JP2014069507A - Decorative sheet and decorative plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet and a decorative plate each imparting a low-gloss appearance, devoid of a turbid appearance, and excellent in terms of cleaning friendliness (wiping friendliness).SOLUTION: The provided decorative sheet possesses at least a surface protective layer atop a substrate; the surface protective layer includes a curable resin and an inorganic filler; the content of the inorganic filler with respect to 100 parts.mass of the curable resin is 12-25 parts.mass; the surface of the surface protective layer opposite the plane thereof facing the substrate has an uneven pattern; the area ratio of valley portions of the uneven pattern is at least 15%; opening widths of the valley portions along the short-side direction thereof, bottom widths of the valley portions along the short-side direction thereof, and the depths of the valley portions simultaneously satisfy specified relations; a decorative plate using the same is also provided.

Description

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

  The decorative sheet may be required to have a low gloss feeling depending on the desired application. As a technique for imparting a low gloss feeling to a decorative sheet, for example, a decorative sheet in which a matting agent such as matte silica is added to the outermost surface layer is known (for example, Patent Documents 1 and 2). However, when a matting agent such as matte silica is used, it is possible to express a low gloss feeling, but it is necessary to add a large amount of matting agent in order to express a rich low gloss feeling. Therefore, the more the low gloss feeling is emphasized, the more the cloudiness of the outermost layer increases, the sharpness of the pattern provided in the lower layer decreases, and the resin component forming the outermost layer decreases. Therefore, there is a problem that surface protection characteristics such as weather resistance, stain resistance and scratch resistance are deteriorated.

  In addition, as a method for imparting a low gloss feeling to a decorative sheet, a method for forming a concavo-convex pattern has also been proposed (for example, Patent Document 3). However, with this method, if the occupancy ratio of the concavo-convex pattern on the decorative sheet is low, a sufficiently low gloss feeling cannot be obtained, and if the occupancy ratio of the concavo-convex pattern is high, a low gloss feeling can be obtained, but easy to clean (wipe) (Easy to remove) may be reduced. This tendency is particularly remarkable when the decorative sheet is used as a flooring or the like. In addition, when a decorative sheet is used as a flooring material, depending on the pattern of the concavo-convex pattern applied to the decorative sheet, fine powdery dirt such as gypsum board powder or wood powder generated when constructing a member using the decorative sheet However, when it falls on the decorative sheet and enters the concave portion of the uneven pattern, it becomes difficult to wipe, and the ease of cleaning (easiness of wiping) may be significantly reduced.

Japanese Patent Laid-Open No. 2004-167779 JP 2004-148632 A JP 2010-100030 A

  Under such circumstances, an object of the present invention is to provide a decorative sheet and a decorative board that have a low gloss feeling and no cloudiness, and are excellent in ease of cleaning (easiness of wiping).

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problem can be solved by the following invention. That is, the present invention provides the following decorative sheet and decorative plate.

1. The substrate has at least a surface protective layer, the surface protective layer contains a curable resin and an inorganic filler, and the content of the inorganic filler is 12 to 25 parts per 100 parts by mass of the curable resin. It is a mass part, has a concavo-convex pattern on the surface opposite to the surface on which the base material of the surface protective layer is provided, the area ratio of the concave portions in the concavo-convex pattern is 15% or more, and the short side direction of the concave portions When the width of the opening is b ₁ (μm), the width of the bottom in the short side direction of the recess is b ₂ (μm), and the depth of the recess is h (μm), A decorative sheet satisfying (3) at the same time.
Formula (1): b ₂ /h≧4.2
Formula (2): b ₂ / b ₁ > 0.22
Formula (3): 130 μm ≧ h ≧ 5 μm
2. The decorative sheet according to 1 above, further satisfying the following mathematical formula (4) when the width of the front edge of the concave portion is s (μm).
Formula (4): b ₁ ≦ s
3. 3. The decorative sheet according to 1 or 2 above, comprising a decorative layer, a thermoplastic resin layer, and a surface protective layer in this order on the substrate.
4). A substrate, an adhesive layer, and a decorative sheet, the decorative sheet having at least a surface protective layer on the substrate, the surface protective layer containing a curable resin and an inorganic filler, and The content of the inorganic filler is 12 to 25 parts by mass with respect to 100 parts by mass of the curable resin, and has a concavo-convex pattern on the surface opposite to the surface facing the substrate of the surface protective layer. The area ratio of the concave portions in the pattern is 15% or more, the width of the front edge in the short side direction of the concave portion is b ₁ (μm), the width of the bottom portion in the short side direction is b ₂ (μm), and A decorative board that satisfies the above mathematical expressions (1) to (3) at the same time when the depth is h (μm).

  According to the present invention, it is possible to obtain a decorative sheet having a low gloss feeling and no cloudiness, and excellent in ease of cleaning (easiness of wiping).

It is a schematic diagram which shows the cross section of one aspect of the decorative sheet of this invention. It is a schematic diagram for demonstrating the recessed part of the uneven | corrugated pattern of the decorative sheet of this invention. It is a schematic diagram for demonstrating the recessed part of the uneven | corrugated pattern of the decorative sheet of this invention.

The decorative sheet of the present invention has at least a surface protective layer on a substrate, the surface protective layer contains a curable resin and an inorganic filler, and the content of the inorganic filler is 100 masses of the curable resin. 12 to 25 parts by mass with respect to the part, having a concavo-convex pattern on the surface opposite to the surface facing the substrate of the surface protective layer, and the area ratio of the recesses in the concavo-convex pattern is 15% or more When the width of the front edge in the short side of the recess is b ₁ (μm), the width of the bottom in the short side of the recess is b ₂ (μm), and the depth of the recess is h (μm), The following mathematical formulas (1) to (3) are satisfied at the same time. The decorative sheet of the present invention will be described with reference to FIGS.
Formula (1): b ₂ /h≧4.2
Formula (2): b ₂ / b ₁ > 0.22
Formula (3): 130 μm ≧ h ≧ 5 μm

(Base material)
If the base material 2 is used as a base material of a decorative sheet, it can be used without a restriction | limiting, A resin sheet is preferable and a polyolefin resin sheet is especially preferable. Examples of the polyolefin resin include polyethylene resin, polypropylene resin, polybutene resin, ethylene / propylene copolymer resin, ethylene / propylene / butene copolymer resin, and olefin thermoplastic elastomer. Polypropylene resin is preferred from the viewpoint of surface protection properties such as weather resistance and scratch resistance.

  Preferred examples of the polypropylene resin include homopolypropylene resins, random polypropylene resins, block polypropylene resins, and α-olefin copolymers having 2 to 20 carbon atoms other than propylene and having a crystal part of polypropylene. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of ethylene, 1-butene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, etc., for example, ethylene / Propylene copolymers, ethylene / propylene / butene copolymers and the like are also preferred.

The substrate 2 is preferably colored with a colorant. This is because from the viewpoint of design properties, it is possible to conceal the foundation such as a substrate on which the decorative sheet is provided. Colorants that can be used for the substrate 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, iso Organic pigments such as indolinone yellow and phthalocyanine blue, or metallic pigments composed of scaly foils such as dyes, aluminum and brass, pearl luster composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate (pearl) A pigment etc. are mentioned preferably.
The amount of the colorant used in the substrate is not particularly limited as long as it does not lower the film-forming property when the substrate is obtained by extrusion molding and the mechanical strength of the substrate.

  Further, the resin sheet used for the substrate 2 may be biaxially stretched. By using a biaxially stretched sheet, excellent scratch resistance is obtained and mechanical strength is also good compared to a non-stretched sheet or a uniaxially stretched sheet.

  The thickness of the substrate 2 is usually preferably 20 to 200 μm, more preferably about 40 to 160 μm, and further preferably 40 to 100 μm from the viewpoint of mechanical strength and ease of handling.

When using a resin sheet as the base material 2, an additive may be blended in the resin composition forming the resin sheet, if necessary. Examples of the additive include a filler, a flame retardant, an antioxidant, a lubricant, a foaming agent, an ultraviolet absorber, and a light stabilizer.
Among the above additives, it is preferable to contain an inorganic filler such as calcium carbonate, barium sulfate, clay, and talc from the viewpoint of obtaining excellent processing characteristics. The content of these inorganic fillers is preferably in the range of 1 to 60% by mass with respect to the substrate 2.

  Further, from the viewpoint of improving the adhesion to the colored solid layer 3 or the like, the base material 2 may be subjected to corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment on one or both sides as desired. A physical or chemical surface treatment such as an oxidation method such as a method or an uneven method such as a sand blast method or a solvent treatment method can be performed.

(Surface protective layer)
The surface protective layer 5 is provided on the outermost surface of the decorative sheet of the present invention, and is a layer that imparts surface protective properties such as weather resistance, stain resistance, scratch resistance, water resistance, and chemical resistance to the decorative sheet. The surface protective layer 5 has a concavo-convex pattern 6 on the surface opposite to the surface facing the substrate 2, and the area ratio of the concave portions 7 in the concavo-convex pattern 6 needs to be 15% or more. This is because if the area ratio of the recesses is less than 15%, a low gloss feeling cannot be obtained. Further, the area ratio of the recesses 7 is preferably 95% or less, more preferably 25 to 85%, from the viewpoint of simultaneously obtaining excellent low gloss and easy cleaning (easy wiping).
Here, the area ratio of the recesses 7 is the ratio of the total area of the front edges of the recesses 7 present on the surface of the surface protective layer 5 to the area of the decorative sheet. For the area ratio, the area of 1 cm × 1 cm on the decorative sheet is taken as one unit, and the area of the frontage of all the recesses at any 10 locations is measured using a surface roughness shape measuring instrument, and the 10 locations are measured. Let the average value of the area ratio of the recessed part 7 be an area ratio of a recessed part. This measuring method is effective for a sheet having an uneven pattern 6 on the entire decorative sheet. However, for a decorative sheet in which the uneven pattern 6 is extremely densely distributed, the concave portions where the uneven patterns 6 are concentrated are arbitrarily measured at ten locations, and the area ratio of the concave portions is determined by the same method as described above. This is because if the distribution of the uneven pattern 6 is extremely rough, the number of the recessed parts 7 is reduced.

Further, the recess 7 has a width of the front edge of the recess 7 in the short side direction b ₁ (μm), a width of the bottom in the short side direction of the recess 7 b ₂ (μm), and a depth of the recess 7 of h (Μm), the following formulas (1) to (3) are satisfied at the same time. By having a concavo-convex pattern 6 constituted by concave portions 7 of b ₁ (μm), b ₂ (μm), and h (μm) that satisfy these three mathematical expressions at the same time, excellent low gloss feeling and cleaning Ease (wiping ease) is obtained.
Formula (1): b ₂ /h≧4.2
Formula (2): b ₂ / b ₁ > 0.22
Formula (3): 130 μm ≧ h ≧ 5 μm

Further, when the width of the front edge of the concave portion 7 is s (μm), it is preferable that the following mathematical formula (4) is further satisfied.
Formula (4): b ₁ ≦ s

The shape of the front edge of the concave portion 7 in the concavo-convex pattern 6 is generally a substantially linear shape, a substantially circular shape, or a substantially elliptical shape, and usually as shown in FIGS. 2 (a) and 2 (b). It has a lot of substantially elliptical shapes. The cross-sectional shape in the depth direction of the recess 7 is usually a semi-elliptical shape as shown in FIG. The width b _{1 in} the short side direction of the front edge of the concave portion 7, the width b _{2 in the} bottom side direction of the concave portion 7, the depth h of the concave portion 7, and the width of the front edge in the long side direction of the concave portion 7 shown in these drawings. s can be measured by using a surface roughness measuring machine, and an average value of measured values obtained by measuring each of 10 concave portions 7 at a measurement length of 10 mm is adopted.
In the present invention, “Surfcom 120A (model number)” (manufactured by Tokyo Seimitsu Co., Ltd.) is used as the surface roughness measuring instrument, and the measurement conditions are cut-off value: 2.50 mm, cut-off filter type: 2RC, inclination correction. Method: Straight line. In this invention, although it measures using said measuring machine, it is not restrict | limited to this.

The shape of the concave portion 7 constituting the concavo-convex pattern 6 is various, but the average value of the measured values for the concave portion 7 at any 10 locations with a measurement length of 10 mm of width b ₁ , width b ₂ , depth h, and width s If the above numerical formula is satisfied, excellent low gloss and easy cleaning (wiping ease) can be obtained. That is, among the recesses 7 at any 10 locations with a measurement length of 10 mm, even if there are recesses 7 that do not satisfy the above formula in some of the recesses 7, the average value of the measured values for the recesses 7 at the 10 locations is If the above formula is satisfied, excellent low gloss and easy cleaning (easiness of wiping) can be obtained.

The measurement method of the width b ₁ , the width b ₂ , the depth h, and the width s in one recess 7 is performed as follows. First, as the width b ₁ , the width of the widest portion in the short side direction of the substantially elliptical shape of the front end of the recess 7 on the surface of the surface protective layer 5 is measured. For example, as shown in Example 1 of FIG. 3, when the concave portion has a shape with two concave portions, it is treated as one concave portion, and the width of the two concave portions is set to the width b. _Set to ₁ . When the recess has a shape having a gentle gradient as shown in Example 3 of FIG. 3, the width of the outermost surface of the opening is defined as a width b ₁ . Moreover, when the surface of the surface protective layer 5 shifts up and down as shown in Example 4 of FIG. 3, the width according to the lower surface is defined as the width b ₁ .

When the width b ₂ has a bottom portion that is substantially horizontal to the width b ₁ as shown in FIG. 2C, the width of the bottom portion is defined as the width b ₂ . In addition, when the recess has a shape with two recesses as shown in Example 1 in FIG. 3, the width of the bottom of the recess having the deeper one of the two recesses. Is the width b ₂ . In addition, when the bottom portion has a shape having a gentle gradient as shown in Example 2 or Example 3 of FIG. 3, when a straight line that is horizontal with the width b ₁ is drawn from the bending point a closest to the bottom portion. The width is defined as width b ₂ .

The depth h is defined as the depth h from the surface on which the width b ₁ is determined to the lowest point of the recess.
For the width s, the width of the longest direction of the substantially elliptical shape of the front end of the recess 7 on the surface of the surface protective layer 5 is measured.

  As shown in Equation (3), the depth h needs to be 5 μm or more and 130 μm or less. If h is less than 5 μm, low gloss cannot be obtained. On the other hand, when the thickness is larger than 130 μm, the thickness of the decorative sheet of the present invention is usually about 160 μm, and the decorative sheet is locally thinned, so that the strength of the decorative sheet is insufficient. For the same reason, h is preferably 10 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or less, and further preferably 10 μm or more and 40 μm or less.

The width b ₂ of the width of the bottom portion in the short side direction of the concave portion 7 is required to be 4.2 times or more of the depth h based on the formula (1). When the width b ₂ (μm) is less than 4.2 times the depth h, it becomes too narrow with respect to the depth h, and it becomes difficult to remove when fine powdery dirt such as gypsum board powder or wood powder enters. , Excellent cleaning ease (wiping ease) cannot be obtained. For the same reason, b ₂ / h is preferably 4.5 times or more, more preferably 5 times or more, and further preferably 7 times or more.
Further, the width b ₂ is preferably 20 to 1500 μm, more preferably 50 to 500 μm, and still more preferably 50 to 300 μm. When the width b ₂ is within the above range, excellent low gloss and easy cleaning (easiness to wipe) can be obtained.

The width b _{1 in} the short side direction of the front edge of the recess 7 is b ₂ / b ₁ larger than 0.22, that is, less than 4.55 times the width b ₂ (1 / 0.22). Less than double). When b ₂ / b ₁ is 0.22 or less (the width b ₁ is 4.55 times or more of the width b ₂ ), the opening of the recess 7 becomes too wide, so that an excellent low gloss feeling is obtained. I can't get it. For the same reason, b ₂ / b ₁ is preferably 0.25 or more, and more preferably 0.3 or more.
In addition, the width b ₁ is preferably 100 to 5000 μm, more preferably 200 to 1500 μm, and further preferably 200 to 500 μm. When the width b ₂ is within the above range, excellent low gloss and easy cleaning (easiness to wipe) can be obtained.

The width s of the front edge of the concave portion 7 is preferably not less than the width b ₁ from the mathematical formula (4), more preferably not less than 1.5 times the width b ₁ , and more preferably twice. That's it. When the width s is within the above range with respect to the width b ₁ , excellent low gloss and easy cleaning (easiness to wipe) are obtained. From the same viewpoint, the width s is preferably 10,000 times or less of the width b ₁ and more preferably 6000 times or less. When it is within this range, a high design property can be obtained when the uneven pattern is a wood grain conduit pattern, a hairline, a single-line groove, or the like.

  The method for forming the concavo-convex pattern 6 is not particularly limited. For example, an embossing process using an embossing plate or a shaping sheet, or a layer having a concavo-convex pattern on the surface using a transfer sheet having a concavo-convex pattern layer is used. Examples thereof include a method of transferring and imparting an uneven pattern. In the present invention, embossing using an embossed plate is preferable from the viewpoint of expressing a lower gloss feeling.

Preferable examples of the pattern shape of the concavo-convex pattern 6 include a wood grain conduit pattern, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain, a hairline, and a ridge groove. In the present invention, if the shape of the front of the concave portion is a pattern shape having many concave portions having a substantially elliptical shape, a more excellent low gloss feeling and ease of cleaning (easy to wipe) can be obtained. , Hairline, and multi-row groove are more preferable, and a wood grain conduit pattern is particularly preferable.
In the case of adopting a wood grain conduit pattern, a more realistic wood grain can be expressed by synchronizing the concave portion 7 of the concavo-convex pattern 6 and the conduit of the decorative layer 3 (particularly the pattern layer 32).

  The surface protective layer 5 contains a curable resin such as a thermosetting resin, a two-component curable resin, or an ionizing radiation curable resin, and an inorganic filler, and the content of the inorganic filler is 100 mass of the curable resin. It is required to be 12 to 25 parts by mass with respect to the part, and is preferably composed of a cured product of a curable resin composition containing a curable resin and an inorganic filler. From the viewpoint of obtaining surface protection characteristics, a two-component curable resin composition containing a two-component curable resin and an inorganic filler, or a cured product of an ionizing radiation curable resin composition containing an ionizing radiation curable resin and an inorganic filler. Preferably, it is configured.

  The two-component curable resin is not particularly limited as long as it is a resin that is cured by the main agent and the curing agent. Preferably, the two-component curable urethane has a polyol (polyhydric alcohol) as the main agent and an isocyanate curing agent as the main agent. Resins are preferred.

As the main agent, for example, polyols such as polyethylene glycol, polypropylene glycol, butylene glycol, neopentyl glycol, and 1,6-hexanediol, as well as polyols having a hydroxyl group as a functional group such as acrylic polyol, polyester polyol, and polyether polyol are included. Preferably mentioned. These can be used individually or in mixture of multiple types.
The glass transition point (Tg) of the main agent is preferably 0 to 150 ° C., and preferably 50 to 125 ° C., from the viewpoint of obtaining excellent surface protection characteristics. In addition, the weight average molecular weight (weight average molecular weight in terms of polystyrene measured by GPC method) of the main agent is preferably 10,000 to 500,000, more preferably 50,000 to 250, from the viewpoint of obtaining excellent surface protection properties. , 000.

  As the isocyanate curing agent, a conventionally known compound may be appropriately used. For example, aromatic isocyanate such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, or 1,6-hexa Polyisocyanates such as aliphatic (or alicyclic) isocyanates such as methylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), and hydrogenated tolylene diisocyanate are used. Further, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers and the like are also used.

  Next, the ionizing radiation curable resin composition preferably used for forming the surface protective layer 5 is a resin composition that is cured by irradiating with ionizing radiation, and the ionizing radiation includes electromagnetic waves or charged particle beams. Those having an energy quantum capable of polymerizing or cross-linking molecules, such as ultraviolet rays (UV) or electron beams (EB), and other charged particles such as electromagnetic waves such as X-rays and γ-rays, α-rays and ion beams Lines are also used.

The ionizing radiation curable resin 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 is not particularly limited as long as it is a (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule, and examples thereof include diethylene glycol di (meth) acrylate and propylene glycol diester. (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) An acrylate etc. are mentioned preferably. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the present invention, the number of functional groups of the polyfunctional (meth) acrylate monomer is not particularly limited as long as it is 2 or more, but 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 singly 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 decorative sheet of the present invention can be provided with excellent surface protection characteristics and the decorative sheet does not shrink during the production process.

  In the present invention, 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. It is because the surface protection characteristic which was excellent in the decorative sheet of this invention can be provided as the number of functional groups is in said range, and it does not shrink | contract in a manufacture process.

  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.

  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 resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin. 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 resin used in the present invention 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 ionizing radiation curable resin composition contains an inorganic filler. As inorganic filler, silica, magnesium carbonate, kaolin, clay, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc , Wollastonite, Potassium titanate, Magnesium sulfate, Calcium sulfate, Magnesium phosphate, Sepiolite, Zonolite, Aluminum borate, Sendust, Alnico magnet, Ferrite and other magnetic powder, Cement, Antimony trioxide, Magnesium oxysulfate, Water Those made of inorganic materials such as Japanese gypsum and alum are preferred. Of these, silica is preferred because it provides excellent low gloss, is easily procured and is inexpensive.
The particle diameter of the inorganic filler is preferably 0.1 to 20 μm, more preferably 0.3 to 10 μm, and still more preferably 0.3 to 5 μm. Further, when the average particle diameter of the inorganic filler is within the above range, surface protection characteristics can be obtained in addition to excellent low gloss.

  Content of an inorganic filler needs to be 12-25 mass parts with respect to 100 mass parts of curable resin. If the content of the inorganic filler is less than 12 parts by mass, an excellent low gloss feeling cannot be obtained. On the other hand, when there is more content of an inorganic filler than 25 mass parts, a cloudiness will become remarkable. From the viewpoint of obtaining an excellent low gloss feeling and preventing the occurrence of cloudiness, the content of the inorganic filler is preferably 15 to 25 parts by mass.

  Further, the curable resin composition forming the surface protective layer 5 may contain a weathering agent such as an ultraviolet absorber (UVA) or a hindered amine light stabilizer (HALS) in order to improve weatherability. These weathering agents are reactive ultraviolet absorbers having reactive functional groups having ethylenic double bonds such as (meth) acryloyl groups, vinyl groups, and allyl groups, or reactive light stabilizers (HALS). It is preferable from the point that stable weather resistance can be obtained without causing bleeding out of the weathering agent.

  In addition, the curable resin composition has various additives such as titanium oxide and aluminum paste for the purpose of improving the concealability of the surface protective layer 5 in the resulting decorative sheet, preventing yellowing of the base material, and improving light resistance. Inorganic color pigments such as carbon black can be appropriately added.

  The thickness of the surface protective layer 5 is preferably 10 to 45 μm, and more preferably 10 to 35 μm. When the thickness of the surface protective layer 5 is within the above range, excellent surface protective properties can be obtained.

(Decoration layer)
The decorative layer 3 gives decorativeness to the decorative sheet. The decorative layer 3 may be a concealing layer 31 (solid printing layer) that is uniformly colored, or various patterns may be printed using ink and a printing machine. The pattern layer 32 may be formed, or a combination of the hiding layer 31 and the pattern layer 32 may be used.

  By providing the concealing layer 31, it is possible to conceal the base such as the substrate 2 or the substrate on which the decorative sheet is provided, and when the base 2 is colored or has color unevenness, an intended color is given to the surface. Color can be adjusted. Further, the concealing layer 31 is usually formed with an opaque color for the purpose of concealing the base material 2 and the base, but it can be formed with a colored transparent color to make use of the pattern of the base material 2. And may be appropriately selected depending on the purpose.

The pattern layer 32 may be a grain pattern imitating the surface of a rock such as a grain pattern, marble pattern (for example, travertine marble pattern), a fabric pattern imitating a texture or cloth pattern, a tiled pattern, a brickwork pattern, or the like. Patterns such as parquet, patchwork, etc., which are a combination of these, can be applied to the decorative sheet, and are formed as flat, concavo-convex, or convex layers. In the present invention, a grain pattern is preferable from the viewpoint of a synergistic effect with the uneven pattern 6.
These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates constituting the pattern. Is done.

  Moreover, fine powdery stains such as gypsum board powder and wood powder are particularly noticeable when the decorative sheet exhibits a dark color, but even if the decorative sheet of the present invention is a dark decorative sheet, Excellent ease of cleaning (easiness of wiping) can be exhibited.

Here, the dark color in the present invention preferably has a CIE 1976 lightness index L ^* value in the L ^* a ^* b ^* color system of 60 or less, more preferably 50 or less, and even more preferably 30 or less. In the dark color according to the present invention, the color coordinate a ^* value in the L ^* a ^* b ^* color system is preferably -20 to 20, more preferably -5 to 5, and further preferably 0 to 5. The color coordinate b ^* value is preferably −20 to 20, more preferably −5 to 5, and further preferably −2 to 3.
The L ^* value, a ^* value, and b ^* value are defined in the color display method of JIS Z8729-2004. These values are, for example, a spectrocolorimeter (“CR-300 (model number)”: Konica It can be measured by Minolta Holdings, Inc.).

  Preferred examples of the colorant contained in the ink composition forming the decorative layer 3 include those exemplified as the colorant contained in the substrate 2 described above. The content of the colorant is not particularly limited as long as the hiding function of the hiding layer 31 and the decorative property of the pattern layer 32 are ensured and the applicability of the ink composition forming these layers is not impaired.

  Moreover, the ink composition which forms the decoration layer 3 can contain an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardening | curing agent, etc. suitably as needed.

  The thickness of the decoration layer 3 is usually about 0.5 to 20 μm, and preferably 1 to 10 μm. If the thickness of the decoration layer 3 exists in the said range, the designability which was excellent in the decorative sheet can be provided, and concealment property can be provided.

(Thermoplastic resin layer)
The thermoplastic resin layer 4 is provided between the base material 2 or the decorative layer 3 and the surface protective layer 5 as required, protects the base material 2 and the decorative layer 3, and is resistant to contamination by exposing these layers. It is a layer that prevents a decrease in scratch resistance.

A preferred example of the thermoplastic resin forming the thermoplastic resin layer 4 is a polyolefin resin.
As polyolefin resin, the polyolefin resin illustrated as a material which comprises the resin sheet of the base material 2 can be employ | adopted preferably. Of these polyolefin resins, polypropylene resins are preferable, and homopolypropylene resins are more preferable.

The thermoplastic resin layer 4 may be constituted by a thermoplastic resin composition containing a colorant, if necessary, and may be translucent as long as the visibility of the decorative layer 3 is ensured. Further, the thermoplastic resin composition may contain other additives such as fillers, flame retardants, antioxidants, lubricants, foaming agents, ultraviolet absorbers, light stabilizers, and the like as necessary. .
Further, one or both surfaces of the thermoplastic resin layer 4 can be subjected to a physical or chemical surface treatment such as the above-described oxidation method or unevenness method.

  The thickness of the thermoplastic resin layer 4 is preferably in the range of 5 to 200 μm from the viewpoint of protecting the substrate 2 and the decoration layer 3 and ensuring mechanical strength, ease of handling, and transparency. Preferably it is 10-150 micrometers, More preferably, it is 10-100 micrometers.

(Adhesive layer)
The adhesive layer 8 is a layer that is preferably provided between the base material 2 and the thermoplastic resin layer 4 when the thermoplastic resin layer 4 is provided, and improves the adhesion between these layers.
The adhesive used in the adhesive layer can be appropriately selected according to the material such as the resin constituting the base material 2 or the decorative layer 3 or the thermoplastic resin layer 4. For example, α- such as polyethylene and polypropylene elastomer can be used. Preferable examples include polyolefin resins, polyester resins, urethane resins, and epoxy resins. Especially, polyester resin is mentioned from viewpoints, such as adhesiveness and heat resistance, and 2 liquid curable polyester resin is especially preferable. When an ionizing radiation curable resin is used as the curable resin for forming the surface protective layer 5, the two-component curable urethane resin exemplified as the curable resin for forming the surface protective layer 5 should be used. Is also preferable.

  The thickness of the adhesive layer 8 varies depending on the type of adhesive used, the material such as the base material 2 or the decorative layer 3, or the resin constituting the thermoplastic resin layer 4. It is preferable to set it to about -30 micrometers, and it is more preferable to set it as 1-15 micrometers.

(Primer layer)
The primer layer 9 is provided between the thermoplastic resin layer 4 and the surface protective layer 5 when the surface protective layer 5 described later is provided on the thermoplastic resin layer 4 to improve the adhesion between these layers. It is a layer to be made.

The resin composition for forming the primer layer 9 is not particularly limited. For example, in addition to a weather resistance improver such as an ultraviolet absorber or a light stabilizer such as a hindered amine based binder resin, an extender pigment, a solvent, a stabilizer, What mixed suitably the plasticizer, the catalyst, the hardening | curing agent, etc. is used.
There is no restriction | limiting in binder resin, For example, ester resin, urethane resin, an acrylic resin, polycarbonate resin, a vinyl chloride-vinyl acetate copolymer etc. are mentioned preferably, These resins may be used individually by 1 type. In addition, two or more kinds may be used in combination. Also preferred are two-component curable resins. 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. Two-component curing in which the main agent is a polyol (polyhydric alcohol) and the curing agent is an isocyanate curing agent. A urethane resin is preferable. Preferred examples of the two-component curable urethane resin used for the primer layer 9 include the main agent and the curing agent exemplified as the two-component curable urethane resin preferably used for the adhesive layer 8, and include the thermoplastic resin layer 4 and the surface protective layer. The material may be selected as appropriate in consideration of the material constituting 5.

  The thickness of the primer layer 9 is usually about 0.5 to 20 μm, and preferably 1 to 10 μm. When the thickness of the primer layer 9 is within the above range, excellent adhesion can be obtained.

(Back primer layer)
The back primer layer (not shown) is a layer preferably provided for the purpose of improving the adhesion between the substrate 2 and various adherends, and is the surface of the substrate 2 on the side where the surface protective layer 5 is provided. Provided on the opposite surface (back surface).
The material used for forming the back primer layer is not particularly limited, and urethane resin, acrylic resin, polyester resin, vinyl chloride / vinyl acetate copolymer, chlorinated polypropylene resin, chlorinated polyethylene resin, and the like are preferable. What is necessary is just to select suitably according to a dressing material.
Moreover, it is preferable that the thickness of a back surface primer layer is about 1-5 micrometers, More preferably, it is 1-3 micrometers. When the thickness is within the above range, excellent performance as a primer layer can be obtained efficiently.

(Production method)
The decorative sheet of the present invention has at least a surface protective layer on the substrate, and has a predetermined concavo-convex pattern on the surface protective layer. The surface protective layer is provided on the substrate by a method described later, It can be manufactured by providing a concavo-convex pattern on the surface protective layer. Hereinafter, a preferable example is demonstrated about the method of manufacturing the decorative sheet of this invention. The decorative sheet of the present invention preferably has, for example, a step (1) a step of providing a decorative layer on a substrate, a step (2) a step of providing a thermoplastic resin layer so as to face the decorative layer, a step (3) It can manufacture by passing through the process of providing a surface protective layer on a thermoplastic resin layer, and the process (4) the process of providing an uneven | corrugated pattern in this surface protective layer. According to this manufacturing method, a decorative sheet having a base material, a decorative layer, a thermoplastic resin layer, and a surface protective layer can be manufactured.

Step (1) is a step of providing the decoration layer 3, that is, the hiding layer 31 and / or the pattern layer 32 on the base material 2.
First, a resin sheet used for the substrate 2, for example, a polyolefin resin composition in which a colorant and other additives are added to a polyolefin resin as desired, a method such as a calendar method, an inflation method, a T-die extrusion method, etc. Can be obtained by forming into a sheet. Biaxial stretching may be performed as necessary.
Moreover, the base material 2 can also perform physical or chemical surface treatments, such as said oxidation method and uneven | corrugated method, on the single side | surface or both surfaces.

The formation method of the concealment layer 31 and the pattern layer 32 is not particularly limited. For example, the concealment layer 31 is formed using the resin composition used for the formation of the concealment layer 3, for example, a roll coating method, a knife coating method, It may be formed by various coating methods such as an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, a flow coating method, and a dip coating method.
Moreover, the pattern layer 32 uses the ink composition used for formation of said pattern layer 32, for example, gravure printing method, offset printing method, screen printing method, flexographic printing method, electrostatic printing method, inkjet printing method, etc. It may be formed by coating by the above method. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the partial vapor deposition method such as metal, the etching method, etc. may be used or used in combination with other forming methods. Good.

  Moreover, when providing a back surface primer layer, what is necessary is just to apply and select suitably the resin composition which forms a back surface primer layer from the formation method illustrated as a formation method of the concealing layer 31 or the pattern layer 32.

Step (2) is a step of providing the thermoplastic resin layer 4 so as to face the decorative layer 3. As a method of providing the thermoplastic resin layer 4, an adhesive layer 8 is provided on the decorative layer 3, and a thermoplastic resin sheet that has been formed into a sheet shape is extruded onto the adhesive layer 8 by extrusion lamination or the thermoplastic layer. Thermal lamination provided by heating and pressurizing the resin sheet, and further, the thermoplastic resin composition forming the thermoplastic resin sheet is heated and melted by using a T-die extruder, and the decorative layer 3 or the adhesive layer 8 is heated. An EC coating method for forming the thermoplastic resin layer 4 and adhering and laminating on the decorative layer 3 or the adhesive layer 8 is preferably performed by flowing down and sandwiching between a rubber roll and a cooled metal roll. Can be mentioned.
Further, the back primer layer may be formed on the base material 2 before the thermoplastic resin layer 4 is provided, or may be formed after the thermoplastic resin layer 4 is provided.

Step (3) is a step of providing the surface protective layer 5 on the thermoplastic resin layer 4 formed in the above step (2).
The surface protective layer 5 is a resin used by applying a curable resin composition containing a curable resin such as the thermosetting resin or ionizing radiation curable resin on the thermoplastic resin layer 4 or the primer layer 9. It is obtained by curing by a curing method suitable for the composition.
When an ionizing radiation curable resin composition is used as the curable resin composition, the surface protective layer 5 is formed by applying the ionizing radiation curable resin composition onto the thermoplastic resin layer 4 or the primer layer 9 and then applying the resin composition. It can be formed by curing the product to obtain a cured product.

  The ionizing radiation curable resin composition is applied to the surface of the thermoplastic resin layer 4 or the primer layer 9 so that the thickness after curing is about 10 to 45 μm, gravure printing method, bar coating method, roll coating method. , A known method such as a reverse roll coating method or a comma coating method, preferably a gravure printing method. The viscosity of the ionizing radiation curable resin composition is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the thermoplastic resin layer 4 or the primer layer 9 by a coating method described later.

Next, the uncured resin layer formed by applying the ionizing radiation curable resin composition is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer, and the ionizing radiation curable resin composition The surface protective layer 5 of the cured product is formed.
When an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer, but it is preferable to cure the uncured resin layer at an accelerating voltage of about 70 to 300 kV.

In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a material that deteriorates due to an electron beam is used as the substrate 2 or the thermoplastic resin layer 4, the transmission depth of the electron beam and the resin layer By selecting an accelerating voltage so that the thicknesses of the base material 2 are substantially equal, it is possible to suppress irradiation of the base material 2 with an extra electron beam and minimize deterioration of the base material 2 due to the excess electron beam. You can stay.
The irradiation dose is preferably such that the crosslinking density of the resin layer is saturated, usually 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 100 kGy (1 to 10 Mrad), more preferably 30 to 70 kGy (3 to 7 Mrad). It is selected in the range.
The electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

When the ionizing radiation is irradiated to cure the ionizing radiation curable resin composition, it can be cured in a low oxygen atmosphere. When cured in this manner, surface protective properties that are particularly excellent in scratch resistance can be obtained.
The oxygen concentration is preferably 2% or less, more preferably 1% or less, and even more preferably 0.5% (500 ppm) or less. The low oxygen atmosphere can be obtained by, for example, nitrogen, argon, hydrogen, etc., preferably nitrogen, or air suction so that the oxygen concentration is about 2% or less.

When the primer layer 9 is provided between the thermoplastic resin layer 4 and the surface protective layer 5, the primer layer 9 may be provided on the thermoplastic resin layer 4 before the surface protective layer 5 is provided.
The primer layer 9 is formed by applying the resin composition forming the primer layer 9 by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. be able to.

  Step (4) is a step of providing the uneven pattern 6 on the surface protective layer 5. The method for forming the concavo-convex pattern 6 is not particularly limited, but an embossing process using an embossed plate or a shaping sheet, or a layer having a concavo-convex pattern is used to transfer a layer having a concavo-convex shape. Examples thereof include a method for imparting an uneven pattern. In the present invention, it is preferable to use embossing from the viewpoint of productivity, and further embossing using an embossed plate is preferable.

  As the embossing, usually an embossing method by heating and pressurization using an embossed plate is preferably used. The embossing method by heating and pressurizing heats the surface of the decorative sheet on the surface protective layer side usually at about 160 to 180 ° C, pressurizes with the embossing plate, shapes the uneven pattern of the embossing plate, cools and fixes A known sheet-fed or rotary embossing machine can be used.

  In addition, although the process (4) of providing the concavo-convex pattern 6 describes the process of providing the concavo-convex pattern 6 by embossing the surface protective layer 5 after the surface protective layer 5 is provided, The method of providing the uneven pattern 6 on the surface protective layer 5 is not limited to this. For example, the uneven pattern 6 can be formed on the surface protective layer 5 by providing the surface protective layer 5 after embossing the thermoplastic resin layer 4. In this case, the concavo-convex shape formed by embossing the thermoplastic resin layer 4 is formed on the surface of the surface protective layer 5 provided thereafter to form the concavo-convex pattern 6.

(Decorative board)
The decorative board of the present invention has a substrate, an adhesive layer, and a decorative sheet in this order, and the decorative sheet has at least a surface protective layer 5 on the substrate 2, and the surface protective layer 5 is made of a curable resin. The surface of the surface protective layer that is opposite to the surface of the surface protective layer that contains an inorganic filler and the content of the inorganic filler is 12 to 25 parts by weight with respect to 100 parts by weight of the curable resin. The concave-convex pattern in the concave-convex pattern has an area ratio of 15% or more, the width of the front edge of the concave portion in the short side direction is b ₁ (μm), and the width of the bottom portion in the short side direction is b ₂ (μm) and when the depth of the recess is h (μm), the above formulas (1) to (3) are satisfied at the same time. That is, the decorative board of the present invention has a substrate, an adhesive layer, and the decorative sheet 1 of the present invention in this order.

  The substrate used for the decorative board of the present invention is not particularly limited, and is a wood board such as a wood veneer, wood plywood, particle board, and MDF (medium density fiber board), a plaster board such as a plaster board, a plaster slag board, Calcium silicate board, asbestos slate board, lightweight foamed concrete board, cement board such as hollow extrusion cement board, fiber cement board such as pulp cement board, asbestos cement board, wood chip cement board, earthenware, porcelain, stoneware, earthenware, glass, Ceramic plates such as steel plates, iron plates, galvanized steel plates, polyvinyl chloride sol coated steel plates, metal plates such as aluminum plates and copper plates, polyolefin resin plates, acrylic resin plates, ABS plates, polycarbonate plates and other thermoplastic resin plates, phenol resin plates , Urea resin plate, unsaturated polyester resin plate, polyurethane resin plate, epoxy resin plate, melamine resin plate Any thermosetting resin plate, phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin, glass fiber nonwoven fabric, fabric, paper, and other various fibrous base materials And a resin plate such as a so-called FRP plate obtained by impregnation and curing. Moreover, as a board | substrate, you may use as a composite substrate which laminated | stacked 2 or more types of the said various board | substrate by well-known means, such as an adhesive agent and heat sealing | fusion.

The adhesive used for the adhesive layer for adhering the substrate and the decorative sheet 1 is not particularly limited. For example, a thermoplastic resin adhesive such as a polyamide-based adhesive, an acrylic adhesive, or a vinyl acetate-based adhesive. Preferable examples include curable resin adhesives such as thermosetting urethane adhesives and epoxy resins. Further, a two-component curable polyurethane adhesive or polyester adhesive using isocyanate as a curing agent can also be applied. Among these, a thermoplastic resin adhesive is preferable because it functions as a cushion layer and has an effect of suppressing cracks in the surface protective layer 5 even during processing under severe conditions.
An adhesive can also be used for the adhesive layer. As the pressure-sensitive adhesive, an acrylic, urethane, silicone, rubber or the like can be appropriately selected and used.
Although there is no restriction | limiting in particular in the thickness of an contact bonding layer, Usually, it is the range of 1-100 micrometers. By setting it as this range, the effect of suppressing the occurrence of cracks in the surface protective layer 5 can be obtained even during excellent adhesiveness and processing under severe conditions.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

(Evaluation method)
1. Evaluation of low glossiness About the decorative boards obtained in Examples and Comparative Examples, the gloss value was measured at a measurement angle of 60 ° using a precision gloss meter (manufactured by Murakami Color Research Laboratory Co., Ltd.). The measured gloss value was evaluated according to the following criteria.
◎ The gloss value was less than 5.
○ The gloss value was 5 or more and less than 8.
△ The gloss value was 8 or more and less than 10.
× The gloss value was 10 or more.
2. Evaluation of cloudiness About the decorative board obtained by the Example and the comparative example, the cloudiness of the surface was confirmed visually and evaluated by the following reference | standard.
◎ There was no cloudiness.
○ There was almost no cloudiness.
Δ Although there was some cloudiness, there was no practical problem.
X A cloudiness was clearly confirmed.
3. Evaluation of Ease of Cleaning (Ease of Wiping) For the decorative boards obtained in Examples and Comparative Examples, gypsum board powder was spread on the decorative boards (thickness: 4.5 μm, average particle diameter of gypsum board powder: 5 μm). After spreading evenly with a wet cloth, it was dried with a dryer. Next, the state of wiping the gypsum board powder when wiped with a clean waste cloth was evaluated according to the following criteria.
◎ We were able to wipe off neatly.
○ Almost no residue was wiped off.
Δ: There was a slight wiping residue, but there was no problem in practical use.
X The remaining wipe was conspicuous.

Example 1
A colored polypropylene sheet (thickness: 60 μm, random polypropylene resin) is prepared as a base material, and a reverse primer layer (thickness) is formed on one surface of the sheet by a gravure coating method using a primer agent (acrylic urethane resin). : 2 μm). Next, on the surface opposite to the surface provided with the back surface primer layer, a woodgrain pattern layer (thickness: 3 μm, thickness of CIE1976 lightness index L ^* value in the L ^* a ^* b ^* color system is 60 or less) ) By a gravure coating method to form an adhesive layer (polyester resin, thickness: 5 μm). A transparent polypropylene resin sheet (thickness: 80 μm) was laminated on the adhesive layer by extrusion lamination. After the corona discharge treatment is applied to the surface of the transparent polyolefin resin sheet, a two-component curable urethane resin composition is applied to form a primer layer (thickness: 2 μm), and an inorganic filler (silica particles (average particle diameter: 11 μm, untreated, pore volume: 5 ml / g or more), content: 14 parts by mass with respect to 100 parts by mass of ionizing radiation curable resin) (80% bifunctional urethane acrylate oligomer) Mass parts (weight average molecular weight: 1500, glass transition temperature (Tg): −55 ° C.) and hexafunctional aliphatic urethane acrylate oligomer (weight average molecular weight: 1500, glass transition temperature (Tg): 200 ° C. or higher, “UA306H ( (Product name) ”, a resin composition containing 20 parts by mass of Kyoeisha Chemical Co., Ltd.) is applied by a roll coating method, and an electron beam irradiation apparatus is used. The surface protective layer was formed by curing the uncured resin layer of the ionizing radiation curable resin composition by irradiating an electron beam under the conditions of oxygen concentration: 200 ppm, acceleration voltage: 175 keV, and irradiation amount: 5 Mrad. Next, embossing is performed (sheet temperature: 120 to 160 ° C., pressure: 10 to 40 kg / cm ² ), and the uneven pattern of the grain 1 on the surface protective layer (the grain ratio 1 is the area ratio of the recess: 50%, width b ₂ / Depth h: 13.8, width b ₂ / width b ₁ : 0.43, depth h: 18 μm, width b ₁ / width s: 1.8 × 10 ⁻⁴ .) The decorative sheet of the present invention was obtained.
Furthermore, the obtained decorative sheet was stuck on a medium density wood fiber board (MDF, thickness: 2.7 mm) through an adhesive layer (vinyl acetate aqueous emulsion adhesive, thickness: 7 μm). The decorative board of the present invention was obtained. Said evaluation was performed about the obtained decorative board, and the evaluation result was shown in Table 1.

Examples 2, 3 and Comparative Examples 1-3
In Example 1, a decorative sheet and a decorative board were obtained in the same manner as in Example 1 except that the content of the inorganic filler in the ionizing radiation curable resin composition forming the surface protective layer was changed to the content shown in Table 1. Got. Said evaluation was performed about the obtained decorative board, and the evaluation result was shown in Table 1.

* 1, ionizing radiation: an example using an ionizing radiation curable resin composition, two-component curing: an example using a two-component curable urethane resin.
* 2. The surface layer is a surface protective layer, and the resin layer is a thermoplastic resin layer.

Examples 4-7 and Comparative Example 4
In Example 2, decorative plates of Examples 4 to 7 and Comparative Example 4 were obtained in the same manner as in Example 2 except that the uneven pattern was changed from wood grain 1 to wood grain 2 to 6. Said evaluation was performed about the obtained decorative board, and the evaluation result was shown in Table 2.

Examples 8 to 10 and Comparative Examples 5 to 9
In Example 2, decorative plates of Examples 8 to 10 and Comparative Examples 5 to 9 were obtained in the same manner as Example 2 except that the uneven pattern was changed from the grain 1 to the grain 7 to 14. Said evaluation was performed about the obtained decorative board, and the evaluation result was shown in Table 3.

Examples 11-12
In Example 2, the formation of the surface protective layer was carried out using a two-part curable urethane resin (acrylic polyol (glass transition point (Tg): 100 ° C., weight average molecular weight: 100,000) 100 parts by mass and hexamethylene diisocyanate 15 parts by mass. The two-component curable urethane resin diluted with a solvent is applied onto a transparent polyolefin resin sheet and then dried to an extent that does not cause blocking in a drying furnace at 80 ° C. In Example 11 and Example 2 except that the surface protective layer was provided by curing for 48 hours or more in the same manner as in Example 2 except that the transparent polyolefin resin sheet was embossed. 12 decorative panels were obtained. Said evaluation was performed about the obtained decorative board, and the evaluation result was shown in Table 4.

Example 13
In Example 12, the two-component curable urethane resin used in Example 11 was used for forming the surface protective layer, and the two-component curable urethane resin diluted with a solvent was applied onto a transparent polyolefin resin sheet and then dried at 80 ° C. The decorative board of Example 13 was prepared in the same manner as in Example 12 except that it was dried to the extent that no blocking occurred in the furnace, and then cured in a curing room at 40 ° C. for 48 hours or more to provide a surface protective layer. Obtained. Said evaluation was performed about the obtained decorative board, and the evaluation result was shown in Table 4.

  The decorative sheet of the present invention has a low gloss feeling and no cloudiness, and is excellent in ease of cleaning (wiping ease). The sheet of the present invention is widely used for building materials such as finishing materials and mounting materials in buildings, or for furniture, etc., and is a member using a decorative sheet from the viewpoint of exhibiting excellent ease of cleaning (wiping ease). It is particularly preferably used for applications such as flooring, in which fine powdery dirt such as gypsum board powder and wood powder generated during construction is applied, or dirt is accumulated in daily life.

1. Cosmetic sheet Base material 3. Decorative layer 31. Concealment layer 32. Pattern layer 4. 4. Thermoplastic resin layer Surface protective layer 6. Uneven pattern Concave part 7a-c. Recesses a to c
8). 8. Adhesive layer Primer layer

Claims (8)

The substrate has at least a surface protective layer, the surface protective layer contains a curable resin and an inorganic filler, and the content of the inorganic filler is 12 to 25 parts per 100 parts by mass of the curable resin. It is a mass part, has a concavo-convex pattern on the surface opposite to the surface facing the base material of the surface protective layer, the area ratio of the concave portion in the concavo-convex pattern is 15% or more, and the short side direction of the concave portion When the width of the opening is b ₁ (μm), the width of the bottom in the short side direction of the recess is b ₂ (μm), and the depth of the recess is h (μm), A decorative sheet satisfying (3) at the same time.
Formula (1): b ₂ /h≧4.2
Formula (2): b ₂ / b ₁ > 0.22
Formula (3): 130 μm ≧ h ≧ 5 μm The decorative sheet according to claim 1, further satisfying the following mathematical formula (4), where s (μm) is the width of the front edge of the recess.
Formula (4): b ₁ ≦ s   The decorative sheet according to claim 1 or 2, wherein the surface protective layer is a cured product of a curable resin composition containing a curable resin and an inorganic filler, and the curable resin is an ionizing radiation curable resin.   The decorative sheet according to any one of claims 1 to 3, further comprising a decorative layer, a thermoplastic resin layer, and a surface protective layer in this order on the substrate.   The decorative sheet according to any one of claims 1 to 4, wherein the uneven pattern is a wood grain conduit pattern.   The decorative sheet according to any one of claims 1 to 5, wherein the inorganic filler is silica.   The decorative sheet according to any one of claims 1 to 6, which is used for flooring. A substrate, an adhesive layer, and a decorative sheet, the decorative sheet having at least a surface protective layer on the substrate, the surface protective layer containing a curable resin and an inorganic filler, and The content of the inorganic filler is 12 to 25 parts by mass with respect to 100 parts by mass of the curable resin, and has a concavo-convex pattern on the surface opposite to the surface facing the substrate of the surface protective layer. The area ratio of the concave portions in the pattern is 15% or more, the width of the front edge in the short side direction of the concave portion is b ₁ (μm), the width of the bottom portion in the short side direction is b ₂ (μm), and A decorative board that satisfies the following mathematical formulas (1) to (3) simultaneously when the depth is h (μm).
Formula (1): b ₂ /h≧4.2
Formula (2): b ₂ / b ₁ > 0.22
Formula (3): 130 μm ≧ h ≧ 5 μm