JP2013056549A - Decorative sheet and decorative board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet that has superior wiping off properties while maintaining a design feeling that has a rich texture and a decorative board using this sheet.SOLUTION: The decorative sheet has, on a base material 2, at least a partially provided a low gloss design ink layer 3; and a surface protection layer 5 that coats the whole surface containing the area where the low gloss design ink layer 3 is formed and the area where the low gloss design ink layer 3 is not formed, while existing and contacting the low gloss design ink layer 3. The low gloss design ink that forms the low gloss design ink layer 3 contains the silica microparticle whose oil absorption (based on JIS K 5101-13-1:2004) is 250 ml/100 g or more. In the decorative sheet, the surface protection layer 5 is formed by curing the ionizing radiation-curable resin composition by crosslinking, and in the surface protective layer, a concave part area that is visually recognized as a concave part is formed at an immediate upper part of the low gloss design ink layer 3 and the neighborhood.

Description

  The present invention relates to a decorative sheet and a decorative board using the decorative sheet.

For decorative panels used in furniture, kitchen product cabinets, floor tiles and wall panels, or around kitchen sinks, for example, a decorative sheet printed with a wood grain pattern, etc., is bonded to the building material substrate with an adhesive. Is commonly used. And the decorative sheet used for such a decorative plate has contamination resistance such as flexibility, machinability, breakability, etc., magic wiping property, etc. for secondary processing such as laminating. Various properties such as suitability for use such as property, scratch resistance, water resistance, chemical resistance and weather resistance are required.
In order to satisfy these requirements, a substrate that sufficiently satisfies the above processing suitability is used, and a surface protective layer is applied to the surface of the substrate, and an ionizing radiation curable resin composition is preferably used. Yes. The ionizing radiation curable resin composition is a composition that is cured by ionizing radiation such as ultraviolet rays and electron beams. When the composition is used, the surface protective layer can be coated and formed without a solvent without using an organic solvent. In addition, since the crosslink density can be increased, various advantages such as easy surface strength such as wear resistance can be obtained.

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, it has become important to impart textures such as unevenness, three-dimensionality, and depth to the decorative sheet. As a decorative sheet that expresses such a texture, various methods have been proposed in which matting or unevenness is imparted according to a specific portion of a pattern (for example, Patent Documents 1 and 2).
However, the decorative sheet disclosed in these documents improves the scratch resistance and the like by imparting a certain hardness to the surface layer by adding inorganic particles to the surface layer provided on the sheet surface side, and Although it can express the texture, there is a problem that it is not sufficient in terms of suitability for use such as contamination resistance, especially magic wiping.

JP 2006-51695 A International Publication No. 2006/035880 Pamphlet

  An object of this invention is to provide the decorative sheet which has the outstanding wiping property, and a decorative board using the same, maintaining the design feeling which has a rich texture in such a condition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a decorative sheet having a base material, a low gloss pattern ink layer and a surface protective layer has a predetermined oil absorption amount in the low gloss pattern ink layer. It has been found that the above problems can be solved by using silica fine particles and using an ionizing radiation curable resin composition for forming the surface protective layer. 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 sheet having a surface protective layer covering the entire surface including the area where the low gloss pattern ink layer is not formed, wherein the low gloss pattern ink forming the low gloss pattern ink layer is oil-absorbing (JIS K). 5101-13-1: 2004) contains silica fine particles of 250 ml / 100 g or more, and the surface protective layer is formed by crosslinking and curing the ionizing radiation curable resin composition. , A decorative sheet in which a recessed region that is visually recognized as a recessed portion is formed immediately above and near the low gloss pattern ink layer,
(2) The decorative sheet according to (1) above, wherein the resin used in the resin composition forming the low gloss pattern ink layer is a non-crosslinkable resin, and (3) (1) or (1) above A decorative board having the decorative sheet according to claim attached to a substrate;
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which has the outstanding wiping property, and the decorative board using the same can be obtained, maintaining the design feeling which has a rich texture.

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

[Decorative sheet]
The decorative sheet of the present invention comprises a low gloss pattern ink layer provided at least partially on a substrate, and the low gloss pattern ink layer is present on and in contact with the low gloss pattern ink layer. A decorative sheet having a surface protective layer covering the entire surface including a formed region and a region where the low gloss pattern ink layer is not formed, and the low gloss pattern ink forming the low gloss pattern ink layer absorbs oil Silica fine particles having an amount (conforming to JIS K 5101-13-1: 2004) of 250 ml / 100 g or more are contained, and the surface protective layer is formed by crosslinking and curing the ionizing radiation curable resin composition. A concave region that is visually recognized as a concave portion is formed in the layer immediately above and near the low gloss pattern ink layer.

A typical structure of the decorative sheet of the present invention will be described with reference to FIGS. 1 and 2 are schematic views showing a cross section of the decorative sheet 1 of the present invention.
In the example shown in FIG. 1, a low gloss pattern ink layer 3 containing predetermined fine particles 10 is laminated on a substrate 2, and a surface protective layer 5 in which an ionizing radiation curable resin composition is crosslinked and cured is laminated thereon. It is a thing. And the low gloss area | region 4 is formed in the surface protective layer in the direct upper part of the low gloss pattern ink layer 3, and its vicinity. When the decorative board of the present invention is viewed from the surface protective layer 5 side, the partially existing low gloss region 4 is visually recognized as a concave portion, and the concave / convex pattern is recognized as a whole. The low gloss region 4 is represented by a set of points in the drawing.

  In the example shown in FIG. 2, a uniform and uniform colored layer 6 covering the entire surface of the substrate 2, a pattern layer 7, a uniform and uniform penetration preventing layer 8, a low gloss pattern ink layer 3 including predetermined fine particles 10, A surface protective layer 5 formed by crosslinking and curing the ionizing radiation curable resin composition is laminated in this order. Similarly to the sheet shown in FIG. 1, the decorative sheet 1 shown in FIG. 2 has a low gloss region 4 formed on the surface protective layer immediately above and near the low gloss pattern ink layer 3, and the low gloss region No. 4 is visually recognized as a recess, and an uneven pattern is recognized as a whole.

<< Substrate 2 >>
The base material 2 used in the present invention is not particularly limited as long as it is usually used for decorative sheets, 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.

Various papers include thin paper, kraft paper, titanium paper, and the like. These paper base materials are made by adding resins such as acrylic resin, styrene butadiene rubber, melamine resin, urethane resin to these paper base materials in order to strengthen the strength between fibers of the paper base material and to prevent the occurrence of scraping. It may be a paper-reinforced paper, a resin-impregnated paper, or the like that has been impregnated with a post-resin or made during papermaking. In addition, various papers often used in the building materials field such as linter paper, paperboard, and base paper for gypsum board, coated paper used for office work and normal printing, packaging, art paper, sulfate paper, glassine paper, parchment paper, Paraffin paper or Japanese paper can also be used.
In addition, woven fabrics and nonwoven fabrics of various fibers can also be used as the base material. Examples of the 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. Examples of the synthetic resin include polyolefin resin, vinyl resin, polyester resin, acrylic resin, polyamide resin, cellulose resin, polystyrene resin, polycarbonate resin, polyarylate resin, and polyimide resin.

  As metal foil, a metal sheet, or a metal plate, what consists of aluminum, iron, stainless steel, copper, etc., and what gave these metals by plating etc. can also be used, for example. Examples of the various wood-based boards include wood fiber boards such as wood veneer, plywood, laminated lumber, particle board, or MDF (medium density fiber board). 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, polyethylene plates sandwiched between two aluminum plates, etc. can also be used as a substrate. .

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.
In addition, the base material may be subjected to a treatment such as forming a primer layer for strengthening the interlayer adhesion between the base material and each layer, coating for adjusting the color, or a pattern from a design standpoint. May be formed in advance.

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 .

<< Low gloss pattern ink layer 3 and low gloss area 4 >>
The low gloss pattern ink layer 3 provided on the decorative sheet of the present invention is partially present on the base material and is directly laminated on the base material 2 as shown in FIG. 1, or as shown in FIG. It is laminated on the colored layer 6, the pattern layer 7, the permeation prevention layer 8, etc. provided as necessary. And the low gloss area | region 4 is formed in the surface protective layer in the direct upper part of this low gloss pattern ink layer 3, and its vicinity.
When the decorative sheet of the present invention is viewed from the surface protective layer 5 side, the low gloss region 4 has a low gloss, and is visually recognized as a concave portion due to the difference between the gloss of the periphery and the low gloss region 4 as a whole. Is visually recognized as an uneven pattern.
The extent of the spread 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 FIGS. It may stay in the middle of the thickness direction of the surface protective layer 5 from the surface of the layer 3 or may reach the outermost surface of the surface protective layer 5.

  The mechanism of gloss difference between the low-gloss area 4 and its surroundings and the mechanism of the intensity of the extent of its spread have not been fully elucidated. From the measurement results, when an uncured product of ionizing radiation curable resin for forming the surface protective layer 5 on the surface of the low gloss pattern ink layer 3 was applied, the combination of materials and the appropriate application conditions were determined. Depending on the selection, the resin component of the low gloss pattern ink layer 3 and the surface protective layer are presumed to be due to some interaction such as elution, dispersion, and 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 having this suspended state, the low gloss region 4 is partially formed in the surface protective layer 5, It is assumed that the part is recognized as if it were a recess.

  In the decorative sheet of the present invention, by utilizing the characteristics of the low gloss pattern ink layer 3, it is possible to visually express the pattern that the pattern layer 7 expresses by combining with the pattern layer 7 that is preferably provided. A pattern having visual recesses due to a difference in gloss can be obtained by synchronizing the portion where the recesses are to be expressed with the low gloss pattern ink layer 3. 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. Further, when the tile layer pattern is to be expressed by the pattern layer 7, the joint groove portion is visually visualized by the difference in gloss by synchronizing the ink portion of the low gloss pattern ink layer 3 with the tile groove joint portion. The pattern which became a recessed part is obtained.

(Low gloss ink)
The low gloss pattern ink that forms the low gloss pattern ink layer 3 contains silica fine particles 10 having an oil absorption (conforming to JIS K 5101-13-1: 2004) of 250 ml / 100 g or more. When the oil absorption amount of the silica fine particles is within the above range, the magic wiping property can be improved while maintaining the design properties of the decorative sheet. The upper limit of the oil absorption amount of the silica fine particles in the present invention is not particularly limited, but is about 700 ml / 100 g for convenience of production of silica fine particles, and the upper limit of easy availability is about 400 ml / 100 g.

  The average particle diameter of the silica fine particles is preferably in the range of 0.1 to 7 μm, more preferably in the range of 0.1 to 5 μm, though it depends on the thickness of the low gloss pattern ink layer. If the average particle size of the silica fine particles is within the above range, the thixotropy of the ink will not be extremely high, and the viscosity of the ink will not increase too much, and printing control will be easy. Since it becomes smaller, the head of the fine particles is relatively pressed down and becomes inconspicuous, so that a visual discomfort is unlikely to occur. Here, the average particle diameter is measured by a Coulter counter method or a laser diffraction method.

The specific surface area of the silica fine particles is preferably 200 m ² / g or more, more preferably 230 m ² / g or more, and further preferably 260 m ² / g or more from the viewpoint of obtaining excellent design properties. Here, the specific surface area is a value measured by the method of JIS K6221 by nitrogen adsorption.

  The concentration of the silica fine particles in the low gloss pattern ink is preferably 1 to 50 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin contained in the low gloss pattern ink described later. Part by mass is more preferable. When the concentration of the silica fine particles is within the above range, the thixotropy of the ink does not become extremely high, the viscosity of the ink does not increase excessively, printing is easily controlled, and sufficient design properties can be obtained.

The binder resin contained in the low gloss pattern ink has a property capable of expressing an interaction such as elution, dispersion, and mixing with the ionizing radiation curable resin composition forming the surface protective layer 5, It is appropriately selected in relation to the ionizing radiation curable resin composition (uncured product). Examples of such binder resins include thermoplastic (non-crosslinked) urethane resins such as polyester urethane resins, acrylic resins, polyester resins, unsaturated polyester resins, and vinyl chloride-vinyl acetate copolymers. However, thermoplastic (non-crosslinked) urethane resins such as polyester urethane resins are preferred.
If necessary, unsaturated polyester resin, acrylic resin, or vinyl chloride-vinyl acetate copolymer is used to adjust the degree of expression of the low gloss area and the contrast of the gloss difference between the low gloss area and the surrounding area. Can be mixed.

The low-gloss pattern ink can contain a colorant and can provide a pattern itself. However, when the color layer 6 or the pattern layer 7 as shown in FIG. It is not necessary to add and color.
Colorants used in low gloss design inks 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 Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metallic pigments consisting of scaly foils such as aluminum and brass, pearl luster consisting of scaly foils such as titanium dioxide-coated mica and basic lead carbonate (pearl) ) Pigments are used.

The coating amount of the low gloss pattern ink is preferably in the range of ^{2 to 20} g / m ² . When it is ² g / m ² or more, the above-described low gloss pattern ink and the ionizing radiation curable resin composition interact with each other, and a sufficiently low gloss region is obtained, so that a sufficient gloss difference on the decorative sheet surface can be obtained. . On the other hand, when it is 20 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 glossy picture ink is more preferably in the range of 5 to 10 g / m ^2.

<< surface protective layer 5 >>
The surface protective layer 5 is formed by crosslinking and curing the ionizing radiation curable resin composition. As described above, the surface protective layer 5 is visually recessed directly above and near the low gloss pattern ink layer 3. Is formed as a low gloss region 4 recognized as 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.

(Ionizing radiation curable resin)
The ionizing radiation curable resin composition used for forming the surface protective layer 5 is a resin composition containing an ionizing radiation curable resin and various additives. The ionizing radiation curable resin preferably used in this ionizing radiation curable resin composition is appropriately selected from polymerizable monomers and polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resins. However, from the viewpoint of obtaining good curing characteristics, those that are difficult to bleed out, have a coating property even as a solid content of about 95 to 100%, and are less likely to cause curing shrinkage upon curing. Representative examples of such ionizing radiation curable resins are described below. “(Meth) acrylate” means “acrylate or methacrylate”.

  As the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and in particular, a polyfunctionality having two or more ethylenically unsaturated bonds in the molecule ( (Meth) acrylate is preferred, and one kind may be used alone, or two or more kinds may be used in combination. As a functional group number, 2-8 are preferable, 2-6 are more preferable, and 3-4 are more preferable.

  In the present invention, together with the polyfunctional (meth) acrylate, for the purpose of adjusting the viscosity, monofunctional (meth) acrylates such as methyl (meth) acrylate are within a range that does not impair the purpose of the present invention. It can be used together as appropriate. A monofunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

  Next, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) Preferred examples include acrylate oligomers. Among these oligomers, polyfunctional polymerizable oligomers are preferable, and the number of functional groups is preferably 2 to 16, more preferably 2 to 8, and still more preferably 2 to 6.

  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 type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group. These polymerizable oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the ultraviolet curable resin. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.

  In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the ionizing radiation curable resin composition in the present invention contains an ultraviolet absorber, and in the case of irradiation with ultraviolet rays, the ultraviolet irradiation amount may be insufficient. Although preparation may be required, in the case of electron beam irradiation, such preparation is unnecessary, and stable curing characteristics can be obtained efficiently.

(Silicone (meth) acrylate)
The ionizing radiation curable resin composition can contain silicone (meth) acrylate. Silicone (meth) acrylate is added for the purpose of controlling the surface tension of the surface protective layer at the same time as imparting surface physical properties such as stain resistance due to a synergistic effect with the ionizing radiation curable resin.
Silicone (meth) acrylate is one of silicone oils made of polysiloxane or modified silicone oil in which (meth) acrylic groups are introduced at one or both ends. Conventionally known silicone (meth) acrylates can be used, and are not particularly limited as long as the organic group is a (meth) acrylic group, and a modified silicone oil having 1 to 6 organic groups can be preferably used. . The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation.

  The content of the silicone (meth) acrylate is preferably 0.5 to 4 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin, from the viewpoint of sufficiently improving the stain resistance and obtaining its use effect. 0-2.5 mass parts is more preferable. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 1000-20000 is mentioned, for example.

<Various additives>
In the present invention, various additives can be blended in the ionizing radiation curable resin composition depending on the desired physical properties to be obtained. Examples of the additive include a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, and a solvent. Is mentioned.

(Formation of surface protective layer 5)
An example of a preferred embodiment for forming the surface protective layer 5 will be described below.
First, ionizing radiation curable resins such as polymerizable monomers and polymerizable oligomers, silicone (meth) acrylate and various additives added as necessary are homogeneously mixed at a predetermined ratio, and ionizing radiation curable resin. A composition is prepared. The viscosity of the ionizing radiation curable resin composition 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, but a solvent is added as necessary. May be.

  Preferred examples of the solvent include water-insoluble organic solvents such as toluene, xylene, ethyl acetate, methyl ethyl ketone, and ethylene glycol monomethyl ether, water-soluble organic solvents such as methanol, ethanol, and isopropyl alcohol, water, and mixed solvents thereof. It is done. The amount of the solvent in the ionizing radiation curable resin composition may be appropriately selected according to the viscosity of the ionizing radiation curable resin composition, but the ionizing radiation curable resin composition is usually 65 to 85 mass on a solid basis. %.

  Application of the ionizing radiation curable resin composition is a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure so that the thickness after curing is 1 to 20 μm. Perform by coating. A surface protective layer having desired performance is obtained when the thickness after curing is 1 μm or more. The thickness of the surface protective layer after curing is preferably 2 to 20 μm from the viewpoint of sufficiently obtaining the effect of providing the surface protective layer.

  The uncured resin layer formed by application of the ionizing radiation curable resin composition becomes a surface protective layer by irradiating with ionizing radiation such as an electron beam and ultraviolet rays and crosslinking and curing. 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 crosslinking density of the ionizing radiation curable resin 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).
The electron beam source is not particularly limited, and 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 are used. be able to.
When ultraviolet rays are used as 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 surface protective layer 5 thus formed has various functions by adding various additives such as a so-called hard coat function, anti-fogging coat function, and anti-fouling coating function having high hardness and scratch resistance. Further, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can be provided.

(Convex shape 9)
The surface protective layer 5 may have a convex shape 9 that is formed to protrude with the formation of the low gloss pattern ink layer 3 or the low gloss region 4. Because the surface of the surface protective layer 5 has such a convex shape, light is scattered at the convex portion, the surface area is increased, and the viewing angle where low gloss can be recognized is widened. Further, in cooperation with the effect of the low gloss region 4, the visual unevenness is further enhanced. In addition, although it does not specifically limit in the range with the effect of this invention about the height of this convex shape, Usually, it is the range of 2-3 micrometers.

Further, on the surface of the surface protective layer 5, particularly on the surface portion of the convex shape immediately above and near the low gloss pattern ink layer 3, there are fine uneven shapes due to the effect of fine particles contained in the low gloss pattern ink layer 3. It may be formed (not shown).
The decorative sheet of the present invention can obtain a design feeling that visually gives a sense of unevenness by the low-gloss area 4 while ensuring the texture due to the effect of the convex shape 9 and the fine uneven shape, and further provides a texture. It becomes possible to obtain excellent wiping properties contrary to the above.

<< Colored layer 6 >>
The colored layer 6 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 sheet of the present invention. The colored layer 6 adjusts the color of the surface of the base material 2 to give the intended color to the surface of the base material 2 when the base material 2 is colored or has color unevenness. The colored layer 6 is usually formed with an opaque color in many cases, but it may be formed with a colored transparent color and use a pattern that the base has. When the base material 2 is appropriately colored, it is not necessary to form the colored layer 6.

  As the ink used for forming the colored layer 6, an ink obtained by appropriately mixing a binder resin with a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used. The binder resin is not particularly limited, and examples thereof include urethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, Preferred examples include polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins. Any of these may be used alone or in combination of two or more. Used. Among the above, urethane resin is preferable.

  Urethane resins preferably used for the colored layer 6 include polyol components such as polyols such as acrylic polyol, polyester polyol and polyether polyol and isocyanate components such as aromatic isocyanates such as tolylene diisocyanate, xylene diisocyanate and diphenylmethane diisocyanate, 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. 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 60 ° C. for oil resistance and scratch resistance.

Examples of the colorant include the same colorants as those used in the low-gloss pattern ink. From these, the colorant may be appropriately selected and used according to the desired pattern.
The thickness of the colored layer 6 is usually about 1 to 20 μm, and is preferably a uniform and uniform printing layer that is coated over the entire surface, as shown in FIG.

"Picture layer 7"
The pattern layer 7 is a layer provided as desired in order to give decorativeness to the decorative sheet of the present invention, and is formed by printing various patterns using ink and a printing machine. Patterns include stone patterns that simulate the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, brickwork patterns, There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, as well as by multicolor printing with special colors prepared by preparing 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.

<< Penetration prevention layer 8 >>
The permeation preventive layer 8 is a layer provided as desired, and has a function of suppressing the penetration of the ionizing radiation curable resin constituting the low gloss design ink and the surface protective layer 5 into the base material 2. This is particularly effective when the substrate 2 is a permeable substrate such as paper or nonwoven fabric. Therefore, the penetration preventing layer 8 may be located 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 pattern layer 7, or in FIG. 2 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 or the like on the substrate 2, these surfaces are smoothed, and the adhesion between them and the low gloss pattern ink layer 3 and the surface protective layer 5 is improved. Is also fulfilled.

Examples of the curable resin suitable for the permeation preventing layer 8 include those used for the binder of the ink for forming the colored layer 6. Especially, said urethane resin is preferable from a viewpoint of scratch-resistant improvement.
The thickness of the penetration preventing layer 8 is usually about 1 to 20 μm.

[Decorative board]
The decorative sheet of the present invention can be used as a decorative plate by sticking to various substrates. Specifically, as shown in FIG. 3, it is obtained by attaching a decorative sheet 1 to a substrate 12 via an adhesive layer 11.
The board | substrate used as a to-be-adhered body is not specifically limited, The thing similar to what is used for the base material 2 can be used. In addition, the substrate may be preliminarily formed with a paint for adjusting the color and a pattern from a design viewpoint. As a substrate to be an adherend, plate materials such as flat plates and curved plates of various materials, or three-dimensional articles (molded products) in which the above materials are used alone or in combination are targeted.

  Further, a backing material such as Japanese paper, Western paper, synthetic paper, non-woven fabric, woven fabric, cold paper, impregnated paper, or synthetic resin sheet may be attached to the decorative sheet. By attaching the backing material, the decorative sheet itself can be reinforced, the decorative sheet can be prevented from cracking and tearing, and the adhesive can be prevented from seeping out from the surface of the decorative sheet. Thus, productivity can be improved.

  Using a bonding device such as a cold press, hot press, roll press, laminator, wrapping, edge pasting machine, vacuum press, etc., on a substrate on which a decorative sheet is placed every leaf or continuously via an adhesive The decorative sheet is bonded to the substrate surface by pressing to form a decorative board.

The adhesive is applied using an application device such as a spray, a spreader, or a bar coater. As the adhesive, vinyl acetate resin-based, urea resin-based, melamine resin-based, phenol resin-based, isocyanate-based adhesives are used alone or as a mixed adhesive obtained by arbitrarily mixing them. As needed, inorganic powders such as talc, calcium carbonate, clay and titanium white, 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 sheet on the substrate is usually performed by forming an adhesive layer on the back surface of the decorative sheet of the present invention and applying the substrate, or applying an adhesive on the substrate and applying the decorative sheet, etc. Depending on the method.

  The decorative board manufactured in this way can be arbitrarily cut by cutting the decorative board, and using a cutting machine such as a router or a cutter on the surface or the end of the decorative board, it can be subjected to optional decoration such as grooving and chamfering. it can. And various uses, for example, interior or exterior materials of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, margins, surface decorative boards for fittings such as malls, kitchens, furniture or light electrical appliances, It can be suitably used for a surface decorative plate of a cabinet such as an OA device, an interior or exterior of a vehicle.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(1) Measurement of gloss value For the decorative sheets obtained in each of the examples and comparative examples, a glossy area (“MMX-203” manufactured by Murakami Color Research Laboratory) was used, and a low gloss region under the condition of an incident angle of 60 degrees. The gloss value was measured. The smaller the value, the lower the gloss (low gloss).
(2) Evaluation of magic wiping property In order to facilitate the evaluation of magic wiping property, in each example and comparative example, the same color as that used in each example and comparative example except that the colorant used was only titanium white. Thus, a decorative sheet was prepared. A square (5 cm × 5 cm) was painted with oily magic on the surface of the obtained decorative sheet, and after 3 minutes, it was wiped with gauze. The square area ratio remaining after wiping was visually observed and evaluated according to the following criteria. An average value obtained by repeating this five times was used as an evaluation of the magic wiping property.
5 Residual rate is less than 1% 4 Residual rate is 1% or more and less than 5% 3 Residual rate is 5% or more and less than 10% 2 Residual rate is 10% or more and less than 50% 1 Residual rate is 50% or more

Example 1: Preparation of decorative sheet As the base material 2, a reinforced paper with a weight of rice of 30 g / m ² is used, and on one side, acrylic resin and nitrified cotton are used as a binder, and titanium white, petal, and yellow lead are colored. Using the ink as the agent, 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, a polyester urethane resin having a number average molecular weight of 30,000 and a glass transition temperature (Tg) of −62.8 ° C. is used as a binder, and silica fine particles (oil absorption: 280 ml / 100 g, average particle size: 2.3 μm) are used as a binder. The low gloss pattern ink layer 3 was formed by gravure printing so that the position of the low gloss pattern ink blended with 5 parts by mass with respect to 100 parts by mass was synchronized with the wood grain pattern conduit.
On these ink layers, an electron beam curable resin composition comprising 100 parts by mass of tetrafunctional urethane acrylate and 1 part by mass of silicone acrylate prepolymer was applied at a coating amount of 5 g / m ² by a gravure offset coater method. After the coating, an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated to cure the electron beam curable resin composition to obtain the surface protective layer 5. Next, curing was performed at 70 ° C. for 24 hours to obtain a decorative sheet.
The gloss value of this decorative sheet was measured, and the magic wiping property was evaluated. The results are shown in Table 1.

Examples 2 and 3 and Comparative Example 1
In Example 1, a decorative sheet was obtained in the same manner as in Example 1 except that the silica fine particles in the low-gloss pattern ink were changed to oil absorption amounts shown in Table 1, respectively. The gloss value of the obtained decorative sheet was measured, and the magic wiping property was evaluated. The results are shown in Table 1.

* 1, Content of silica fine particles per 100 parts by mass of resin (parts by mass)

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which has the outstanding wiping property, and the decorative board using the same can be obtained, maintaining the design feeling which has a rich texture. The decorative sheet and decorative plate of the present invention are suitably used for interior or exterior materials for buildings, surface decorative plates for fittings, surface decorative plates for furniture, and vehicle interiors and exteriors.

1. Cosmetic sheet 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 shape 10. Fine particles 11. Adhesive layer 12. substrate

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have provided an uneven pattern by embossing inside the decorative sheet for insert molding, and filled the uneven pattern with a resin, thereby I found that it could be solved. The present invention has been completed based on such findings.
That is, the present invention
(1) A pattern ink layer is formed by partially applying a pattern ink containing silica fine particles having an oil absorption (based on JIS K 5101-13-1: 2004) of 250 ml / 100 g or more on a substrate. And a region where the pattern ink layer is formed and a region where the pattern ink layer is not formed, and the ionizing radiation curable resin composition is present on and is in contact with the pattern ink layer. The substrate, the design ink layer, the surface protection layer, and the surface protection layer, which have the steps of coating the entire surface so as to cover the surface, and crosslinking and curing to form a surface protection layer. A method for producing a decorative sheet having a low-gloss area at the top or in the vicinity thereof,
(2) The method for producing a decorative sheet according to (1) above, wherein the resin used in the resin composition for forming the pattern ink layer is a non-crosslinkable resin, and (3) the amount of oil absorption (JIS ) on the substrate. A step of partially applying a pattern ink containing silica fine particles having a particle size of 250 ml / 100 g or more (based on K 5101-13-1: 2004) to form a pattern ink layer, and an ionizing radiation curable resin composition It is applied on the entire surface including the area where the pattern ink layer is formed and the area where the pattern ink layer is not formed. A base material, a pattern ink layer, a surface protection layer, and a cosmetic sheet having a low gloss region immediately above or near the pattern ink layer in the surface protection layer. Process of preparation and method of manufacturing a decorative laminate comprising the step of Paste via the adhesive layer and the base material and the substrate of the decorative sheet in order,
Is to provide.

Claims (3)

  A low gloss pattern ink layer provided at least partially on the substrate, and a region on 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 A decorative sheet having a surface protective layer covering the entire surface including a region where no glossy pattern ink layer is formed, and the low glossy pattern ink forming the low glossy pattern ink layer absorbs oil (JIS K 5101-13). -1: Conforms to 2004) containing silica fine particles of 250 ml / 100 g or more, and the surface protective layer is formed by crosslinking and curing the ionizing radiation curable resin composition. A decorative sheet in which a recessed region that is visually recognized as a recessed portion is formed immediately above and near the glossy pattern ink layer.   The decorative sheet according to claim 1, wherein the resin used for the resin composition forming the pattern ink layer is a non-crosslinkable resin.   A decorative board comprising the decorative sheet according to claim 1 attached to a substrate.