curing an ionizing radiation curable resin composition and the low gloss pattern ink for constituting the low gloss pattern ink layer contains a non-crosslinked urethane resin as a binder and the ionizing radiation curable resin composition contains a (meth)acrylate monomer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cosmetic material in which a pattern is formed on a surface, has a gloss difference according to the pattern, has a visual unevenness, and has excellent durability on the surface including the pattern.

As a decorative sheet for furniture and kitchen cabinets, for example, a wood sheet, an inorganic material, a synthetic resin material, a metal sheet such as a steel plate, and a decorative sheet printed with a wood grain pattern, for example, is used as an adhesive. The thing of the structure bonded together by is used.
The decorative sheet used for such a surface decorative plate has appropriate flexibility for secondary processing such as laminating, lapping, and V-cut processing, suitability for processing such as machinability and rupture resistance, and usage conditions. Various properties such as weather resistance, light resistance, heat resistance, water resistance, solvent resistance, surface hardness, abrasion resistance, and scratch resistance are required.
In order to satisfy these requirements, a base material that sufficiently satisfies the processability is used, and a surface protective layer is applied to the surface of the base material, and the surface protective layer is an ionizing radiation curable resin composition. Is preferably used.

By the way, due to the recent trend toward high-end products by consumers, there is a demand for a high-class feeling for floor tiles, wall panels, furniture, and cabinets for kitchen products. Those having a high-quality appearance are desired. For this reason, in addition to various types of printing on the surface of each base sheet and the provision of a film having a pattern layer, it is also important to add texture, and gloss is applied to specific parts of the pattern. Various methods have been proposed for applying eraser and unevenness.
For example, after forming an area in which the wettability with respect to the electron beam curable paint or the photocurable paint is different from the substrate surface by the coating surface provided in a pattern on the substrate, the electron beam curable type is formed on the substrate. There has been proposed a method in which a paint or a photocurable paint is applied, the surface of the paint is depressed in an area that is easily wetted with respect to the paint, and the surface of the paint is raised in an area that is difficult to wet (for example, Patent Document 1 and Claims). Range). However, this method has a problem that unevenness does not appear cleanly when the concave portion, that is, an easily wettable area is thin. In addition, when there is a concave portion with a certain thickness, an uneven pattern can be obtained on the surface of the substrate, but at the boundary region between the depressed portion and the raised portion, the edge that transitions from the convex portion to the concave portion due to the surface tension of the paint, etc. The part is rounded and lacks the sharpness of the unevenness, and a convex part that is higher than the height of the raised part occurs. For example, in the case of a wood grain pattern, there is no real feeling, and the appearance and touch feeling are not good There's a problem.

Also, a solventless paint in which a film on which a multicolor pattern is printed with an ink containing a curing retarder that delays the resin curing of the solventless paint and an ink that does not contain the resin is applied on the substrate in advance. A method has been proposed in which a resin film is coated and cured in a curing atmosphere, and then the film is peeled off and transferred (see Patent Document 2 and claims). According to this method, it is possible to dent and transfer only a color pattern portion printed with ink containing a curing retarder. However, this method has a problem that special ink is required and the curing reaction of the resin coating film of the solventless paint is unstable.
Furthermore, on the base material, two kinds of pattern layers of a pattern layer made of a normal ink and a convex pattern layer made of an electron beam curable composition are sequentially provided, and a transparent resin layer is coated thereon, and after coating, A cosmetic material in which a convex pattern is cured by irradiating an electron beam through the transparent resin layer has been proposed (see Patent Document 3 and Claims). However, since such a decorative material has relatively large unevenness physically, the convex portion is easily damaged, and particularly when the area of the convex portion is large, it becomes a problem and becomes a problem. In addition, this method is used when, for example, it is desired to give glossiness such as wood grain tone, i.e., when there is a concave portion with a very large width and a very narrow width, such as a wood grain conduit groove. There is a problem that the concave portion is buried by the flow of the constituent paint, and the degree of filling varies, which is inappropriate. Furthermore, there is a problem that the touch feeling is not good due to physical unevenness.

In addition, solid paper is printed with UV curable printing ink containing matting agent on thin paper, and this is irradiated with actinic rays, and then a wood grain pattern is printed on it with high gloss UV curable printing ink. A decorative paper having a wood grain pattern irradiated with actinic rays has been proposed (see Patent Document 4 and claims). According to this decorative paper, the portion using the high glossy ink appears to be a convex portion, and the portion of the ink containing the matting agent appears to be a concave portion, thereby obtaining a wood texture. However, the decorative paper proposed here does not have an overcoat transparent coating as a protective coating, so the so-called conduit ink portion for printing wood grain patterns has weather resistance, water resistance, and abrasion resistance. Further, the scratch resistance and the like are inevitably lowered, and the durability is inferior.
Furthermore, a pattern is formed with an ionizing radiation shielding material on either the front or back surface of the ionizing radiation transmitting release substrate having a peelable surface, and the release substrate and an uncured layer of ionizing radiation curable resin on the surface After irradiating with ionizing radiation from the peeling substrate side and curing only the ionizing radiation curable resin corresponding to the portion without the pattern formed with the ionizing radiation shielding material A method has been proposed in which the resin in the uncured portion of the ionizing radiation curable resin layer is removed together with the release substrate to form a concavo-convex pattern (see Patent Document 5 and Claim 8). According to the present invention, the patterned portion formed of the ionizing radiation shielding material adheres to the peeling substrate without curing the ionizing radiation curable resin, and is removed together with the peeling substrate, Since the ionizing radiation curable resin is cured and remains in the portion without the pattern formed of the ionizing radiation shielding material, an uneven pattern synchronized with the pattern is formed. However, this method has a disadvantage in that it requires a material such as a release material or an ionizing radiation shielding material, and the method of attaching and removing uncured resin to the release substrate forms a deep and clear recess. There is a disadvantage that it can not. Furthermore, when an electron beam curable resin is used as the ionizing radiation curable resin, there is a drawback that it is difficult to select a material that shields the electron beam.

In addition, after applying a synthetic resin that performs radiation polymerization to a substrate with printed or decorative paper, the irradiation is stopped when the synthetic resin is in a semi-cured state by applying radiation, and a cold press such as a roll press with an uneven pattern is applied. There has been proposed a method of manufacturing a decorative board having a concavo-convex pattern in which a synthetic resin is completely cured after being pressurized with a pressure body (see, for example, Patent Document 6 and Claims). However, it is not easy to specify the conditions for stably making the resin into a semi-cured state of a certain degree, and the semi-cured synthetic resin is unstable, and curing is performed in two stages. There is a problem that it is complicated.
Therefore, the electron beam curable resin is applied onto the base material using a coating device, and is continuously cured by irradiating with an electron beam while forming the unevenness of the mold roll by bringing it into contact with the mold roll in an electron beam irradiation machine. In general, a method for forming irregularities has been proposed (see, for example, Patent Document 7, Claims, and FIG. 1). However, this method requires a special mold roll device, and there is a disadvantage that irregularities cannot be formed by a normal printing apparatus, and the speed of forming by the mold roll is limited, and productivity is increased. Has the disadvantage of being low.

  Furthermore, the surface of the substrate has a coating layer, a pattern layer, and a surface protective layer obtained by crosslinking and curing the ionizing radiation curable resin composition. The pattern layer is ionizing radiation curable compared to the coating layer. A cosmetic material having a high permeability of the resin composition has been proposed (see, for example, Patent Document 8, Claims, and FIGS. 1 and 2). According to this decorative material, since the ionizing radiation curable resin composition easily penetrates into a portion where a pattern exists, a concave portion is formed in the portion, and a decorative material having an uneven surface is obtained. However, this cosmetic material needs to add a large amount of extender pigments and porous materials in order to give sufficient absorption permeability to the pattern layer. In this case, the pattern layer becomes porous and brittle. The durability and contamination resistance of the recesses are reduced. On the other hand, if it is attempted to suppress the formation of a porous pattern layer in order to improve the durability and stain resistance of the recess, there is a problem in that a recess having a sufficient depth and sharpness cannot be formed. Moreover, since this decorative material is physically uneven, there is room for further improvement in that the touch feeling is not good.

Japanese Patent Publication No. 51-26937 Japanese Patent Publication No.51-33454 Japanese Examined Patent Publication No. 1-41505 JP-A-51-84910 JP-A-1-253449 Japanese Patent Publication No.49-28264 Japanese Examined Patent Publication No. 63-50066 JP 2001-199028 A

  Under such circumstances, the present invention is a cosmetic material having a texture on the surface, in which a pattern is formed on the surface, has a gloss difference corresponding to the pattern, and the gloss difference is visually recognized as a concave portion. It is another object of the present invention to provide a decorative material having high solvent resistance, wear resistance, or interlayer strength.

  As a result of intensive studies to achieve the above object, the present inventor has found that the low gloss pattern ink layer provided at least partially on the substrate and the low gloss pattern ink layer are present on the low gloss pattern ink layer. A cosmetic material having a surface protective layer covering the entire surface including the region where the low gloss pattern ink layer is formed and the region where the low gloss pattern ink layer is not formed, the surface protective layer Is obtained by crosslinking and curing the ionizing radiation curable resin composition, the low gloss pattern ink constituting the low gloss pattern ink layer contains a non-crosslinked urethane resin as a binder, and the ionizing radiation curable resin composition is (meth) It has been found that a cosmetic material containing an acrylate monomer can solve the above problems. The present invention has been completed based on such findings.

That is, the present invention
(1) A low gloss pattern ink layer provided at least partially on a substrate, and a region present on and in contact with the low gloss pattern ink layer, and in which the low gloss pattern ink layer is formed And a decorative material having a surface protective layer covering the entire surface including the region where the low gloss pattern ink layer is not formed, wherein the surface protective layer is obtained by crosslinking and curing the ionizing radiation curable resin composition. A makeup characterized in that the low gloss pattern ink constituting the low gloss pattern ink layer contains a non-crosslinked urethane resin as a binder, and the ionizing radiation curable resin composition contains a (meth) acrylate monomer Material,
(2) The cosmetic material according to the above (1), wherein the low gloss pattern ink constituting the low gloss pattern ink layer contains a non-crosslinked urethane resin and an unsaturated polyester resin as a binder,
(3) The cosmetic material according to (1) or (2), wherein the ionizing radiation curable resin composition comprises a (meth) acrylate monomer,
(4) The cosmetic material according to any one of (1) to (3), wherein the ionizing radiation curable resin composition is an electron beam curable resin composition,
(5) The above (1) to (1), wherein a low gloss region visually recognized as a concave portion is formed immediately above and in the vicinity of a partially provided low gloss pattern ink layer in the surface protective layer. (4) the cosmetic material according to any one of
(6) The cosmetic material according to (5), wherein the surface of the surface protective layer located above the low gloss region has a convex shape,
(7) The cosmetic material according to any one of (1) to (6), further including a penetration preventing layer between the base material and the low gloss pattern ink layer,
(8) The cosmetic material according to (7), wherein the base material is a permeable base material,
(9) A colored layer, a pattern layer, and a permeation preventive layer are laminated on a substrate, and the low gloss pattern ink is present on and in contact with the low gloss pattern ink layer and the low gloss pattern ink layer. The cosmetic material according to any one of the above (1) to (8), which has a surface protective layer covering the entire surface including a region where the layer is formed and a region where the low gloss pattern ink layer is not formed,
(10) The decorative layer according to (9) above, wherein the pattern layer forms a wood grain pattern, and the low gloss pattern ink forms a conduit part, and (11) the above (1) to (10) A decorative board in which the decorative material according to any one is attached to a substrate,
Is to provide.

  According to the present invention, a decorative material having a concavo-convex feeling on the surface, in which a pattern is formed on the surface, has a gloss difference corresponding to the pattern, and the gloss difference is visually recognized as a concave portion, A decorative material having high solvent resistance, abrasion resistance, or interlayer strength can be obtained.

The decorative material of the present invention comprises a low-gloss pattern ink layer that is at least partially provided on a substrate, and the low-gloss pattern ink layer that is present on and in contact with the low-gloss pattern ink layer. And a surface protective layer covering the entire surface including the region where the low gloss pattern ink layer is not formed, and the surface protective layer is obtained by crosslinking and curing the ionizing radiation curable resin composition. The low gloss pattern ink constituting the low gloss pattern ink layer includes a non-crosslinked urethane resin as a binder, and the ionizing radiation curable resin composition includes a (meth) acrylate monomer. It is characterized by that.
A typical structure of the decorative material of the present invention will be described with reference to FIGS. FIG.1 and FIG.2 is a schematic diagram which shows the cross section of the decorative material 1 of this invention. In the example shown in FIG. 1, a low gloss pattern ink layer 3 is laminated on a substrate 2, and a surface protective layer 5 obtained by crosslinking and curing an ionizing radiation curable resin composition is laminated thereon. Next, in the example shown in FIG. 2, the uniform and uniform colored layer 6, the pattern layer 7, the uniform and uniform penetration preventing layer 8, the low gloss pattern ink layer 3, and the ionizing radiation curing that covers the entire surface of the substrate 2. The surface protective layer 5 obtained by crosslinking and curing the conductive resin composition is laminated in this order.

Hereinafter, the present invention will be described in detail with reference to FIG. 2 showing one preferred embodiment of the present invention.
The base material 2 used in the present invention is not particularly limited as long as it is usually used as a cosmetic material, such as various papers, plastic films, plastic sheets, metal foils, metal sheets, metal plates, and wood. A wooden board, a ceramic material, etc. can be suitably selected according to a use. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper or a composite of paper and a plastic film.
When using these substrates, particularly plastic films or plastic sheets, as a substrate, an oxidation method or a concavo-convex method may be applied to one or both sides as desired in order to improve the adhesion to the layer provided thereon. Physical or chemical surface treatment can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
Further, the substrate may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

As various papers used as the substrate, thin paper, kraft paper, titanium paper and the like can be used. These paper base materials are used to reinforce the interlaminar strength between the fibers of the paper base material or between the other layers and the paper base material, and to prevent the occurrence of scuffing, in addition to these paper base materials, acrylic resin, styrene butadiene rubber, A resin such as a melamine resin or a urethane resin may be added (resin impregnation after paper making or embedded during paper making). For example, inter-paper reinforced paper, resin-impregnated paper and the like.
In addition to these, various papers often used in the field of building materials such as linter paper, paperboard, base paper for gypsum board, or a vinyl wallpaper raw material in which a vinyl chloride resin layer is provided on the surface of the paper can be mentioned. Furthermore, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, or the like used in the office field or normal printing and packaging can also be used. Moreover, although distinguished from these papers, woven fabrics and non-woven fabrics of various fibers having an appearance and properties similar to paper can be used as the base material. Examples of various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers, or synthetic resin fibers such as polyester fibers, acrylic fibers, and vinylon fibers.

  As a plastic film or a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 And polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, and the like.

  As metal foil, a metal sheet, or a metal plate, what consists of aluminum, iron, stainless steel, or copper, for example can be used, and what gave these metals by plating etc. can also be used. Examples of the various wood-based boards include wood fiberboards such as wood veneer, plywood, laminated wood, particle board, or MDF (medium density fiberboard). Examples of the ceramic material include ceramic building materials such as gypsum board, calcium silicate board, and wood cement board, ceramics, glass, firewood, and fired tile. In addition to these, composites of various materials, such as fiber reinforced plastic (FRP) plates, paper honeycombs with iron plates pasted on both sides, and two aluminum plates sandwiched with polyethylene resin can also be used as the base material. .

Although there is no restriction | limiting in particular about the thickness of the base material 2, When using the sheet | seat which uses a plastic as a raw material, thickness is about 20-150 micrometers normally, Preferably it is the range of 30-100 micrometers, and a paper base material is used. When used, the basis weight is usually about ²⁰ to 150 g / m ² , preferably 30 to 100 g / m ² .

The uniform and uniform colored layer 6 covered over the entire surface shown in FIG. 2 is also referred to as a concealing layer or a full surface solid layer provided as desired for the purpose of improving the design of the decorative material of the present invention. . The colored layer 6 is formed when the color of the surface of the base material 2 is adjusted so that the base material 2 itself is colored or uneven in color, and gives the intended color to the surface of the base material 2. is there. Usually, it is formed with an opaque color, but it may be formed with a colored transparent color to make use of the pattern of the base. When making use of the fact that the base material 2 is white, or when the base material 2 itself is appropriately colored, it is not necessary to form the colored layer 6.
As the ink used for forming the colored layer, an ink in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, and polyesters. Arbitrary resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins and the like may be used alone or in combination of two or more.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
The colored layer 6 is preferably a so-called solid print layer having a thickness of about 1 to 20 μm.

The pattern layer 7 shown in FIG. 2 gives decorativeness to the base material 2 and is formed by printing various patterns using ink and a printing machine. As patterns, there are stone patterns imitating the surface of rocks, such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth or cloth-like patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done.
As the pattern ink used for the pattern layer 7, the same ink as that used for the colored layer 6 can be used. In the cosmetic material of the present invention, since the makeup can be applied by the low gloss pattern ink layer 3 described in detail later, the pattern layer 7 is not an essential component.

  The penetration preventing layer 8 shown in FIG. 2 is a layer provided as desired, and the ionizing radiation curable resin constituting the low gloss pattern ink and the surface protective layer 5 constituting the low gloss pattern ink layer 3 described later, It has a function of suppressing permeation into the base material 2 and is particularly effective when the base material 2 is a permeable base material such as paper or nonwoven fabric. Therefore, the penetration preventing layer 8 may be positioned between the base material 2 and the low gloss pattern ink layer 3, for example, between the base material 2 and the colored layer 6, between the colored layer 6 and the picture layer 7, or in FIG. As shown, it is provided between the pattern layer 7 and the low gloss pattern ink layer 3. Usually, a uniform and uniform layer in which the curable resin is cross-linked and cured has an adhesiveness with the ionizing radiation curable resin constituting the surface protective layer 5, and the pattern layer 7 and the low gloss pattern ink layer as shown in FIG. 3 is provided. As a result, when there is a colored layer 6, a pattern layer 7, etc. on the substrate 2, the function of smoothing these surfaces and improving the adhesion between them and the low gloss pattern ink layer 3 and the surface protective layer 5 Is also fulfilled.

The low gloss pattern ink layer 3 in the decorative material of the present invention is directly laminated on the base material 2 as shown in FIG. 1, or as shown in FIG. It is laminated on the layer 7, the permeation preventive layer 8 and the like, and is a layer that causes a difference in pattern gloss.
In the present invention, the low gloss pattern ink constituting the low gloss pattern ink layer includes a non-crosslinked urethane resin as a binder. When the low gloss pattern ink contains a non-crosslinked urethane resin as a binder, an interaction with the ionizing radiation curable resin composition forming the surface protective layer 5 described in detail later occurs, thereby forming a pattern gloss difference. is there. Here, in order to adjust the degree of interaction with the surface protective layer, other resin can be mixed in the binder of the low gloss pattern ink. As other resin used here, a polyester resin is preferable, and an unsaturated polyester resin is particularly preferable. In addition, the content of the urethane resin is 50% by mass or more from the viewpoint of strengthening the interaction with the ionizing radiation curable resin composition forming the surface protective layer 5 and obtaining further pattern gloss difference. Is more preferable.
The urethane resin used in the present invention is a non-crosslinked type, that is, a three-dimensionally crosslinked thermoplastic resin having a linear molecular structure rather than a networked three-dimensional molecular structure. It is important to choose one. Examples of such non-crosslinked urethane resins include polyol components such as polyols such as acrylic polyols, polyester polyols and polyether polyols, and isocyanate components such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate and other aromatic isocyanates, and isophorone diisocyanate. And a urethane resin obtained by reacting an isocyanate such as an aliphatic or alicyclic isocyanate such as hexamethylene diisocyanate and hydrogenated tolylene diisocyanate. Usually, the number of hydroxyl groups in one molecule of polyol and the number of isocyanate groups in one molecule of isocyanate are two on average. In addition, the average molecular weight of the urethane resin is about 10,000 to 50,000, and the glass transition temperature (Tg) is preferably about -70 to -40 ° C in order to develop a low gloss region.
Also, in order to adjust the degree of expression of the low gloss area and the contrast of gloss between the low gloss area and its surroundings, an unsaturated polyester resin is used as a binder for low gloss design inks in addition to non-crosslinked urethane resins. It may be added. The addition amount of the unsaturated polyester resin is preferably in the range of 10 to 50% by mass with respect to the total amount of the binder of the low gloss design ink. Within this range, it is possible to obtain a sufficient enhancement effect for developing the low gloss region. The unsaturated polyester resin is not particularly limited as long as it is a reaction product of an unsaturated dicarboxylic acid and a glycol. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and the like. Examples include ethylene glycol, diethylene glycol, propylene glycol, and butylene glycol.

The low-gloss pattern ink forming the low-gloss pattern ink layer 3 has a colorant like the ink composition used in the colored layer 6 and the pattern layer 7, and can provide a pattern pattern by itself. In the case of having the colored layer 6 and the picture layer 7 as shown in FIG. 4, since the base 2 is already provided with a color and pattern, the low-gloss picture ink composition for forming the low-gloss picture ink layer 3 It is not always necessary to add a colorant and color. That is, when the pattern layer 7 is provided, the gloss difference is obtained by synchronizing the portion of the pattern that the pattern layer 7 intends to express with the matte portion of the pattern to be visually expressed and the low gloss pattern ink layer 3. A pattern having a visual recess is obtained. For example, when a wood grain pattern is to be expressed by the pattern layer 7, the conduit portion is visually recessed due to the gloss difference by synchronizing the ink portion of the low gloss pattern ink layer 3 with the wood grain conduit portion. A pattern is obtained. Alternatively, when a tiled pattern is to be expressed by the pattern layer 7, the joint groove portion is visually visualized due to the difference in gloss by synchronizing the ink portion of the low gloss pattern ink layer 3 with the tiled joint groove portion. The pattern which became a recessed part is obtained.
The coating amount of the low gloss pattern ink that forms the low gloss pattern ink layer is preferably in the range of 1 to 30 g / m ² . When it is 1 g / m ² or more, the above-mentioned low gloss pattern ink has sufficient interaction with the ionizing radiation curable resin composition, and a sufficient gloss difference on the surface of the decorative material can be obtained. On the other hand, when it is 30 g / m ² or less, there is no mechanical restriction when printing low gloss pattern ink, and it is economically advantageous. From the above viewpoint, the coating amount of the low gloss pattern ink is preferably in the range of 5 to 10 g / m ² .

Moreover, it is preferable that an extender pigment is contained in the low gloss pattern ink composition for forming the low gloss pattern ink layer 3. By containing extender pigments, it is possible to impart thixotropy to the low gloss pattern ink composition, and the shape of the low gloss pattern ink composition is maintained when the low gloss pattern ink layer 3 is printed using a plate. Is done. As a result, the sharpness of the unevenness at the end portion that transitions from the convex portion to the concave portion can be emphasized, and a sharp design expression is possible.
The extender pigment used in the present invention is not particularly limited, and is suitably selected from, for example, silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. Of these, silica, which is a material having a high degree of freedom in material design such as oil absorption, particle size, pore volume, etc., and excellent in designability, whiteness, and coating stability as an ink, is preferred. Is preferred. As a particle size of a silica, the range of 0.1-5 micrometers is preferable. When it is 0.1 μm or more, the thixotropy of the ink does not become extremely high when it is added to the ink, and the viscosity of the ink does not increase too much, so that printing can be controlled easily. Also, when trying to express the matte of the conduit pattern portion, the ink coating thickness of the conduit pattern portion is usually 5 μm or less, and if the silica particle size is smaller than the coating thickness, the head of the particle is relatively suppressed. Because it is inconspicuous, visual discomfort is unlikely to occur.
The content of these extender pigments in the low gloss pattern ink composition is preferably in the range of 5 to 15% by mass. When the content is 5% by mass or more, sufficient thixotropy can be imparted to the low gloss pattern ink composition, and when it is 15% by mass or less, the effect of imparting low gloss is not observed at all.

Next, the surface protective layer 5 is composed of a material obtained by crosslinking and curing the ionizing radiation curable resin composition as described above. Here, the ionizing radiation curable resin composition is one having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, crosslinking or curing by irradiating ultraviolet rays or electron beams. Refers to a resin composition.
In the present invention, the ionizing radiation curable resin composition includes a (meth) acrylate monomer. By including the (meth) acrylate monomer, an interaction with the above-described low gloss pattern ink occurs, and a pattern gloss difference is formed. The content of the (meth) acrylate monomer is more preferably 50% by mass or more from the viewpoint of further strengthening the interaction with the low gloss pattern ink and obtaining a further difference in gloss of the pattern. It is preferable that the ionizing radiation curable resin composition consists only of (meth) acrylate monomers. Here, “(meth) acrylate” means “acrylate or methacrylate”.

  The (meth) acrylate monomer used in the present invention is preferably a polyfunctional (meth) acrylate. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  The ionizing radiation curable resin composition may be mixed with a polymerizable oligomer together with the (meth) acrylate monomer within a range that does not impair the effects of the present invention. Examples of the polymerizable oligomer include epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.
In the present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator and can provide stable curing characteristics.

Moreover, various additives can be mix | blended with the ionizing radiation-curable resin composition in this invention according to the desired physical property of the cured resin layer obtained. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.
Here, as the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. The ultraviolet absorber may be either inorganic or organic, and as the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-) is specifically mentioned. Amylphenyl) benzotriazole, 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol, and the like. On the other hand, examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2). , 6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate and the like. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

Examples of the wear resistance improver include, for inorganic substances, spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like, and are not particularly limited, but a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 30 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.
Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
Examples of the colorant include known coloring pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.

In the present invention, a polymerizable monomer, a polymerizable oligomer and various additives, which are the ionizing radiation curable components, are uniformly mixed at predetermined ratios to prepare a coating liquid composed of an ionizing radiation curable resin composition. To do. The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.
In the present invention, the coating liquid prepared in this way is applied to the surface of the substrate so that the thickness after curing is 1 to 20 μm, gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, preferably gravure coating, to form an uncured resin layer. When the thickness after curing is 1 μm or more, a cured resin layer having a desired function is obtained. The thickness of the surface protective layer after curing is preferably about 2 to 20 μm.

In the present invention, the uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.
When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
The cured resin layer thus formed has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, and anti-fouling coat having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can be imparted.

Next, the effect of the decorative material having the configuration of the present invention will be described below with reference to FIGS. 3 and 4. 3 and 4 are schematic views showing a cross section of the decorative material 1. In the example shown in FIG. 3, a uniform and uniform colored layer 6, a pattern layer 7, a uniform and uniform penetration preventing layer 8, a low gloss pattern ink layer 3, and an ionizing radiation curable resin composition covering the entire surface of the substrate 2. A surface protective layer 5 obtained by crosslinking and curing the product is laminated in this order. In the present invention, the low gloss pattern ink in the low gloss pattern ink layer 3 contains a non-crosslinked urethane resin as a binder, and the ionizing radiation curable resin composition constituting the surface protective layer 5 is a single (meth) acrylate. It is characterized by containing a mer, and a pattern gloss difference is formed by these interactions.
The mechanism of gloss difference generation in the present invention has not been fully elucidated, but ionization for forming the surface protective layer 5 on the surface of the low gloss pattern ink layer 3 based on the results of various experiments, observations and measurements. When an uncured product of radiation curable resin is applied, the resin component of the low gloss pattern ink layer 3 and the surface protective layer are partly eluted, dispersed, or the like, depending on the combination of materials and the appropriate selection of application conditions. This is presumably due to the interaction such as mixing. At this time, each resin component in the ink of the low gloss pattern ink layer 3 and the uncured product of the ionizing radiation curable resin becomes a suspended state instead of being completely compatible in a short time. It is considered that the portion in the immediate upper part of the ink layer 3 and in the vicinity thereof and in a suspended state scatters light to form a low gloss region. When this state is fixed by crosslinking and curing the surface protective layer while maintaining this suspended state, the low gloss region 4 is partially formed in the surface protective layer. It is assumed that is recognized as a concave. The low gloss region 4 is represented by a set of points in FIGS.
Further, depending on the types of the low gloss pattern ink and the ionizing radiation curable resin composition, the upper part of the low gloss region 4 on the outermost surface of the surface protective layer 5 is raised with the formation of the low gloss pattern ink layer 3. A convex shape 9 may be formed. Since the surface of the surface protective layer 5 has such a convex shape, light is scattered even in this portion, the surface area is increased, and the viewing angle for recognizing low gloss is widened. In addition, the visual unevenness is further enhanced in cooperation with the effect of the above, which is further preferable. In addition, about the height of this convex shape 9, it is preferable that it is the height which is the range which has the effect of this invention, and it is the range of 2-3 micrometers normally.
The extent of spreading of the low gloss region 4 formed in the surface protective layer 5 is not particularly limited as long as it is within the range where the effects of the present invention can be achieved. As shown in FIG. May remain in the middle of the thickness direction of the surface protective layer 5, or may reach the outermost surface of the surface protective layer 5 as shown in FIG. Furthermore, a convex shape may be formed on the outermost surface of the surface protective layer 5 as shown in FIG.

The decorative material of the present invention can be used as a decorative plate by sticking to various substrates. Specifically, as shown in FIG. 5, the decorative material 1 is attached to the substrate 11 via the adhesive layer 10.
The board | substrate used as a to-be-adhered body is not specifically limited, A plastic board, a metal board, woody board | plates, such as a timber, a ceramic material, etc. can be selected suitably according to a use. When these substrates, particularly plastic sheets, are used as substrates, physical or chemical surface treatment such as oxidation or unevenness is applied to one or both sides as desired in order to improve adhesion to the decorative material. Can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  As a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 And polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, and the like.

As a metal plate, what consists of aluminum, iron, stainless steel, or copper, for example can be used, and what gave these metals by plating etc. can also be used.
Examples of wood-based boards include veneer of various materials such as cedar, firewood, firewood, pine, lawan, teak and melapie, and wood materials such as wood veneer, wood plywood, particle board, and medium density fiber board (MDF). . These can be used alone or in a laminated manner. The wooden board includes not only a wooden board but also a plastic board containing paper powder and reinforced paper having strength.
Examples of the ceramic material include ceramic building materials such as a gypsum plate, a calcium silicate plate, and a wood piece cement plate, ceramics, glass, firewood, fired tiles, plates made mainly of volcanic ash, and the like.
In addition to these, composites of various materials, such as fiber reinforced plastic (FRP) plates, paper honeycombs with iron plates pasted on both sides, and two aluminum plates sandwiched with polyethylene resin can also be used as the base material. .

  Further, the substrate may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance. As a substrate to be an adherend, plate materials such as flat plates and curved plates of various materials, or three-dimensional shaped articles (molded products) in which the above materials are used alone or in combination are targeted.

  A backing material such as Japanese paper, Western paper, synthetic paper, non-woven fabric, woven fabric, cold paper, impregnated paper, synthetic resin sheet, or the like may be attached to the decorative material. By sticking the backing material, it acts to reinforce the cosmetic material itself, prevent cracking and tearing of the cosmetic material, prevent bleeding of the adhesive to the cosmetic material surface, and prevent the occurrence of defective products, Handling becomes easy and productivity can be improved.

  Thus, a substrate on which a cosmetic material is placed every leaf or continuously via an adhesive is attached to a cold press, hot press, roll press, laminator, wrapping, edge applicator, vacuum press, etc. The decorative material is bonded to the substrate surface by pressing with an apparatus to obtain a decorative board.

The adhesive is applied using an application device such as a spray, spreader, or bar coater. As the adhesive, vinyl acetate resin-based, urea resin-based, melamine resin-based, phenol resin-based, isocyanate-based adhesives, etc., are used alone or as a mixed adhesive obtained by arbitrarily mixing them. As needed, talc, calcium carbonate, clay, titanium white and other inorganic powders, wheat flour, wood flour, plastic powder, coloring agents, insect repellents, fungicides and the like can be added and mixed in the adhesive. . In general, the adhesive is applied to the substrate surface with a solid content of 35 to 80% by mass and an application amount of 50 to 300 g / m ² .
Adhesion of the decorative material on the substrate is usually performed by forming an adhesive layer on the back surface of the decorative material of the present invention and adhering the substrate or applying the adhesive on the substrate and adhering the decorative material. Etc.

  The decorative board manufactured as described above is also optionally cut by the decorative board, and optionally decorated such as grooving and chamfering on the surface and the mouth using a cutting machine such as a router or a cutter. Can be applied. And various uses, for example, interior or exterior materials of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, surrounding edges, surface decorative panels for fittings such as malls, kitchens, furniture or light electrical appliances, It can be used for surface decorative boards of cabinets such as OA equipment, interiors and exteriors of vehicles.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation methods)
The cosmetic materials obtained in each example were evaluated by the following methods.
(1) Evaluation of Gloss Using a gloss meter (“MMX-203” manufactured by Murakami Color Research Laboratory), the gloss values in the high gloss region and the low gloss region were measured under the condition of an incident angle of 75 degrees. The higher the number, the higher the gloss (high gloss), and the lower the number, the lower the gloss (low gloss).
(2) Water resistance A water-filled cup is fixed upside down on the surface of the decorative material, left for 24 hours and then removed. Then, it was left to stand at room temperature for 24 hours, and it was visually observed whether changes such as swelling occurred on the surface. Judgment criteria were evaluated as follows.
◎ There is no change △ There is a change, but it is minor and there is no problem in practical use. × The change such as swelling is clear. (3) Peeling over time Cellophane tape (cellophane adhesive tape made by Nichiban Co., Ltd.) on the cosmetic material surface , “Cerotape (trademark)” 2.5 mm width) was adhered, left at room temperature (25 ° C.) and 50 ° C. for 24 hours, and then forcibly peeled off. The peeled surface of the decorative material was visually observed and evaluated according to the following criteria.
◎ There is no peeling of the pattern at any temperature. △ There is peeling of the pattern, but it is minor and has no problem in practical use. × The peeling of the pattern is remarkable. (4) Contamination resistance Contamination according to JIS K-6902 The object was applied to the surface of the decorative material, and the remaining state of the contaminants after wiping was visually observed. Judgment criteria were evaluated as follows.
◎ No contamination remains △ There is no contamination, but there is no problem in practical use × Contamination remains remarkably (5) Merling performance Load of 29.4 kPa (300 g / cm ² ) Steel wool (# 0000) was attached to the weight adjusted as described above, and the surface of the decorative material was rubbed 50 times, and the change in gloss of the surface was visually observed. Judgment criteria were evaluated as follows.
◎ There is no change △ There is a change, but it is minor and there is no problem in practical use × Significant change

Example 1
As the base material 2, a reinforced paper between building materials with a weight of 30 g / m ² of rice is used, and an acrylic resin and nitrified cotton are used as a binder on one side thereof, and an ink containing titanium white, petal, and yellow lead as a colorant, A (full surface solid) layer having a coating amount of 5 g / m ² was applied by gravure printing to form a colored layer 6. A woodgrain pattern layer 7 was formed by gravure printing using an ink containing nitrified cotton as a binder and a colorant mainly composed of a petiole.
Subsequently, using a coating composition having a polyisocyanate composed of a polyester urethane resin having a number average molecular weight of 20,000 and a glass transition temperature (Tg) of −59.8 ° C. and tolylene diisocyanate as a binder, the coating amount is 7 g / m. ² and gravure printing was performed on the entire surface to form a permeation preventive layer 8 (primer layer).
Next, 10 silica particles having an average particle diameter of 1.5 μm are added to 100 parts by mass of a transparent ink using a polyester urethane resin having a number average molecular weight of 30,000 and a glass transition temperature (Tg) of 62.8 ° C. as a binder. A low-gloss pattern ink layer 3 was formed by gravure printing so as to synchronize the position of the wood-patterned conduit portion using the ink composition blended in mass parts.
On these ink layers, 60 parts by mass of ethylene oxide-modified trimethylolpropane ethylene oxide triacrylate as a trifunctional acrylate monomer, 40 parts by mass of dipentaerythritol hexaacrylate as a hexafunctional acrylate monomer, and silica particles having an average particle diameter of 5 μm An electron beam curable resin composition comprising 8 parts by mass and 1 part by mass of a silicone acrylate prepolymer was applied at a coating amount of 5 g / m ² by a gravure offset coater method. After coating, an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) was then applied to cure the electron beam curable resin composition, whereby the surface protective layer 5 was obtained. Next, curing was performed at 70 ° C. for 24 hours to obtain a cosmetic material.
The decorative material was evaluated for gloss, water resistance, peelability with time, stain resistance and marling performance. The results are shown in Table 1.

Example 2
The same procedure as in Example 1 was performed except that the ink binder for forming the low gloss pattern ink layer was a mixture of 80% by mass of the polyester urethane resin described in Example 1 and 20% by mass of the unsaturated polyester resin. A cosmetic material was obtained.
The decorative material was evaluated for gloss, water resistance, peelability with time, stain resistance and marling performance. The results are shown in Table 1.

Example 3
The back side of the decorative material produced in Example 1 and the lauan plywood 10 having a thickness of 2.5 mm as a substrate are made of wood with an ethylene / vinyl acetate adhesive “BA-820” which is an aqueous emulsion manufactured by Chuo Rika Co., Ltd. A woody decorative board was produced by adhering to a plywood through an adhesive layer formed by coating at a coating amount of 60 g / m ² (wet).

The cosmetic material obtained in Example 1 and Example 2 was observed by magnifying the cross section with a microscope. As a result, it was found that the upper surface of the low gloss pattern ink layer in the surface protective layer and the vicinity thereof scattered light. It was observed that the other surface layers did not scatter light and were in a highly transparent state. And when this cosmetic material was visually observed from the surface protective layer side, the low gloss pattern ink layer part was recognized as a recessed part.
In addition, the appearance of the conduit portion in the wood grain pattern of the decorative material obtained in Example 2 was such that the visual concavity of the conduit portion looked more vivid than in Example 1.

  According to the present invention, a decorative material having a concavo-convex feeling on the surface, in which a pattern is formed on the surface, has a gloss difference corresponding to the pattern, and the gloss difference is visually recognized as a concave portion, A decorative material having high solvent resistance, abrasion resistance, or interlayer strength can be obtained. In particular, when used in a wood grain pattern, the difference in gloss and unevenness of the conduit portion can be expressed realistically, and the same texture as the material using actual wood can be obtained.

It is a schematic diagram which shows the cross section of the decorative material of this invention. It is a schematic diagram which shows the cross section of the decorative material of this invention. It is a schematic diagram which shows the cross section of the decorative material of this invention. It is a schematic diagram which shows the cross section of the decorative material of this invention. It is a schematic diagram which shows the cross section of the decorative board of this invention.

Explanation of symbols

1. Cosmetic material2. Base material 3. Low gloss pattern ink layer 4. 4. Low gloss area Surface protective layer 6. 6. Colored layer Picture layer 8. 8. Penetration preventing layer Convex shape10. Adhesive layer 11. substrate

Claims (11)

  A low gloss pattern ink layer provided at least partially on the substrate, and the low gloss pattern ink layer that is present on and in contact with the low gloss pattern ink layer, and the low gloss pattern ink layer and the low gloss pattern ink layer are formed on the substrate. A decorative material having a surface protective layer covering the entire surface including a region where a glossy pattern ink layer is not formed, wherein the surface protective layer is obtained by crosslinking and curing an ionizing radiation curable resin composition. A cosmetic material characterized in that the low gloss pattern ink constituting the pattern ink layer contains a non-crosslinked urethane resin as a binder, and the ionizing radiation curable resin composition contains a (meth) acrylate monomer.   The cosmetic material according to claim 1, wherein the low gloss pattern ink constituting the low gloss pattern ink layer contains a non-crosslinked urethane resin and an unsaturated polyester resin as binders.   The cosmetic material according to claim 1 or 2, wherein the ionizing radiation curable resin composition comprises only a (meth) acrylate monomer.   The cosmetic material according to any one of claims 1 to 3, wherein the ionizing radiation curable resin composition is an electron beam curable resin composition.   The low-gloss area | region recognized visually as a recessed part is formed in the surface protective layer in the upper part of the low gloss pattern ink layer provided in part and its vicinity in any one of Claims 1-4. Cosmetic material according to.   The cosmetic material according to claim 5, wherein the surface of the surface protective layer located above the low gloss region has a convex shape.   The cosmetic material according to any one of claims 1 to 5, further comprising a penetration preventing layer between the substrate and the low gloss pattern ink layer.   The cosmetic material according to claim 7, wherein the base material is a permeable base material.   A colored layer, a pattern layer, and an anti-penetration layer are laminated on a substrate, and a low gloss pattern ink layer and a low gloss pattern ink layer are present on and contact with the low gloss pattern ink layer to form the low gloss pattern ink layer. The cosmetic material according to any one of claims 1 to 8, further comprising a surface protective layer covering the entire surface including the formed region and the region where the low gloss pattern ink layer is not formed.   The cosmetic material according to claim 9, wherein the pattern layer forms a wood grain pattern, and the low gloss pattern ink layer forms a conduit portion. The decorative board which stuck the decorative material in any one of Claims 1-10 on the board | substrate.

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