JP2018126949A - Cosmetic sheet and cosmetic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having an excellent stereoscopic feeling and a decorative material.SOLUTION: A decorative sheet 100 has, on a substrate 10, a brilliant ink layer 20 having any pattern and, in a region right above the brilliant ink layer 20, a transparent resin layer 30 synchronized with the pattern of the brilliant ink layer 20.SELECTED DRAWING: Figure 1

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.
These decorative sheets may be provided with a pattern layer such as a natural wood grain pattern, a stone pattern such as travertine, a tile pattern, a brick pattern or the like in order to enhance the design.

  Moreover, in order to improve the designability of the decorative sheet mentioned above, the decorative sheet which provided the three-dimensional effect like patent documents 1-3 is developed.

In Patent Document 1, after forming a non-glossy (relatively low specular gloss) positive printing (for example, a pattern in a conduit groove region of a wood grain), a glossy part is formed where no positive printing is formed ( There is disclosed a building material paper on which negative printing (for example, a transparent coating film covering an area other than a conduit groove of wood) having a relatively high specular gloss is formed. Such building 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 the plane. When a relatively high-gloss area and a low-gloss area coexist, a high-gloss area that has projections and depressions in synchronism with the pattern is achieved by a synergistic effect with the effect that the high-gloss area visually protrudes from the low-gloss area. Can be reproduced.
Patent Document 2 discloses a grain-enhanced decorative board in which the surface of a softwood material is brushed to form irregularities, the convex portions are colored, and 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.

Japanese Patent Publication No.53-331 Japanese Patent Publication No.61-7355 JP-A-2-103141 JP 2001-138469 A

The building material paper of Patent Document 1 has a problem that it is extremely inferior in three-dimensional effect when the registration between the negative and the positive is shifted. In addition, even if the registration is accurately adjusted, the reproduction of the three-dimensional effect depends on the film thickness difference of the ink (or coating film) of about several μm, and the gloss difference between the glossy part and the dull part Is insufficient, and there is a problem that the stereoscopic effect is poor.
The wood grain embossed decorative board of Patent Document 2 has a problem that the brushing process is complicated, and after the protective layer is formed on the entire surface and the surface is smoothed, there are portions that are recessed by brushing and other portions. There is a problem that the gloss difference is insufficient and the three-dimensional effect is poor.
The cosmetic 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 portions is insufficient. There was a problem that the three-dimensional effect was poor.

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

In order to solve the above problems, the present inventors provide the following decorative sheets and cosmetic materials [1] to [8].
[1] A decorative sheet having a glittering ink layer having an arbitrary pattern on a substrate, and a transparent resin layer in synchronization with the pattern of the glittering ink layer in a region immediately above the glittering ink layer .
[2] The decorative sheet has a low gloss region and a high gloss region, and when the decorative sheet is observed from the surface having the transparent resin layer with respect to the base, the glitter ink layer and The decorative sheet according to the above [1], wherein the high gloss region is formed by a region having the transparent resin layer in synchronism with this.
[3] The decorative sheet according to [1] or [2], wherein at least one surface of the substrate is roughened, and the glitter ink layer is provided on the roughened surface.
[4] The decorative sheet according to any one of [1] to [3], wherein the base further has a pattern layer.
[5] Difference between arithmetic average roughness Ra of JIS B0601: 2001 on the surface of the high gloss region and arithmetic average roughness Ra of JIS B0601: 2001 on the surface of the low gloss region [Ra-high in low gloss region The decorative sheet according to the above [2], wherein Ra of the gloss region is 3 μm or more.
[6] Difference between 60 degree specular gloss of JIS Z8741: 1997 in the high gloss area and 60 degree gloss of JIS Z8741: 1997 in the low gloss area [60 degree gloss of high gloss area−low gloss area The decorative sheet according to the above [2], wherein the 60 degree glossiness is 3 or more.
[7] The decorative sheet according to any one of [1] to [6], wherein an arbitrary pattern of the glitter ink layer has light and shade, and the light and shade are formed by density of halftone dots.
[8] A decorative material obtained by laminating and integrating an adherend and a surface opposite to the surface having the transparent resin layer of the decorative sheet according to any one of [1] to [7].

  The decorative sheet and the decorative material of the present invention have good appearance of the design appearance due to the difference in glitter between the in-plane regions, that is, the appearance of glitter contrast. In addition, by combining the difference in glitter between the areas and the difference in gloss (difference in specular gloss) between the areas, the stereoscopic effect can be improved 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 other embodiment of the decorative sheet of this invention. It is sectional drawing which shows other embodiment of the decorative sheet of this invention. It is sectional drawing which shows other embodiment of the decorative sheet of this invention. It is sectional drawing which shows other embodiment of the decorative sheet of this invention.

[Decorative sheet]
The decorative sheet of the present invention has a glittering ink layer having an arbitrary pattern on a substrate, and has a transparent resin layer in synchronization with the pattern of the glittering ink layer in a region immediately above the glittering ink layer. It will be.

1-5 is sectional drawing which shows embodiment of the decorative sheet 100 of this invention. The decorative sheet 100 of FIGS. 1 to 5 has a glittering ink layer 20 having an arbitrary pattern on a substrate 10, and a transparent resin synchronized with the pattern of the glittering ink layer in a region immediately above the glittering ink layer 20. It has a layer 30. The decorative sheet 100 of FIGS. 2 to 5 has a pattern layer 2. Moreover, the base 10 of the decorative sheet shown in FIGS. 2 to 4 includes a support 1 and a pattern layer 2.
When the decorative sheet 100 is observed from the surface side with the transparent resin layer 30 on the basis of the base 10, the region having the glittering ink layer 20 and the transparent resin layer 30 synchronized with the pattern of the glittering ink layer Forms a high gloss region G, and other regions form a low gloss region M.

<Substrate>
The base | substrate 10 is comprised from the support body 1 at least as shown to FIGS.

(Support)
The material of the support is not particularly limited, and various papers, plastic films, wood-based boards such as wood, ceramic materials, and the like can be appropriately selected according to the application. 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.

  Examples of paper include thin paper, kraft paper, titanium paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper and Japanese paper, and inter-paper reinforced paper and resin-impregnated paper. Among these papers, those composed of paper such as thin paper, kraft paper, and titanium paper are preferable from the viewpoint of thermal stability and strength. From the viewpoint of moisture resistance, two sheets of polyethylene film are used. A composite of paper and a plastic film called polysand paper sandwiched between papers is preferable.

  Specific examples of the resin constituting the plastic film include polyolefin resins such as polyethylene and polypropylene, vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer, polyethylene terephthalate, and polybutylene. Examples thereof include polyester resins such as terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, and polyethyl methacrylate, 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.

Although there is no restriction | limiting in particular in the thickness of a support body, when a support body is a plastic film, 20-200 micrometers is preferable, 40-160 micrometers is more preferable, 40-100 micrometers is further more preferable. 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 shape, and may be a special shape such as a three-dimensional shape.
On the support, easy adhesion treatment such as physical treatment or chemical surface treatment may be performed on one side or both sides in order to improve adhesion to a layer provided on the support.

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

(Picture layer)
As shown in FIG. 2, the pattern layer 2 is formed in a region on the support 1 where the glitter ink layer 20 is formed (≈region where the transparent resin layer is formed), or as shown in FIG. 1 may be formed in a region where the glitter ink layer 20 is not formed (≈a region where a transparent resin layer is not formed), or may 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 glittering ink layer 20 and / or the transparent resin layer 30. However, when the pattern layer is formed on the glitter ink layer or the transparent resin layer, from the viewpoint of maintaining the high gloss region G and maintaining the three-dimensional effect, the glitter ink is used when the decorative sheet is observed from the surface direction. It is preferable not to cover the entire surface of the layer with a pattern layer.
Moreover, although not shown in figure, the structure which has a pattern layer on a support body, and also has a pattern layer on a glittering ink layer and / or a transparent resin layer may be sufficient.

The pattern layer is preferably formed by dividing a pattern that appears convex and a pattern that appears concave.
The region where the glitter ink layer 20 is formed on the support 1 (≈the 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. For this reason, it is preferable that the pattern layer 2 </ b> A formed in the region has a pattern that is projected. For example, when the design to be applied is a wood grain pattern, the pattern layer 2A is preferably a bark pattern (a part other than the conduit groove pattern and / or the knot pattern), and when the design to be applied is a stone pattern such as travertine, the pattern The layer 2A is preferably a pattern other than the recessed part, and when the design to be applied is a tile pattern or a brick pattern, the pattern layer 2A is preferably a tile part or a brick part.
On the other hand, a region where the glitter ink layer 20 is not formed on the support 1 (≈a region where the transparent resin layer 30 is not formed) corresponds to a low gloss region M (a region that looks concave) of the decorative sheet 100. For this reason, it is preferable that the pattern layer 2 </ b> B formed in the region has a pattern that is shown in a concave shape. For example, when the design to be applied 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 applied is a stone pattern such as travertine, the pattern layer 2B is a recess pattern. Preferably, when the design to be applied is a tile pattern or a brick pattern, the pattern layer 2B is preferably a joint pattern.

  The pattern layer is formed by printing, for example. More specifically, the pattern layer is formed by multicolor printing using normal yellow, red, blue, and black process colors, and a multicolor by special colors prepared by preparing individual color plates constituting the pattern. It is also formed by color printing or the like.

Examples of the ink used for forming the picture 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. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, Examples include petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. 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, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue, and other inorganic pigments, quinacridone red, and isoindolinone yellow. , Organic pigments such as phthalocyanine blue, or dyes.

  The thickness of the pattern layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the intended 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.

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

(Roughening)
Although not shown, at least one surface of the substrate is preferably roughened.
Since the base is roughened, the gloss difference between the high gloss region G and the low gloss region M of the decorative sheet can be easily increased, and the three-dimensional effect can be increased. Specifically, when a glittering ink layer having an arbitrary pattern, which will be described later, and a transparent resin layer synchronized therewith are formed on the roughened surface of the substrate, the glittering ink layer and the transparent resin layer are formed. The area that has not been made can be the low gloss area M based on the rough surface. In addition, the region where the glittering ink layer and the transparent resin layer are formed is filled with the rough irregularities on the rough surface and smoothed by these two layers, and the surface of the transparent resin layer, which is the outermost surface, exhibits a specular reflectivity. It becomes the heel region 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 of the surface may be roughened. When at least a part of one surface of the substrate is roughened, the roughened portion is preferably made to correspond to a portion where the glitter ink layer is not formed (≈a portion which functions mainly as the low gloss region M).

Examples of the substrate having at least one surface roughened include a substrate having a mat layer, and a substrate roughened by blasting, etching, embossing, or the like.
These roughened substrates may have a picture layer. In the case of a substrate having a support, a mat layer, and a pattern layer, in order to improve the sharpness of the pattern, it is preferable to arrange the support, the mat layer, and the pattern layer in this order based on the thickness direction.

The mat layer includes, for example, a mat 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 polymethyl methacrylate, polystyrene, silicone resin and polyester.

The average particle size of the matting agent is preferably from 0.1 to 10.0 μm, more preferably from 0.5 to 6.0 μm, from the viewpoint of the balance between imparting low gloss and suppressing the matting agent from falling off. . In the present specification, the average particle diameter of the matting agent and the luster pigment described later means the median diameter of the volume-based particle size distribution measured by a laser diffraction scattering method.
From the same viewpoint, the ratio of [average particle diameter of matting agent / thickness of matting 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 with respect to 100 parts by mass of the binder resin, and 10 to 30 parts by mass 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 the 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, glitter ink layer, etc.), a cured product of the thermosetting resin composition is preferable.

Examples of thermosetting resin compositions include polyester resin compositions, epoxy resin compositions, polyurethane resin compositions, aminoalkyd resin compositions, melamine resin compositions, guanamine resin compositions, urea resin compositions, and thermosetting acrylic resins. Examples thereof include compositions. These thermosetting resin compositions include monomers and / or prepolymers constituting each resin, and a curing agent added as necessary.
Among these thermosetting resin compositions, a polyurethane resin composition is preferable from the viewpoints of adhesion to the upper and lower layers of the mat layer and coating properties. Examples of the polyurethane resin composition include a composition having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent).
As the ionizing radiation curable resin composition, the same ionizing radiation curable resin composition as the transparent resin layer described later can be used.

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

  The roughened surface of the substrate preferably has an arithmetic average roughness Ra of JIS B0601: 2001 of 5 to 100 μm, and more preferably 10 to 50 μm. By setting the lower limit value to 5 μm or more, it is possible to easily give a low gloss region M that visually shows a low wrinkle (low gloss or frosted) appearance, and by setting the upper limit value to 100 μm or less, unevenness constituting a rough surface. It is possible to suppress a decrease in design properties due to excessive unevenness due to the visual recognition of the shape itself.

<Bright ink layer>
The glitter ink layer is formed in an arbitrary pattern on the substrate, and constitutes a high glitter area with high luster of pearl luster tone or gold foil foil tone. With such a glittering ink layer and a transparent resin layer described later, a high gloss region G is formed in the surface of the decorative sheet, and the three-dimensional effect of the decorative sheet can be enhanced.

The glitter ink layer includes, for example, a glitter pigment and a binder.
Examples of glitter pigments include pearl pigments and metal pigments. Among these, since the pearl pigment can easily suppress a decrease in the light transmittance of the glitter ink layer, when the pattern layer exists under the glitter ink layer, it is difficult to impair the visibility of the pattern layer. This is preferable 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 base particle is coated with a metal oxide. As the base 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. One kind of metal oxide may be used alone, or two or more kinds may be used.
Specific examples of the pearl pigment include titanium dioxide-coated mica, iron oxide-coated mica, mica coated with titanium dioxide and iron oxide, and the like. A pearl pigment may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of the metal pigment include pigments made of metals such as aluminum, brass, stainless steel, tin, zinc, copper, nickel, gold powder and silver, and alloys of these metals. A metal pigment may be used individually by 1 type and may be used in combination of 2 or more types.

The average particle diameter of the glitter pigment is preferably 1 to 500 μm, and more preferably 5 to 100 μm, from the viewpoint of imparting glitter and suppressing dropping of the glitter pigment.
From the same viewpoint, the ratio of [average particle diameter of glitter pigment / thickness of glitter ink layer] is preferably from 0.01 to 15, and more preferably from 0.5 to 10.

Examples of the binder of the glitter ink layer include a thermoplastic resin and a cured product of the 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.

Examples of the thermosetting resin composition for the glitter ink layer 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 composition etc. are mentioned. These thermosetting resin compositions include monomers and / or prepolymers constituting each resin, and a curing agent added as necessary.
As the ionizing radiation curable resin composition of the glitter ink layer, the same ionizing radiation curable resin composition of the transparent resin layer described later can be used.

The content of the glitter pigment in the glitter ink layer is preferably 10 to 90 parts by mass, 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, the gloss of the high gloss region G can be easily made sufficiently, and by setting the content of the glitter pigment to 90 parts by mass or less, the lower layer has a pattern 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 glitter ink layer is preferably 1 to 30 μm, and more preferably 5 to 20 μm.

  The arbitrary pattern of the glitter ink layer varies depending on the design to be applied. For example, the arbitrary pattern is preferably a bark pattern (a part other than a conduit groove pattern and / or a knot pattern) when a grain pattern is given to the entire decorative sheet, and the entire decorative sheet is made of a stone such as travertine. When applying a pattern, it is preferable to use a pattern other than the recessed portion, and when applying a tile pattern or a brick pattern on the entire decorative sheet, it is preferable to use a tile portion or a brick portion.

  It is preferable that the arbitrary pattern of the glitter ink layer has light and shade in order to improve design properties. The shading may be formed from the size of the halftone dots or the thickness of the halftone dots, but is preferably formed from the density of the halftone dots (the size of the halftone dots is uniform and the density is formed at the density of the halftone dots). . By forming the density of the glitter ink layer from the density of the halftone dots, it is possible to suppress the dots of the glitter ink from protruding from the originally intended region and to suppress the deterioration of the design. In other words, by forming the density of the glitter ink layer from the density of the halftone dots, it is possible to suppress the halftone dots of the glitter ink from protruding into the low gloss region M and to suppress the deterioration of the design. Moreover, in order to make the above-mentioned effect easy to obtain, the diameter of the dot of the glittering ink layer is preferably 10 to 800 μm, and more preferably 50 to 300 μm.

  The glitter ink layer can be formed, for example, by a general-purpose printing means such as gravure printing using a glitter ink layer forming coating solution containing a material constituting the glitter ink layer. Note that when the density of the glitter ink layer is formed from the density of the 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 the region immediately above the glitter ink layer in synchronization with the pattern of the glitter ink layer.
By forming the transparent resin layer in synchronization with the pattern of the glitter ink layer, it is possible to form a high gloss region G in the surface of the decorative sheet, and to make the decorative sheet have excellent three-dimensional effect. . In addition, when the transparent resin layer is formed on the entire surface of the decorative sheet, the gloss difference between the region having the glittering ink layer and the other region is lowered, so that the stereoscopic effect cannot be improved.

In the present invention, the synchronism between the pattern of the glitter ink layer and the transparent resin layer includes an error that is generally permitted in printing. Specifically, when the decorative sheet is observed from the surface direction, the difference between the pattern of the glitter ink layer and the transparent resin layer, particularly the edge E of the glitter ink layer 20 and the transparent resin layer 30, that is, glitter. If the positional deviation of the ink layer 20 and the transparent resin layer 30 at the boundary line in contact with the non-formation region in a plan view is 200 μm or less, it is included in the tuning of this specification.
Note that the detection limit visible to human eyes is about 30 to 50 μm. For this reason, the difference between the pattern of the glitter 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 with respect to the total solid content constituting the transparent resin layer, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 98%. It is at least mass%.

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

  As a thermosetting resin composition of a transparent resin layer, the same thing as the thermosetting resin composition of a mat | matte 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. The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as γ rays, and charged particle beams such as α rays and ion rays can also be used.

The ionizing radiation curable compound can be appropriately selected from conventionally used polymerizable monomers and polymerizable oligomers or prepolymers.
As the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable, and among them, a polyfunctional (meth) acrylate monomer is preferred.
The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule, such as diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Preferable examples include trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. It is done. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

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

Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate. Preferred are (meth) acrylate oligomers such as oligomers and acrylic (meth) acrylate oligomers, and these oligomers can be used alone or in combination of two or more.
Of the above polymerizable (meth) acrylate oligomers, polyfunctional urethane (meth) acrylate oligomers are preferred. This is because the polyfunctional urethane (meth) acrylate oligomer can impart excellent surface protection properties and can suppress shrinkage of the decorative sheet during the production 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 2 to 8 is preferable and 2 to 6 is more preferable from the viewpoint of surface protection characteristics and suppression of shrinkage during production.

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

As the ionizing radiation curable compound, a 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, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and the like. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

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 with respect to 100 parts by mass of the ultraviolet curable compound. The initiator for photopolymerization can be appropriately selected from those conventionally used, and is not particularly limited. For example, the initiator for photopolymerization such as benzoin, acetophenone, phenylketone, benzophenone, and anthraquinone An agent is preferably mentioned.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  The ionizing radiation curable compound is preferably electron beam curable. In the case of electron beam curable, solvent-free is possible, which is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and stable curing characteristics can be obtained.

  The thickness of the transparent resin layer should just be the thickness which can provide desired glossiness, 1-30 micrometers is preferable and 2-20 micrometers is more preferable.

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

  The transparent resin layer can be formed by using a general-purpose printing means such as gravure printing, for example, a coating solution for forming a transparent resin layer containing a material constituting the transparent resin layer. When the density of the transparent resin layer is formed from the density of the 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 picture layer, between the picture layer and the glitter ink layer, and the like, as necessary, in order to improve the adhesion between the layers.
The primer layer is preferably composed mainly of a resin. Examples of the resin for the primer layer include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, and the like. 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 component, and the two-component curable resin in which the main component is a polyol (polyhydric alcohol) and the curing agent is an isocyanate curing agent. A urethane resin is preferred.
The thickness of a primer layer is about 0.5-20 micrometers normally, and 1-10 micrometers is preferable.

<Backside primer layer>
The back primer layer is a layer preferably provided on the surface of the substrate opposite to the side having the glittering ink layer for the purpose of improving the adhesion between the decorative sheet and various adherends.
The material used for forming the back primer layer is not particularly limited, and examples thereof include urethane resin, acrylic resin, polyester resin, vinyl chloride / vinyl acetate copolymer, chlorinated polypropylene resin, and chlorinated polyethylene resin. What is necessary is just to select suitably according to the material of a material.
The thickness of the back primer layer is preferably 1 to 5 μm, and more preferably 1 to 3 μm.

<Physical properties of high gloss area and low gloss area>
The decorative sheet has a difference between the arithmetic average roughness Ra of JIS B0601: 2001 on the surface of the high gloss region G and the arithmetic average 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 effect of the decorative sheet can be easily improved. Further, if a difference in arithmetic mean roughness Ra is given to some extent, the difference in specular gloss between the high wrinkle region G and the low wrinkle region M, and further, the effect of expression of the vertical feeling due to the cooperation with the glitter ink layer is saturated. If the difference of the arithmetic average roughness Ra is increased more than necessary, the surface of the low wrinkle region becomes too rough, and it is visually recognized as a concavo-convex shape rather than erasure. Therefore, the difference is more preferably 150 μm or less, and further preferably 100 μm or less.
The arithmetic average roughness Ra of JIS B0601: 2001 on the surface of the high gloss region G is preferably 0.01 to 1 μm. The arithmetic average roughness Ra of JIS B0601: 2001 on the surface of the low gloss region M is preferably 3 to 150 μm.
The arithmetic average roughness Ra of JIS B0601: 2001 is a value with a cutoff value of 0.8 mm.

The decorative sheet has a difference between the 60 ° specular glossiness of JIS Z8741: 1997 in the high gloss region G and the 60 ° glossiness of JIS Z8741: 1997 in the low gloss region M [60 ° glossiness of the high gloss region G−low. The 60 degree glossiness of the gloss region M] is preferably 3 or more.
By setting the difference to 3 or more, the gloss difference between the high gloss region G and the low gloss region M becomes clear, and the stereoscopic effect 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 still more preferably 10 or more and 60 or less.
The 60 degree specular gloss of the high gloss region G is preferably 11 or more and 70 or less. The 60 ° specular glossiness of the surface of the low gloss region M is preferably 1 or more and 30 or less.

[Cosmetic materials]
The decorative material of the present invention is formed by laminating an adherend and a surface opposite to the surface having the transparent resin layer of the decorative sheet of the present invention described above, and integrating them.

  Adhering materials are, for example, wood veneer, wood plywood, particle board, MDF (medium density fiber board), laminated board such as laminated wood; gypsum board such as gypsum board and gypsum slag board; , Cement boards such as lightweight foamed concrete board and hollow extruded cement board; fiber cement boards such as pulp cement board, asbestos cement board, wood chip cement board; ceramic boards such as earthenware, porcelain, earthenware, glass, firewood; iron plate, galvanized Metal plate such as steel plate, polyvinyl chloride sol coated steel plate, aluminum plate, copper plate; thermoplastic resin plate such as polyolefin resin plate, acrylic resin plate, ABS plate, polycarbonate plate; phenol resin plate, urea resin plate, unsaturated polyester resin plate Thermosetting resin plates such as polyurethane resin plates, epoxy resin plates, melamine resin plates; phenol resins, urea resins, unsaturated Examples include so-called FRP plates in which a resin such as a reester resin, polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin is impregnated and cured on a glass fiber nonwoven fabric, fabric, paper, or other various fibrous base materials. These may be used alone, or may be used as a composite substrate in which two or more of these are laminated.

  The method of laminating the decorative sheet on the various adherends is not particularly limited, and for example, a method of sticking the sheet to the adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, and the like.

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

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example. “Part” is based on mass unless otherwise specified.

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 average roughness Ra (JIS B0601: 2001, cut-off value 0.8 mm) of the surface 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 under the following measurement conditions using a trade name SE-340 manufactured by Kosaka Laboratory.
[Surface probe for surface roughness detection]
Product name SE2555N manufactured by Kosaka Laboratory Ltd. (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 cut-off value λc (0.8 × 5 = 4.0 mm)
・ Feeding speed of stylus: 0.5mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

1-2. Specular Gloss For the decorative sheets of Examples and Comparative Examples, the 60-degree specular gloss on the surface 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. Designability (three-dimensional effect)
20 subjects evaluated and averaged 2 points for those who felt a strong stereoscopic effect, 1 for those that could not be said to be either, and 0 for those that felt poor in stereoscopic effect. “AA” having an average score of 1.7 or more, “A” having an average score of 1.4 or more and less than 1.7, “B” having an average score of 1.0 or more and less than 1.4, A sample having an average score of less than 1.0 was designated as “C”.

2. Preparation of decorative sheet [Example 1]
On a support 1 of an easily adhesive polyethylene terephthalate film (Mitsubishi Chemical Polyester Co., Ltd., Diafoil Z350, thickness 45 μm), a mat layer forming coating liquid having the following formulation was applied and dried to form a mat layer having a thickness of 1 μm. . Next, on the mat layer, by the gravure multicolor printing, the conduit groove pattern picture layer 2B and the conduit groove pattern are formed of an ink containing 60 parts by mass of an acrylic polyol and 40 parts by mass of hexamethylene diisocyanate and containing a black-brown pigment. A wood grain pattern layer 2 having a thickness of 1 μm composed of a bark pattern layer 2A other than a conduit portion formed of an ink containing a yellow-brown pigment in the same binder resin as the ink was formed. Next, in a plan view, a glittering ink layer forming coating liquid having the following prescription is applied to the base 10 composed of the support 1 and the pattern layer 2 so as to correspond to the portion immediately above the portion where the wood pattern image layer 2A is formed. By applying and drying by a printing method, a glittering ink layer having a thickness of 3 μm was formed. Next, a transparent resin layer forming coating solution having the following formulation is applied and dried by a gravure printing method so as to be positioned directly above the glitter ink layer in plan view, thereby forming a transparent resin layer 30 having a thickness of 10 μm. The decorative sheet 100 of Example 1 having the laminated structure shown in the sectional view of FIG. 4 was obtained. The resulting decorative sheet 100 had a positional deviation in plan view between the pattern of the glitter ink layer 20 and the pattern of the transparent resin layer 30 within 30 μm, which is the detection limit of human eyes.
The gravure printing plate used for forming the glitter ink layer and the transparent resin layer is one in which the cells of the plate are formed by FM screen, and the pattern and area of the cells (halftone dots) of both plates are the same. There is something. The plate on which the glitter ink layer 20 and the transparent resin layer 30 were printed had no cells in the region corresponding to the portion directly above the picture layer 2B having a conduit groove pattern in plan view. As a result, there was no ink transfer in the glittering ink layer 20 and the transparent resin layer 30 immediately above the pattern layer 2B in the duct groove pattern in a plan view of the decorative sheet.

<Matte layer forming coating solution>
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 glittering ink layer formation>
・ 35 parts by weight of pearl pigment (white pearl, particle size 25 μm)
・ Acrylic resin 65 parts by mass

<Coating liquid for forming transparent resin layer>
-30 parts by mass of urethane acrylate oligomer (number average molecular weight 1500, average functional group number 5)
・ 70 parts by mass of urethane acrylate polymer (number average molecular weight 8000, average functional group number 10)
・ Diluting solvent

[Example 2]
The pattern layer was formed directly on the easily adhesive polyethylene terephthalate film without forming the mat layer. In addition, in the ink for printing the conduit groove pattern picture layer 2B, in addition to the black-brown pigment, 26 parts by mass of a matting agent of silica (average particle size: 2 μm) is added to 100 parts by mass of the binder resin. It was. Other than that was carried out similarly to Example 1, and obtained the decorative sheet of Example 2. FIG.

[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 The gloss difference in the decorative sheet surface can be increased. For this reason, the decorative sheet of Examples 1-2 was excellent in a three-dimensional effect, and was excellent in the designability.
On the other hand, the decorative sheets of Comparative Examples 1 and 2 had inadequate gloss difference in the decorative sheet surface 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 have an extremely good design.

1: support 2: picture layer 10: substrate 20: glitter ink layer 30: transparent resin layer 100: decorative sheet

Claims (8)

  A decorative sheet comprising a glittering ink layer having an arbitrary pattern on a substrate, and a transparent resin layer in synchronization with the pattern of the glittering ink layer in a region immediately above the glittering ink 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 respect to the base, the glitter ink layer and the same are synchronized with the decorative sheet. The decorative sheet according to claim 1, wherein the high gloss region is formed by the region having the transparent resin layer.   The decorative sheet according to claim 1 or 2, wherein at least one surface of the substrate is roughened, and the glitter ink layer is provided on the roughened surface.   The decorative sheet according to any one of claims 1 to 3, wherein the base further has a pattern layer.   The difference between the arithmetic average roughness Ra of JIS B0601: 2001 of the surface of the high gloss area and the arithmetic average roughness Ra of JIS B0601: 2001 of the surface of the low gloss area [Ra of the low gloss area-of the high gloss area Ra] is 3 micrometers or more, The decorative sheet of Claim 2.   Difference between 60 degree specular gloss of JIS Z8741: 1997 in the high gloss area and 60 degree gloss of JIS Z8741: 1997 in the low gloss area [60 degree gloss of high gloss area−60 degrees of low gloss area The decorative sheet according to claim 2, wherein the glossiness is 3 or more.   The decorative sheet according to any one of claims 1 to 6, wherein an arbitrary pattern of the glitter ink layer has a light and shade, and the light and shade is formed by a density of halftone dots.   A decorative material obtained by laminating and integrating an adherend and a surface of the decorative sheet according to any one of claims 1 to 7 opposite to the surface having the transparent resin layer.