JP6907573B2 - Decorative sheets and materials - Google Patents

Description

The present invention relates to a decorative sheet and a decorative material.

In building materials, furniture, home appliances, etc., a decorative sheet is generally used when it is desired to decorate the surface of a member to be used.
In order to enhance the design, these decorative sheets may be formed with a pattern layer such as a wood grain pattern of natural wood, a stone pattern such as travertine, a tile pattern, or a brick pattern.

Further, in order to further enhance the design of the above-mentioned decorative sheet, a decorative sheet having a three-dimensional effect has been developed as in Patent Documents 1 to 3.

In Patent Document 1, after forming a matte (relatively low mirror glossiness) positive print (for example, a pattern in a conduit groove region of wood grain), a portion where the positive print is not formed is glossy (for example,). A building material paper on which negative printing (for example, a transparent coating film covering an area other than a conduit groove of wood grain) is formed (which has a relatively high mirror glossiness) is disclosed. Such building material paper has physical surface irregularities between the positive printing area (relatively convex) and the negative printing area (relatively concave), and the so-called gloss-matte effect, that is, in a plane. When a relatively high-gloss area and a low-gloss area coexist, the high-gloss area visually protrudes from the low-gloss area and is visually recognized. Can be reproduced.
Patent Document 2 discloses a wood grain emphasizing decorative board in which the surface of a softwood is brushed to form irregularities, the convex portions are colored, and then a protective layer is formed on the entire surface.
Patent Documents 3 and 4 disclose a decorative material in which a transparent resin layer is partially formed on a matte layer formed on the entire surface.

Special Publication No. 53-331 Special Publication No. 61-7355 Japanese Unexamined Patent Publication No. 2-103141 Japanese Unexamined Patent Publication No. 2001-138469

The building material paper of Patent Document 1 has a problem that it is extremely inferior in three-dimensional effect when the negative and the positive are misaligned. Moreover, even if the register is accurately adjusted, the reproduction of the three-dimensional effect depends on the film thickness difference of the ink (or the coating film) of about several μm, and the gloss difference between the glossy part and the non-glossy part. However, there was a problem that the three-dimensional effect was poor.
The wood grain emphasizing decorative board of Patent Document 2 has a problem that the brushing process is complicated, and after forming a protective layer on the entire surface to smooth the surface, a portion recessed by brushing and a portion other than that are recessed. There was a problem that the gloss difference with the above was insufficient and the three-dimensional effect was poor.
The decorative materials of Patent Documents 3 and 4 can solve the process problems as in Patent Documents 1 and 2, but the gloss difference between the portion having the transparent resin layer and the other portion is insufficient. However, there was a problem that it lacked a three-dimensional effect.

An object of the present invention is to provide a decorative sheet and a decorative material having an excellent three-dimensional effect.

In order to solve the above problems, the present inventors provide the following decorative sheets and materials [1] to [8].
[1] A decorative sheet having a brilliant ink layer having an arbitrary pattern on a substrate, and a transparent resin layer synchronized with the pattern of the brilliant ink layer in a region directly above the brilliant ink layer. ..
[2] When the decorative sheet has a low gloss region and a high gloss region, and the decorative sheet is observed from the side having the transparent resin layer with reference to the substrate, the bright ink layer and the bright ink layer and the decorative sheet are observed. The decorative sheet according to the above [1], wherein the high gloss region is formed by the region having the transparent resin layer synchronized with the region.
[3] The decorative sheet according to the above [1] or [2], wherein at least one surface of the substrate is roughened and the bright ink layer is provided on the roughened surface.
[4] The decorative sheet according to any one of the above [1] to [3], wherein the substrate further has a pattern layer.
[5] Difference between the arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the high gloss region and the arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the low gloss region [Ra-height of the low gloss region The decorative sheet according to the above [2], wherein Ra] of the glossy region is 3 μm or more.
[6] Difference between the 60-degree mirror surface gloss of JIS Z8741: 1997 in the high-gloss region and the 60-degree gloss of JIS Z8741: 1997 in the low-gloss region [60-degree gloss of the high-gloss region-low-gloss region The decorative sheet according to the above [2], which has a [60-degree glossiness] of 3 or more.
[7] The decorative sheet according to any one of [1] to [6] above, wherein any pattern of the brilliant ink layer has shading, and the shading is formed from the density of halftone dots.
[8] A decorative material obtained by laminating and integrating the adherend and the surface of the decorative sheet according to any one of [1] to [7] on the side opposite to the surface having the transparent resin layer.

The decorative sheet and the decorative material of the present invention have good appearance of the design due to the difference in the brilliance between the in-plane regions, that is, the expression of the contrast of the brilliance. Further, by making the difference in brilliance between the regions and the difference in gloss between the regions (difference in mirror glossiness) cooperate with each other, the three-dimensional effect can be made excellent, and the design is extremely good. Can be.

It is sectional drawing which shows one Embodiment of the decorative sheet of this invention. It is sectional drawing which shows the other embodiment of the decorative sheet of this invention. It is sectional drawing which shows the other embodiment of the decorative sheet of this invention. It is sectional drawing which shows the other embodiment of the decorative sheet of this invention. It is sectional drawing which shows the other embodiment of the decorative sheet of this invention.

[Cosmetic sheet]
The decorative sheet of the present invention has a brilliant ink layer having an arbitrary pattern on the substrate, and has a transparent resin layer synchronized with the pattern of the brilliant ink layer in a region directly above the brilliant ink layer. It is made up of.

1 to 5 are cross-sectional views showing an embodiment of the decorative sheet 100 of the present invention. The decorative sheets 100 of FIGS. 1 to 5 have a glitter ink layer 20 having an arbitrary pattern on the substrate 10, and a transparent resin synchronized with the pattern of the glitter ink layer 20 in a region directly above the glitter ink layer 20. It has a layer 30. Further, the decorative sheet 100 of FIGS. 2 to 5 has a pattern layer 2. Further, the base 10 of the decorative sheet of FIGS. 2 to 4 is composed of the support 1 and the pattern layer 2.
A region having a brilliant ink layer 20 and a transparent resin layer 30 synchronized with the pattern of the brilliant ink layer when the decorative sheet 100 is observed from the surface of the side having the transparent resin layer 30 with reference to the substrate 10. Form a high gloss region G, and other regions form a low gloss region M.

<Hpokeimenon>
As shown in FIGS. 1 to 5, the substrate 10 is composed of at least the support 1.

(Support)
The material of the support is not particularly limited, and various types of paper, plastic film, wood-based boards such as wood, ceramic-based materials, and the like can be appropriately selected according to the intended use. Each of these materials may be used alone, or may be a laminate obtained by any combination such as a composite of papers or a composite of paper and a plastic film.

Examples of papers include thin leaf paper, kraft paper, titanium paper, coated paper, art paper, sulfate paper, glassin paper, parchment paper, paraffin paper and Japanese paper, and interstitial reinforced paper and resin impregnated paper of these papers. Among these papers, those composed of thin paper, kraft paper, titanium paper, etc. are preferable from the viewpoint of thermal stability and strength, and two polyethylene films are used from the viewpoint of moisture resistance. A composite of paper and plastic film called polysand paper sandwiched between papers is suitable.

Specific examples of the resin constituting the plastic film include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins, vinylidene chloride resins, polyvinyl alcohols, vinyl resins such as ethylene-vinyl alcohol copolymers, polyethylene terephthalates, and polybutylene. Examples thereof include polyester resins such as terephthalate, acrylic resins such as polymethylmethacrylate, methylpolyacrylate and ethylpolymethacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate and polycarbonate. Among these, polyolefin resins, vinyl chloride resins, polyester resins, or acrylic resins are preferable from the viewpoints of various physical properties such as weather resistance and water resistance, printability, molding processability, and price.

The thickness of the support is not particularly limited, but when the support is a plastic film, it is preferably 20 to 200 μm, more preferably 40 to 160 μm, and even more preferably 40 to 100 μm. When the support is a paper, the basis weight, usually preferably ^{20~150g / m 2, 30~100g / m} 2 is more preferable.

The shape of the support is not limited to a flat plate shape, and may be a special shape such as a three-dimensional shape.
On the support, in order to improve the adhesion to the layer provided on the support, one side or both sides may be subjected to an easy adhesion treatment such as a physical treatment or a chemical surface treatment.

As shown in FIGS. 2 to 4, the substrate 10 may be composed of the support 1 and the pattern layer 2. When the substrate 10 has the pattern layer 2, it is preferable to form the glitter ink layer 20 and the transparent resin layer 30 on the surface of the substrate 10 on the side having the pattern layer 2 as shown in FIGS.

(Pattern layer)
The pattern layer 2 is formed in a region on the support 1 where the bright ink layer 20 is formed (≈ region where the transparent resin layer is formed) as shown in FIG. 2, or the support is formed as shown in FIG. It can be formed in a region where the brilliant ink layer 20 is not formed on No. 1 (≈ a region where a transparent resin layer is not formed), or can be formed on the entire surface of the support 1 as shown in FIG.
Further, as shown in FIG. 5, the pattern layer 2 may be formed on the brilliant ink layer 20 and / or on the transparent resin layer 30. However, when the pattern layer is formed on the brilliant ink layer or the transparent resin layer, the brilliant ink is obtained when the decorative sheet is observed from the surface direction from the viewpoint of securing the high gloss region G and maintaining the three-dimensional effect. It is preferable not to cover the entire surface of the layer with the pattern layer.
Further, although not shown, the structure may have a pattern layer on the support and further have a pattern layer on the brilliant ink layer and / or the transparent resin layer.

It is preferable that the pattern layer is formed by separately forming a pattern that appears convex and a pattern that appears concave.
The region on the support 1 where the brilliant ink layer 20 is formed (≈ region where the transparent resin layer 30 is formed) corresponds to the high gloss region G (region that looks convex) of the decorative sheet 100. Therefore, it is preferable that the pattern layer 2A formed in the region has a pattern that looks convex. For example, when the design to be given is a wood grain pattern, the pattern layer 2A is preferably a wood surface pattern (a part other than the conduit groove pattern and / or the knot pattern), and when the design to be given is a stone pattern such as travertin, the pattern is used. The layer 2A preferably has a pattern other than the recessed portion, and when the design to be imparted is a tile pattern or a brick pattern, the pattern layer 2A preferably has a tile portion or a brick portion.
On the other hand, the region on the support 1 where the bright ink layer 20 is not formed (≈ the region where the transparent resin layer 30 is not formed) corresponds to the low gloss region M (the region which looks concave) of the decorative sheet 100. Therefore, it is preferable that the pattern layer 2B formed in the region has a pattern that looks concave. For example, when the design to be given is a wood grain pattern, the pattern layer 2B is preferably a conduit groove pattern and / or a knot pattern, and when the design to be given is a stone pattern such as travertin, the pattern layer 2B is a concave pattern. When the design to be given is a tile pattern or a brick pattern, the pattern layer 2B is preferably a joint pattern.

The pattern layer is formed by, for example, printing. More specifically, the pattern layer is formed by multicolor printing with ordinary yellow, red, blue, and black process colors, and is also multicolored by preparing plates of individual colors that make up the pattern. It is also formed by color printing or the like.

Examples of the ink used for forming the pattern layer include a binder mixed with a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent.
The binder is not particularly limited, and for example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, etc. Examples thereof include petroleum-based resins, ketone resins, epoxy-based resins, melamine-based resins, fluorine-based resins, silicone-based resins, fibrous derivatives, and rubber-based resins. These resins can be used alone or in admixture of two or more.
Examples of the colorant include carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, petal pattern, cadmium red, ultramarine blue, cobalt blue and other inorganic pigments, quinacridone red, and isoindolinone yellow. , Organic pigments such as phthalocyanine blue, dyes and the like.

The thickness of the pattern layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the desired design. The pattern layer may contain additives such as an antioxidant and an ultraviolet absorber as long as the effects of the present invention are not impaired.

The substrate may have a colored layer. The colored layer is a solid layer on the entire surface, and mainly has the purpose of imparting concealment. The colored layer can be formed, for example, between the support of the substrate and the pattern layer.
As the ink used for forming the colored layer, the same ink as the ink used for forming the pattern layer can be used.

(Roughening)
Although not shown, it is preferable that at least one surface of the substrate is roughened.
Since the surface of the substrate is roughened, it is possible to make it easier to increase the gloss difference between the high gloss region G and the low gloss region M of the decorative sheet, and it is possible to enhance the three-dimensional effect. Specifically, when a brilliant ink layer having an arbitrary pattern and a transparent resin layer synchronized with the brilliant ink layer, which will be described later, are formed on the roughened surface of the substrate, the brilliant ink layer and the transparent resin layer are formed. The unfinished region can be a low gloss region M based on the rough surface. Further, the region where the brilliant ink layer and the transparent resin layer are formed is filled with the fine irregularities on the rough surface by both layers and smoothed, and as a result, the surface of the transparent resin layer, which is the outermost surface, exhibits specular reflection. It becomes the 艷 area G.
Further, it is not necessary that the entire surface of at least one surface of the substrate is roughened, and at least a part thereof may be roughened. When at least a part of one surface of the substrate is roughened, it is preferable that the roughened portion corresponds to a portion where the bright ink layer is not formed (≈ a portion that mainly functions as a low gloss region M).

Examples of the substrate having at least one surface roughened include a substrate having a matte layer and a substrate that has been roughened by blasting, etching, embossing, or the like.
These roughened substrates may have a pattern layer. In the case of a substrate having a support, a matte layer and a pattern layer, it is preferable to arrange the support, the matte layer and the pattern layer in this order with reference to the thickness direction in order to enhance the sharpness of the pattern.

The mat layer contains, for example, a matting agent and a binder.
Examples of the matting agent include inorganic particles such as silica, alumina, zirconia, titania and magnesium carbonate, and resin particles made of polymethylmethacrylate, polystyrene, silicone resin and polyester.

The average particle size of the matting agent is preferably 0.1 to 10.0 μm, more preferably 0.5 to 6.0 μm, from the viewpoint of imparting low gloss and suppressing the removal of the matting agent. .. In the present specification, the average particle size of the matting agent and the bright pigment described later means the median size of the volume-based particle size distribution measured by the laser diffraction / scattering method.
From the same viewpoint, the ratio of [average particle size of matting agent / thickness of matte layer] is preferably 0.01 to 10, and more preferably 0.1 to 7.

The content of the matting agent in the mat layer is preferably 5 to 50 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of imparting low gloss and balancing the coating film strength. More preferably.

Examples of the binder for the mat layer include a thermoplastic resin and a cured product of a curable resin composition, and a cured product of the curable resin composition is preferable from the viewpoint of durability.
Examples of the cured product of the curable resin composition include a cured product of the thermosetting resin composition and a cured product of the ionizing radiation curable resin composition. From the viewpoint of adhesion to the upper and lower layers of the mat layer (support, pattern layer, brilliant ink layer, etc.), a cured product of the thermosetting resin composition is preferable.

Examples of the thermosetting resin composition include a polyester resin composition, an epoxy resin composition, a polyurethane resin composition, an aminoalkyd resin composition, a melamine resin composition, a guanamine resin composition, a urea resin composition and a thermosetting acrylic resin. Examples include compositions. These thermosetting resin compositions include a monomer and / or a prepolymer constituting each resin, and a curing agent or the like added as needed.
Among these thermosetting resin compositions, a polyurethane resin composition is preferable from the viewpoint of adhesion to the upper and lower layers of the mat layer and filmability. Examples of the polyurethane resin composition include a composition in which a polyol (polyhydric alcohol) is used as a main component and an isocyanate is used as a cross-linking agent (curing agent).
As the ionizing radiation curable resin composition, the same composition as the ionizing radiation curable resin composition of the transparent resin layer described later can be used.

The thickness of the mat layer may be such that a low gloss region M can be formed, and is usually about 1 to 20 μm.
As the mat layer, for example, a coating liquid for forming a mat layer containing a material constituting the mat layer can be formed by a general-purpose coating means such as gravure coating.

The roughened surface of the substrate preferably has an arithmetic mean roughness Ra of JIS B0601: 2001 of 5 to 100 μm, more preferably 10 to 50 μm. By setting the lower limit value to 5 μm or more, it is possible to easily impart a low gloss region M exhibiting a low gloss (low gloss or matte) appearance visually, and by setting the upper limit value to 100 μm or less, unevenness forming a rough surface can be easily provided. It is possible to suppress a decrease in design due to excessive unevenness due to the shape itself being visually recognized.

<Glittering ink layer>
The brilliant ink layer is formed on the substrate in an arbitrary pattern, and constitutes a highly brilliant region having a pearl luster tone or a gold leaf powder tone. The brilliant ink layer and the transparent resin layer described later form a high gloss region G in the surface of the decorative sheet, and the three-dimensional appearance of the decorative sheet can be enhanced.

The glitter ink layer includes, for example, a glitter pigment and a binder.
Examples of the brilliant pigment include pearl pigments and metal pigments. Among these, the pearl pigment can easily suppress the decrease in the light transmittance of the brilliant ink layer, so that when the pattern layer exists under the brilliant ink layer, the visibility of the pattern layer is not easily impaired. It is suitable in terms of points.

The pearl pigment is a pigment that can impart pearl luster, and examples thereof include those in which the surface of the parent particles is coated with a metal oxide. As the matrix particles, scaly particles such as mica are preferable. Examples of the metal oxide include oxides of metals such as titanium, iron, zirconium, silicon, aluminum and cerium. The metal oxide may be used alone or in combination of two or more.
Specific examples of the pearl pigment include titanium dioxide-coated mica, iron oxide-coated mica, titanium dioxide and iron oxide-coated mica. The pearl pigment may be used alone or in combination of two or more.

Examples of the metal pigment include metals such as aluminum, brass, stainless steel, tin, zinc, copper, nickel, gold powder and silver, and pigments made of alloys of these metals. One type of metal pigment may be used alone, or two or more types may be used in combination.

The average particle size of the brilliant pigment is preferably 1 to 500 μm, more preferably 5 to 100 μm, from the viewpoint of imparting brilliance and suppressing the brilliant pigment from falling off.
From the same viewpoint, the ratio of [average particle size of bright pigment / thickness of bright ink layer] is preferably 0.01 to 15, and more preferably 0.5 to 10.

Examples of the binder of the glittering ink layer include a thermoplastic resin and a cured product of a curable resin composition, and a cured product of the curable resin composition is preferable from the viewpoint of durability.
Examples of the cured product of the curable resin composition include a cured product of the thermosetting resin composition and a cured product of the ionizing radiation curable resin composition. From the viewpoint of adhesion to the upper and lower layers (support, pattern layer, transparent resin layer, etc.) of the glitter ink layer, a cured product of the thermosetting resin composition is preferable.

The thermosetting resin composition of the glittering ink layer includes a polyester resin composition, an epoxy resin composition, a polyurethane resin composition, an aminoalkyd resin composition, a melamine resin composition, a guanamine resin composition, a urea resin composition, and the like. Examples thereof include thermosetting acrylic resin compositions. These thermosetting resin compositions include a monomer and / or a prepolymer constituting each resin, and a curing agent or the like added as needed.
As the ionizing radiation curable resin composition of the glittering ink layer, the same one as the ionizing radiation curable resin composition of the transparent resin layer described later can be used.

The content of the brilliant pigment in the brilliant ink layer is preferably 10 to 90 parts by mass, and more preferably 50 to 80 parts by mass with respect to 100 parts by mass of the binder. By setting the content of the glitter pigment to 10 parts by mass or more, it is possible to make the gloss of the high gloss region G sufficiently easy, and by setting the content of the glitter pigment to 90 parts by mass or less, a pattern layer is provided in the lower layer. In this case, it is possible to prevent the visibility of the pattern from being impaired.
From the same viewpoint, the thickness of the brilliant ink layer is preferably 1 to 30 μm, more preferably 5 to 20 μm.

Any pattern of the glitter ink layer depends on the design to be applied. For example, the arbitrary pattern is preferably a wood surface pattern (a portion other than the conduit groove pattern and / or the knot pattern) when the wood grain pattern is given to the entire decorative sheet, and the entire decorative sheet is made of stone such as travertin. When giving a pattern, it is preferable to use a pattern other than the recessed portion, and when giving a tile pattern or a brick pattern to the entire decorative sheet, it is preferable to use a tile portion or a brick portion.

Any pattern of the glitter ink layer preferably has shades in order to enhance the design. The shading may be formed from the size of the halftone dots and the thickness of the halftone dots, but it is preferable to form the halftone dots from the density of the halftone dots (the size of the halftone dots is uniform and the halftone dots are formed with the density of the halftone dots). .. By forming the shading of the brilliant ink layer from the density of the halftone dots, it is possible to prevent the halftone dots of the brilliant ink from protruding from the originally intended region and to prevent the design from being deteriorated. In other words, by forming the shading of the brilliant ink layer from the density of the halftone dots, it is possible to suppress the halftone dots of the brilliant ink from protruding into the low gloss region M, and it is possible to suppress the deterioration of the design. Further, in order to facilitate the above-mentioned effect, the diameter of the halftone dots of the brilliant ink layer is preferably 10 to 800 μm, more preferably 50 to 300 μm.

As the brilliant ink layer, for example, a coating liquid for forming a brilliant ink layer containing a material constituting the brilliant ink layer can be formed by a general-purpose printing means such as gravure printing. When the shading of the brilliant ink layer is formed from the density of halftone dots, the halftone dots of the printing plate may be formed by an FM (frequency modulation) screen.

<Transparent resin layer>
The transparent resin layer is a layer formed in a region directly above the brilliant ink layer in synchronization with the pattern of the brilliant ink layer.
By forming the transparent resin layer in synchronization with the pattern of the brilliant ink layer, a high gloss region G can be formed in the surface of the decorative sheet, and the three-dimensional effect of the decorative sheet can be improved. .. When the transparent resin layer is formed on the entire surface of the decorative sheet, the gloss difference between the region having the glitter ink layer and the other regions is reduced, so that the three-dimensional effect cannot be improved.

In the present invention, the synchronization between the pattern of the brilliant ink layer and the transparent resin layer includes an error generally allowed in printing. Specifically, when the decorative sheet is observed from the plane direction, the pattern of the brilliant ink layer and the transparent resin layer are misaligned, particularly the edge portion E of the brilliant ink layer 20 and the transparent resin layer 30, that is, the brilliance. If the positional deviation of the ink layer 20 and the transparent resin layer 30 at the boundary line in contact with the non-formed region in a plan view is 200 μm or less, it is included in the tuning of the present specification.
The detection limit that humans can see is about 30 to 50 μm. Therefore, the deviation between the pattern of the brilliant ink layer and the transparent resin layer is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 30 μm or less.

The transparent resin layer preferably contains a resin as a main component. Here, the main component means that the resin is contained in an amount of 50% by mass or more based on the total solid content constituting the transparent resin layer, preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 98% by mass. It is mass% or more.

Examples of the resin of the transparent resin layer include a thermoplastic resin and a cured product of a curable resin composition. Among these, a cured product of a curable resin composition is preferable from the viewpoint of scratch resistance, a cured product of an ionizing radiation curable resin composition is preferable, and a cured product of an electron beam curable resin composition is preferable. ..

As the thermosetting resin composition of the transparent resin layer, the same one as the thermosetting resin composition of the mat layer can be used.

The ionizing radiation curable resin composition is a composition containing a compound (ionizing radiation curable compound) that is cured by irradiation with ionizing radiation. Ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but other X-rays. , Electromagnetic waves such as γ-rays, charged particle beams such as α-rays and ion rays can also be used.

The ionizing radiation curable compound can be appropriately selected and used from the commonly used polymerizable monomers and polymerizable oligomers or prepolymers.
As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable.
The polyfunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule. For example, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, etc. Preferable examples include trimerol propanetri (meth) acrylate, trimerol propaneethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Be done. One of these (meth) acrylate monomers may be used alone, or two or more thereof may be used in combination.

The number of functional groups of the polyfunctional (meth) acrylate monomer is preferably 2 or more, preferably 2 to 8 from the viewpoint of obtaining excellent surface protection properties, and more preferably 3 to 6.

Next, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate. (Meta) acrylate oligomers such as oligomers and acrylic (meth) acrylate oligomers are preferably mentioned, and these oligomers can be used alone or in combination of two or more.
Among the above polymerizable (meth) acrylate oligomers, polyfunctional urethane (meth) acrylate-based oligomers are preferable. This is because the polyfunctional urethane (meth) acrylate-based oligomer can impart excellent surface protection properties and can suppress shrinkage of the decorative sheet in the manufacturing process.
The number of functional groups of the polyfunctional (meth) acrylate oligomer is not particularly limited as long as it is 2 or more, but it is preferably 2 to 8 and more preferably 2 to 6 from the viewpoint of surface protection characteristics and suppression of shrinkage during production.

The weight average molecular weight of the polyfunctional (meth) acrylate oligomer (polystyrene-equivalent weight average molecular weight measured by the GPC method) is preferably 1,000 to 20,000, preferably 1,000 to 10,000. Is more preferable.

As the ionizing radiation curable compound, monofunctional (meth) acrylate may be used in order to adjust the hardness and the viscosity of the ionizing radiation curable resin composition.
Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl (meth) acrylate. ) Acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate and the like. One of these monofunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

When an ultraviolet curable compound is used as the ionizing radiation curable compound, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator to 100 parts by mass of the ultraviolet curable compound. The photopolymerization initiator can be appropriately selected from those conventionally used, and is not particularly limited. For example, benzoin-based, acetophenone-based, phenylketone-based, benzophenone-based, anthraquinone-based, and the like initiators for photopolymerization are started. Agents are preferred.
Further, as the photosensitizer, for example, p-dimethylbenzoic acid ester, tertiary amines, thiol-based sensitizer and the like can be used.

The ionizing radiation curable compound is preferably electron beam curable. This is because, in the case of electron beam curability, solvent-free is possible, which is more preferable from the viewpoint of environment and health, and stable curing characteristics can be obtained without the need for a photopolymerization initiator.

The thickness of the transparent resin layer may be as long as it can impart a desired luster, preferably 1 to 30 μm, and more preferably 2 to 20 μm.

The transparent resin layer preferably has a pattern synchronized with an arbitrary pattern of the bright ink layer.

As the transparent resin layer, for example, a coating liquid for forming a transparent resin layer containing a material constituting the transparent resin layer can be formed by a general-purpose printing means such as gravure printing. When the shading of the transparent resin layer is formed from the density of halftone dots, the halftone dots of the printing plate may be formed by an FM screen.

<Primer layer>
The primer layer is provided between the support and the pattern layer, between the pattern layer and the brilliant ink layer, and the like, if necessary, in order to improve the adhesion between the layers.
The primer layer preferably contains a resin as a main component. Examples of the resin of the primer layer include ester resin, urethane resin, acrylic resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer and the like. Further, the resin of the primer layer may be a two-component curable resin. Of these resins, a two-component curable resin is preferable from the viewpoint of adhesion.
The two-component curable resin is not particularly limited as long as it is a resin that is cured by adding a curing agent to the main agent. The two-component curable resin is a polyol (polyhydric alcohol) as the main agent and an isocyanate curing agent as the curing agent. Urethane resin is preferable.
The thickness of the primer layer is usually about 0.5 to 20 μm, preferably 1 to 10 μm.

<Backside primer layer>
The back surface primer layer is a layer preferably provided on the surface of the substrate opposite to the side having the glitter ink layer for the purpose of improving the adhesiveness between the decorative sheet and various adherends.
The material used for forming the back surface primer layer is not particularly limited, and examples thereof include urethane resin, acrylic resin, polyester resin, vinyl chloride / vinyl acetate copolymer, chlorinated polypropylene resin, chlorinated polyethylene resin, and the like. It may be appropriately selected depending on the material of the material.
The thickness of the back surface primer layer is preferably 1 to 5 μm, more preferably 1 to 3 μm.

<Physical characteristics of high gloss area and low gloss area>
The decorative sheet has a difference between the arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the high gloss region G and the arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the low gloss region M [Ra of the low gloss region G]. -Ra of the high gloss region M] is preferably 3 μm or more.
By setting the above difference to 3 μm or more, more preferably 4 μm, the gloss difference between the high gloss region G and the low gloss region M can be easily increased, and the three-dimensional appearance of the decorative sheet can be easily improved. Further, if a difference in arithmetic mean roughness Ra is given to a certain extent or more, the difference in mirror glossiness between the high-grade region G and the low-grade region M, and further, the effect of expressing the standing feeling by the cooperation with the bright ink layer is saturated. If the difference in the arithmetic mean roughness Ra is increased more than necessary, the surface of the low area becomes too rough and is visually recognized as a mere uneven shape rather than erasing. Therefore, the above difference is more preferably 150 μm or less, and further preferably 100 μm or less.
The arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the high gloss region G is preferably 0.01 to 1 μm. The arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the low gloss region M is preferably 3 to 150 μm.
The arithmetic mean roughness Ra of JIS B0601: 2001 is a value at a cutoff value of 0.8 mm.

The decorative sheet has a difference between the 60-degree mirror surface gloss of JIS Z8741: 1997 in the high-gloss region G and the 60-degree gloss of JIS Z8741: 1997 in the low-gloss region M [60-degree gloss-low in the high-gloss region G. The 60-degree glossiness of the glossy region M] is preferably 3 or more.
By setting the above difference to 3 or more, the gloss difference between the high gloss region G and the low gloss region M becomes clear, and the three-dimensional appearance of the decorative sheet can be easily improved. The difference is more preferably 3 or more and 90 or less, further preferably 5 or more and 80 or less, and further preferably 10 or more and 60 or less.
The 60-degree mirror surface glossiness of the high gloss region G is preferably 11 or more and 70 or less. The 60-degree mirror glossiness of the surface of the low-gloss region M is preferably 1 or more and 30 or less.

[Cosmetic material]
The decorative material of the present invention is formed by laminating and integrating the adherend and the surface of the decorative sheet of the present invention on the side opposite to the surface having the transparent resin layer.

The adherend is, for example, a single wood board, a wood plywood board, a particle board, an MDF (medium density fiber board), a wood board such as an laminated material; a plaster board such as a plaster board or a plaster slag board; a calcium silicate board, an asbestos slate board. , Lightweight foamed concrete board, hollow extruded cement board, etc.; fiber cement board, pulp cement board, asbestos cement board, wood piece cement board, etc.; ceramic board, pottery, porcelain, earthenware, glass, amber, etc.; iron plate, zinc plating Metal plates such as steel plates, polyvinyl chloride sol coated steel plates, aluminum plates and copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates and polycarbonate plates; phenol resin plates, urea resin plates and unsaturated polyester resin plates , Thermo-curable resin plate such as polyurethane resin plate, epoxy resin plate, melamine resin plate; resin such as phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin, glass fiber Examples thereof include a so-called FRP plate obtained by impregnating and curing a non-woven fabric, cloth, paper, or other various fibrous base materials to form a composite, and these may be used alone or as a composite substrate in which two or more of these are laminated. You may.

The method of laminating the decorative sheet on various adherends is not particularly limited, and for example, a method of adhering the sheet to the adherend with an adhesive or the like can be adopted. The adhesive may be appropriately selected from known adhesives according to the type of adherend and the like. For example, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer and the like, as well as butadiene-acrylic nitrile rubber, neoprene rubber, natural rubber and the like can be mentioned.

Decorative materials are preferably used as, for example, interior materials for buildings such as walls, ceilings, and floors; fittings such as window frames, doors, and handrails; furniture; housings for home appliances, OA equipment, etc.; exterior materials such as entrance doors. be able to.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example. Unless otherwise specified, "part" is based on mass.

1. 1. Measurement and Evaluation The following measurements and evaluations were performed on the decorative sheets of Examples and Comparative Examples. The results are shown in Table 1.

1-1. Surface Roughness For the decorative sheets of Examples and Comparative Examples, the arithmetic mean roughness Ra (JIS B0601: 2001, cutoff value 0.8 mm) of the surfaces of the high gloss region G and the low gloss region M was measured. In the decorative sheet of the comparative example, the outermost surface of the region having the glitter ink layer was regarded as the high gloss region G, and the outermost surface of the region not having the glitter ink layer was regarded as the low gloss region M.
The measurement was performed using the trade name SE-340 manufactured by Kosaka Research Institute Co., Ltd., and the following measurement conditions were used.
[Needle of surface roughness detector]
Product name SE2555N manufactured by Kosaka Research Institute (tip radius of curvature: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
-Evaluation length (reference length): 5 times the cutoff value λc (0.8 x 5 = 4.0 mm)
・ Feeding speed of stylus: 0.5 mm / s
-Preliminary length: (cutoff value λc) x 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

1-2. Mirror glossiness For the decorative sheets of Examples and Comparative Examples, the 60-degree mirror glossiness of the surfaces of the high gloss region G and the low gloss region M was measured according to (JIS Z8741: 1997). In the decorative sheet of the comparative example, the outermost surface of the region having the glitter ink layer was regarded as the high gloss region G, and the outermost surface of the region not having the glitter ink layer was regarded as the low gloss region M.

1-3. Design (three-dimensional effect)
Twenty subjects evaluated and calculated the average score, with 2 points for those who strongly felt the three-dimensional effect, 1 point for those who could not say either, and 0 points for those who felt that the three-dimensional effect was poor. An average score of 1.7 or more is "AA", an average score of 1.4 or more and less than 1.7 is "A", and an average score of 1.0 or more and less than 1.4 is "B". Those with an average score of less than 1.0 were designated as "C".

2. Preparation of decorative sheet [Example 1]
A mat layer having a thickness of 1 μm was formed by applying a coating liquid for forming a mat layer of the following formulation on a support 1 of an easily adhesive polyethylene terephthalate film (manufactured by Mitsubishi Chemical Polyester, Diafoil Z350, thickness 45 μm) and drying it. .. Next, on the matte layer, the binder resin was composed of 60 parts by mass of acrylic polyol and 40 parts by mass of hexamethylene diisocyanate by gravure multicolor printing. A wood grain pattern layer 2 having a thickness of 1 μm was formed of a wood grain pattern pattern layer 2A other than the conduit portion by an ink containing a yellowish brown pigment in the same binder resin as the ink. Next, in a plan view, the coating liquid for forming a brilliant ink layer of the following formulation is gravurely applied to the portion directly above the portion where the wood-skin pattern pattern layer 2A is formed on the substrate 10 composed of the support 1 and the pattern layer 2. It was applied and dried by a printing method to form a glittering ink layer having a thickness of 3 μm. Next, the transparent resin layer forming coating liquid of the following formulation is applied and dried by a gravure printing method so as to be position-synchronized directly above the brilliant ink layer in a plan view to form a transparent resin layer 30 having a thickness of 10 μm. , A decorative sheet 100 of Example 1 having a laminated structure shown in the cross-sectional view of FIG. 4 was obtained. In the obtained decorative sheet 100, the positional deviation between the pattern of the brilliant ink layer 20 and the pattern of the transparent resin layer 30 in a plan view was within 30 μm, which is the detection limit of the human eye.
The gravure printing plate used to form the brilliant ink layer and the transparent resin layer is a plate cell formed by an FM screen, and the cell (halftone dot) pattern and area of both plates are the same. There is. The plate on which the brilliant ink layer 20 and the transparent resin layer 30 were printed had no cells in the region corresponding to the area directly above the pattern layer 2B having the conduit groove pattern in a plan view. As a result, there was no ink transfer between the brilliant ink layer 20 and the transparent resin layer 30 in the decorative sheet immediately above the pattern layer 2B having the conduit groove pattern in a plan view.

<Coating liquid for forming a mat layer>
-Acrylic polyol 60 parts by mass-Hexamethylene diisocyanate 40 parts by mass-Silica (average particle size: 5.5 μm) 26 parts by mass-Diluting solvent Appropriate amount

<Coating liquid for forming a glittering ink layer>
-Pearl pigment 35 parts by mass (white pearl, particle size 25 μm)
・ Acrylic resin 65 parts by mass ・ Diluting solvent Appropriate amount

<Coating liquid for forming a transparent resin layer>
-Urethane acrylate oligomer 30 parts by mass (number average molecular weight 1500, average number of functional groups 5)
-Urethane acrylate polymer 70 parts by mass (number average molecular weight 8000, average number of functional groups 10)
・ Appropriate amount of diluting solvent

[Example 2]
The pattern layer was formed directly on the easily adhesive polyethylene terephthalate film without forming the matte layer. Further, in the ink for printing the pattern layer 2B of the conduit groove pattern, in addition to the black-brown pigment, an ink in which 26 parts by mass of silica (average particle size: 2 μm) is added to 100 parts by mass of the binder resin is used. board. A decorative sheet of Example 2 was obtained in the same manner as in Example 1 except for the above.

[Comparative Example 1]
A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the transparent resin layer was formed on the entire surface of the decorative sheet.

[Comparative Example 2]
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the transparent resin layer was not formed.

As shown in Table 1, in the decorative sheets of Examples 1 and 2, since the glitter ink layer and the transparent resin layer are synchronized, the gloss of the region can be increased, while the other regions can be enhanced. It was possible to suppress the luster of the ink and increase the luster difference in the surface of the decorative sheet. Therefore, the decorative sheets of Examples 1 and 2 have an excellent three-dimensional effect and an excellent design.
On the other hand, the decorative sheets of Comparative Examples 1 and 2 had insufficient gloss difference in the surface of the decorative sheet and were inferior in three-dimensional effect.

The decorative sheet of the present invention is useful in that it has an excellent three-dimensional effect and can make the design extremely good.

1: Support 2: Picture layer 10: Hypokeimenon 20: Bright ink layer 30: Transparent resin layer 100: Decorative sheet

Claims (6)

A decorative sheet, the decorative sheet on a substrate, has a brilliant ink layer having an arbitrary pattern, in the area just above the brilliant ink layer, tuned to the pattern of the brilliant ink layer Has a transparent resin layer ,
When the decorative sheet has a low gloss region and a high gloss region, and the decorative sheet is observed from the surface having the transparent resin layer with reference to the substrate, the brilliant ink layer and the same are synchronized with the decorative sheet. The high gloss region is formed by the region having the transparent resin layer.
Difference between the arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the high gloss region and the arithmetic mean roughness Ra of JIS B0601: 2001 on the surface of the low gloss region [Ra of the low gloss region-high gloss region Ra] is 3 μm or more, a decorative sheet. The decorative sheet according to claim 1, wherein at least one surface of the substrate is roughened and the brilliant ink layer is provided on the roughened surface. The decorative sheet according to claim 1 or 2 , wherein the substrate further has a pattern layer. Difference between the 60-degree mirror surface gloss of JIS Z8741: 1997 in the high-gloss region and the 60-degree gloss of JIS Z8741: 1997 in the low-gloss region [60-degree gloss of the high-gloss region-60 degrees of the low-gloss region The decorative sheet according to claim 1 , wherein the glossiness is 3 or more. A bright ink layer having an arbitrary pattern is provided on the substrate, and a transparent resin layer synchronized with the pattern of the bright ink layer is provided in a region directly above the bright ink layer.
A decorative sheet in which any pattern of the brilliant ink layer has shading, and the shading is formed from the density of halftone dots. A decorative material obtained by laminating and integrating the adherend and the surface of the decorative sheet according to any one of claims 1 to 5, which is opposite to the surface having the transparent resin layer.

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