JP2016061046A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet that mitigates intensity of regular reflection light and prevents whitening, at the same time retaining sheen that creates a luxurious feeling.SOLUTION: A decorative sheet has an irregular surface at least on one side, of which an arithmetic average roughness (Ra) prescribed in JIS B 0601:1994 when a cut-off value in any direction of the irregular surface is assumed to be 2.5 mm, and an arithmetic average roughness (Ra) prescribed in JIS B 0601:1994 when the cut-off value is assumed to be 0.08 mm satisfy the following equations (1) and (2): 0.82 μm≤Ra≤3.80 μm (1); and Ra≤0.39 μm (2).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 to decorate the members to be used.
Since these decorative sheets impair the appearance when external light such as illumination is reflected, the surface of the decorative sheet may be subjected to a low gloss treatment by making the surface uneven.

As means for reducing the gloss of the decorative sheet, (1) means for directly making the decorative sheet substrate uneven by sandblasting, chemical etching, embossing, etc., (2) means for forming an uneven layer on the substrate, etc. Is mentioned. As a means of (2), after forming a concavo-convex layer containing particles and a binder resin on a substrate, or after forming a transparent layer on a substrate, the transparent layer is subjected to sand blasting, chemical etching, embossing, etc. Means for making irregularities and the like can be mentioned.
Patent Documents 1 to 3 and the like are disclosed as examples of the above-described means for reducing gloss.

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

Patent Documents 1 and 2 disclose a decorative sheet having a gloss adjusting resin layer made of a crosslinked cured product of an ionizing radiation curable resin composition containing matte silica on a base material.
Patent Document 3 discloses a decorative sheet formed by embossing using an embossed plate that has been sandblasted.

The decorative sheets of Patent Documents 1 to 3 do not have a big problem regarding low gloss.
However, if the gloss is too low, light diffusion due to surface irregularities becomes excessive and whitening occurs, and there is a problem that the gradation level and sharpness of the pattern located at the lower part of the decorative sheet are lowered, and the design property is impaired. .
In recent years, a decorative sheet has been required to have a high-class feeling, and the decorative sheet has a high-class feeling even by gloss. However, the decorative sheet simply having a high gloss has a problem in that the intensity of the specular reflection light becomes too strong, causing discomfort to the viewer.

  An object of the present invention is to provide a decorative sheet and a decorative material that have a high-class feeling due to luster, suppress the intensity of regular reflection light, and do not cause whitening.

  In order to solve the above problems, the present inventors have intensively studied, and as a result, divided the uneven surface of the decorative sheet into a high-frequency unevenness that is a roughness component and a low-frequency unevenness that is a swell component, and these two unevennesses. It has been found that the above-mentioned problems can be solved by setting the above to a predetermined condition. That is, the present invention provides the following decorative sheets and cosmetic materials [1] to [10].

[1] A decorative sheet in which at least one surface is an uneven surface, and the arithmetic average roughness (Ra _{2.5) according} to JIS B0601: 1994 when the cut-off value is 2.5 mm in any direction of the uneven surface. ) And an arithmetic average roughness (Ra _0.08 ) of JIS B0601: 1994 when the cut-off value is 0.08 mm, a decorative sheet satisfying the following conditions (1) and (2).
0.82 μm ≦ Ra _2.5 ≦ 3.80 μm (1)
Ra _0.08 ≦ 0.39 μm (2)
[2] The decorative sheet according to [1], further satisfying the following condition (3) in an arbitrary direction of the uneven surface.
0.05 ≦ Ra _0.08 / [Ra _2.5 −Ra _0.08 ] ≦ 0.50 (3)
[3] The above-mentioned [1] in which the ten-point average roughness (Rz _2.5 ) of JIS B0601: 1994 when the cut-off value is 2.5 mm satisfies the following condition (4) in any direction of the uneven surface Or the decorative sheet as described in [2].
Rz _2.5 ≦ 15.00μm (4)
[4] The above-mentioned [1] in which the ten-point average roughness (Rz _0.08 ) of JIS B0601: 1994 satisfies the following condition (5) when the cut-off value is 0.08 mm in any direction of the uneven surface -The decorative sheet in any one of [3].
Rz _0.08 ≦ 1.80μm (5)

[5] In any direction of the uneven surface, the average interval (Sm _2.5 ) of the unevenness of JIS B0601: 1994 when the cut-off value is 2.5 mm satisfies the following condition (6). The decorative sheet according to any one of [4].
350μm ≦ Sm _2.5 (6)
[6] The decorative sheet according to any one of the above [1] to [5], which has a concavo-convex layer on a substrate, and the surface of the concavo-convex layer is the concavo-convex surface.
[7] The decorative sheet according to [6], in which a design layer is provided between the base material and the uneven layer.
[8] The decorative sheet according to [7], wherein the design layer includes a wood grain pattern.
[9] A decorative material obtained by laminating and integrating an adherend and a surface opposite to the uneven surface of the decorative sheet according to any one of [1] to [8].
[10] The decorative material according to [9], which is used as a decorative material for floors.

  The decorative sheet and the decorative material of the present invention can prevent a viewer from feeling uncomfortable because the specular reflection light has an excessively strong intensity while having a high-class feeling with an appropriate gloss. Furthermore, the decorative sheet and the decorative material of the present invention can suppress deterioration in the gradation level and sharpness of the pattern due to whitening, and can improve the design.

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.

[Decorative sheet]
The decorative sheet of the present invention is a decorative sheet in which at least one surface is an uneven surface, and the arithmetic average roughness of JIS B0601: 1994 when the cut-off value is 2.5 mm in any direction of the uneven surface. (Ra _2.5 ) and arithmetic average roughness (Ra _0.08 ) of JIS B0601: 1994 when the cut-off value is 0.08 mm satisfy the following conditions (1) and (2).
0.82 μm ≦ Ra _2.5 ≦ 3.80 μm (1)
Ra _0.08 ≦ 0.39 μm (2)

FIG.1 and FIG.2 is sectional drawing which shows one Embodiment of the decorative sheet 10 of this invention. 1 and 2 has a design layer 2, an adhesive layer 3, a thermoplastic resin layer 4, and a concavo-convex layer 5 on one surface of a substrate 1, and the decorative sheet 10 on the concavo-convex layer 5 side of the decorative sheet. The surface is uneven. 1 is composed of a low-frequency concavo-convex layer 51 and a high-frequency concavo-convex layer 52. The concavo-convex layer 5 in FIG. 2 is composed of a high-frequency concavo-convex layer 52 and is embossed from the high-frequency concavo-convex layer 52 side. Yes.
In addition, the decorative sheet of the present invention may be any sheet as long as at least one surface is an uneven surface and satisfies the conditions (1) and (2) in any direction of the uneven surface, as shown in FIG. Each layer is an optional component.

Irregular surface The decorative sheet of the present invention is such that at least one surface is an irregular surface, and satisfies the above conditions (1) and (2) in any direction of the irregular surface. Conditions (1) and (2) define the arithmetic average roughness (Ra) of JIS B0601: 1994 with different cut-off values. Hereinafter, the technical significance of defining Ra with different cutoff values will be described.
The cutoff value is a value indicating the degree to which the swell component (low frequency component) is cut from the cross-sectional curve composed of the roughness component (high frequency component) and the swell component (low frequency component). In other words, the cutoff value is a value indicating the fineness of the filter that cuts the swell component (low frequency component) from the cross-sectional curve. More specifically, when the cut-off value is large, the filter is coarse, so that a large swell of the swell component (low frequency component) is cut, but a small swell is not cut. That is, when the cutoff value is large, the value includes a swell component (low frequency component). On the other hand, if the cut-off value is small, the filter is fine, so that most of the swell component (low frequency component) is cut. That is, when the cut-off value is small, the roughness component (high frequency component) that does not substantially include the swell component (low frequency component) is accurately reflected.
In JIS B0633 referred to in JIS B0601, it is stipulated that a specific cut-off value (reference length) is adopted according to the degree of surface roughness. In the case of a general-purpose decorative sheet, the cut-off value is 2.5 mm, and in the conventional decorative sheet, the surface roughness is managed only by the cut-off value of 2.5 mm.
However, when the Ra of one cut-off value is used, it is not possible to design surface irregularities intended for both the roughness component (high frequency component) and the waviness component (low frequency component). There is a limit.
In the present invention, it is possible to design the surface unevenness reflecting both the roughness component (high frequency component) and the waviness component (low frequency component) by using two cutoff values.

Condition (1) has an arithmetic average roughness Ra _2.5 of 0.82 μm or more and 3.80 μm or less. If Ra _2.5 is less than 0.82 μm, the range of the angular distribution (diffuse reflection intensity distribution) of the light reflected on the decorative sheet surface becomes narrow, and as a result, the glossy range in the surface of the decorative sheet becomes narrow, and is visually recognized. The person becomes difficult to feel a sense of quality. On the other hand, if Ra _2.5 is less than 0.82 μm, the specular reflection intensity becomes too strong, and the viewer is uncomfortable. On the other hand, if Ra _2.5 exceeds 3.80 μm, the diffuse reflection intensity distribution becomes too wide. As a result, the difference in diffuse reflection intensity near the center of the visual field of the viewer is reduced, and the viewer cannot recognize the gloss. On the other hand, when Ra _2.5 exceeds 3.80 μm, the diffuse reflection intensity at each angle is reduced within the reflected light distribution range, and the viewer is less likely to feel gloss.
In other words, the viewer recognizes the gloss based on the absolute value of the diffuse reflection intensity and the difference in the diffuse reflection intensity near the center of the field of view, and also recognizes the high-class feeling that the gloss recognition range is not too narrow or too wide. doing. And gloss with a high-class feeling can be provided by condition (1).
Condition (1) is more preferable to satisfy the 1.00μm ≦ Ra _2.5 ≦ 3.50μm, it is more preferable to satisfy the 1.25μm ≦ Ra _2.5 ≦ 3.00μm.

In addition, in this invention, conditions (1) and (2) and the other conditions mentioned later are taken as the average value at the time of measuring 20 times.
Moreover, in this invention, conditions (1) and (2) and the other conditions mentioned later should just satisfy | fill in at least arbitrary directions of a decorative sheet. For example, when a decorative sheet is used as a flooring, the direction perpendicular to the window (the direction in which sunlight enters through the window) is important because it has a strong diffuse reflection intensity and is deeply related to gloss recognition. The vertical direction (the direction in which a person walks toward the door) is important in that it easily enters the human field of view. Therefore, if the conditions (1) and (2) and other conditions described later are satisfied in an arbitrary direction, the effect of each condition can be sufficiently exhibited in the direction.

Condition (2) is that Ra _0.08 is 0.39 μm or less. When Ra _0.08 exceeds 0.39 μm, the angle distribution (diffuse reflection intensity distribution) of the light reflected on the decorative sheet surface is large (resulting in a widening of the reflection angle distribution diagram) and whitening occurs. . When whitening occurs in the decorative sheet, the gradation level and sharpness of the pattern are degraded. Even if the condition (1) is satisfied, if Ra _0.08 exceeds 0.39 μm, the diffuse reflection intensity distribution becomes wide and it becomes difficult to feel gloss.
The lower limit of Ra _0.08 is not particularly limited, but when Ra _0.08 is set to a predetermined value or more, the distribution of diffuse reflection intensity can be relaxed, and the deterioration of visibility due to a sudden change in diffuse reflection intensity can be suppressed. Is preferable. For example, if there is a place where a sudden angle change occurs in the unevenness of the low frequency component, an angle at which the reflection intensity changes abruptly in the reflection intensity distribution is recognized as a defect, but Ra _0.08 is a predetermined value or more. By providing unevenness of a high frequency component, it is possible to relieve sudden changes in reflection intensity and make it difficult to recognize as a defect.
Condition (2) preferably satisfies 0.10 μm ≦ Ra _0.08 ≦ 0.35 μm, and more preferably satisfies 0.20 μm ≦ Ra _0.08 ≦ 0.35 μm.

The uneven surface preferably further satisfies the following condition (3) in an arbitrary direction.
0.05 ≦ Ra _0.08 / [Ra _2.5 −Ra _0.08 ] ≦ 0.50 (3)
By satisfying the condition (3), low-frequency components and high-frequency components are appropriately contained in the surface irregularities, and uniform and smooth gloss can be imparted without causing whitening.
Condition (3) preferably satisfies 0.10 ≦ Ra _0.08 / [Ra _2.5 −Ra _0.08 ] ≦ 0.40, and satisfies 0.10 ≦ Ra _0.08 / [Ra _2.5 −Ra _0.08 ] ≦ 0.30. It is more preferable to satisfy.

In addition, from the same viewpoint as the condition (3), the uneven surface preferably further satisfies the following condition (3 ′) in an arbitrary direction.
0.50 μm ≦ Ra _2.5 −Ra _0.08 ≦ 3.50 μm (3 ′)
Condition (3 ') is more preferable to satisfy the _{0.75μm ≦ Ra 2.5 -Ra 0.08 ≦ 3.00μm} , it is more preferable to satisfy the _{1.00μm ≦ Ra 2.5 -Ra 0.08 ≦ 2.75μm} .

Moreover, it is preferable that the ten-point average roughness (Rz _2.5 ) of JIS B0601: 1994 when the cut-off value is 2.5 mm satisfies the following condition (4) in any direction.
Rz _2.5 ≦ 15.00μm (4)
The ten-point average roughness (Rz) is obtained by dividing the roughness curve of the evaluation length N times the sampling length equal to the cut-off value into N equal parts, and the height from the first place to the fifth place for each section. This is an arithmetic average value of N Rz's when the interval Rz 'between the average altitude at the summit and the average altitude at the bottom from the first to fifth depths is obtained. In this way, Rz is a value that focuses on high and low elevations in the roughness curve. On the other hand, the arithmetic average roughness (Ra) is an average value of the elevation of the entire roughness curve. That is, it can be said that Rz represents the degree of roughness of the roughness curve as in Ra, but represents the randomness of the roughness of the roughness curve.

By setting Rz _2.5 to 15.00 μm or less, it is possible to suppress the randomness of the low-frequency component and to prevent unevenness in gloss. In addition, when the irregularity of the shape of the uneven surface is strong, it tends to look like an artificial object. However, when Rz _2.5 is set to a predetermined value or more, the appearance of the decorative sheet is natural due to the randomness of the low frequency component. Can be granted. Further, when Rz _2.5 is set to a predetermined value or more, it is preferable in that the defect of the decorative sheet can be made inconspicuous.
Therefore, condition (4) is more preferable to satisfy the 3.50μm ≦ Rz _2.5 ≦ 13.00μm, it is more preferable to satisfy the 4.50μm ≦ Rz _2.5 ≦ 12.00μm.

Moreover, it is preferable that the ten-point average roughness (Rz _0.08 ) of JIS B0601: 1994 when the cut-off value is 0.08 mm satisfies the following condition (5) in any direction.
Rz _0.08 ≦ 1.80μm (5)
By setting Rz _0.08 to 1.80 μm or less, it is possible to suppress randomness of high-frequency components and to easily suppress whitening. Further, when Rz _0.08 is set to a predetermined value or more, it is preferable in that the appearance of the decorative sheet can be given a natural feeling and defects can be made inconspicuous due to the randomness of the high frequency component.
For this reason, the condition (5) more preferably satisfies 0.50 μm ≦ Rz _0.08 ≦ 1.50 μm, and more preferably satisfies 0.75 μm ≦ Rz _0.08 ≦ 1.20 μm.

Also, uneven surface, in any direction, the cut-off time of the 2.5mm the value JIS B0601: average distance 1994 of the unevenness (Sm _2.5) preferably satisfies the following condition (6).
350μm ≦ Sm _2.5 (6)
By setting Sm _2.5 to 350 μm or more, it is possible to make the gloss more easily felt. Condition (6) more preferably satisfies 400 μm ≦ Sm _2.5 μm, and more preferably satisfies 500 μm ≦ Sm _2.5 . If Sm _2.5 is too large, the diffuse reflection intensity tends to be uniform over a wide range in the decorative sheet surface. Therefore, Sm _2.5 is preferably 800 μm or less, and more preferably 700 μm or less. .

  The uneven surface described above can be formed by means such as (a) physical or chemical treatment such as embossing, sandblasting, etching, (b) molding by mold, (c) formation of a resin layer having unevenness by coating, and the like.

  The uneven surface by the means (a) can be formed by subjecting a base material or a layer formed on the base material to a physical or chemical treatment such as embossing, sand blasting or etching.

The uneven surface by the means (b) can be formed by preparing a mold having a shape complementary to the uneven surface, pouring a material for forming the uneven surface into the mold, and then removing the mold from the mold. Here, a decorative sheet having a concavo-convex layer on the substrate is obtained by using a material constituting the concavo-convex layer as the material, overlaying the base material after pouring the material into the mold, and removing the concavo-convex layer from the mold together with the base material Can be obtained. Moreover, if the material which comprises a base material is poured into a type | mold and it takes out from a type | mold, the decorative sheet which consists of a base material single layer and has an uneven surface on the base-material surface can be obtained.
When using a curable resin composition (thermosetting resin composition or ionizing radiation curable resin composition) as a material to be poured into a mold, it is preferable to cure the curable resin composition before removing it from the mold.
Formation of the concavo-convex surface with a mold is preferable in terms of excellent reproducibility of the concavo-convex shape.

The uneven surface by the means (c) is applied to a plastic film by applying a coating solution for forming an uneven layer containing a resin component and particles onto a plastic film by a known application method such as gravure coating or bar coating, and is dried if necessary. It can be formed by curing.
As a means for forming the uneven surface by the means (c) alone, first, a means for forming the uneven surface with a single uneven layer can be considered. Specifically, there can be considered a means for controlling the aggregation so that the uneven layer contains two types of particles and the degree of aggregation of the particles is different. However, it is difficult to control the aggregation of a plurality of particles. For this reason, when forming an uneven surface by means of (c) alone, a layer having a high-frequency unevenness (high-frequency uneven layer) is laminated on a layer having a low-frequency unevenness (low-frequency uneven layer). Is preferred.

The uneven surface can also be formed by a combination of the above means (a) to (c). As a combination, for example, a method of forming a high-frequency concavo-convex layer by means of (c) and adding a low-frequency component by means of (a), or forming a low-frequency concavo-convex layer by means of (c), (a ) To add a high frequency component.
Among the above-described concavo-convex surface forming methods, a method of laminating a high-frequency concavo-convex layer by means of (c) on a low-frequency concavo-convex layer formed by means of (c), and a high-frequency concavo-convex layer formed by means of (c) In addition, a method of adding a low-frequency component by means of (a) (embossing is suitable as the means of (a) in this case) and a method of means (b) alone are suitable.

The decorative sheet of the present invention may be composed of a single substrate layer (in this case, the surface of the substrate becomes an uneven surface), or may have an uneven layer on the substrate. Good.
The base material is not particularly limited, and examples thereof include plastic films such as polyester, polyolefin, and polyvinyl chloride, papers, and composites thereof. Among these, a polyolefin resin sheet is 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. From the viewpoint of surface protection properties such as weather resistance and scratch resistance, polypropylene resin is preferred. These base materials may be colored from the viewpoint of design properties.
Moreover, when using a plastic film as a base material, the biaxially stretched thing is suitable from a viewpoint of mechanical strength.
The thickness of the substrate is preferably 20 to 200 μm, more preferably 40 to 160 μm, and still more preferably 40 to 100 μm from the viewpoint of mechanical strength and handleability.
Moreover, 80-400 micrometers is preferable, as for the total thickness of a decorative sheet, 100-300 micrometers is more preferable, and 130-250 micrometers is further more preferable.

  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 / Also included are propylene copolymers, ethylene / propylene / butene copolymers, and the like.

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

The concavo-convex layer The concavo-convex layer preferably contains a resin component, and preferably further contains particles as necessary.
The uneven layer may have a multilayer structure in which a high-frequency uneven layer is laminated on a low-frequency uneven layer, for example.
Although the total thickness of the concavo-convex layer varies depending on the concavo-convex shape to be applied or the configuration of the layer (thermoplastic resin layer, etc.) located closer to the substrate than the concavo-convex layer, it cannot be generally stated, but is preferably 0.1 to 60 μm. 10 to 45 μm is more preferable, and 10 to 35 μm is more preferable.
The thickness of the concavo-convex layer is calculated, for example, by measuring the thickness at 20 locations from a cross-sectional image taken using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) and calculating the average value of the 20 locations. it can. When the film thickness to be measured is on the order of μm, it is preferable to use SEM, and when it is on the order of nm, it is preferable to use TEM or STEM. In the case of SEM, the acceleration voltage is preferably 1 to 10 kV and the magnification is preferably 1000 to 7000 times. In the case of TEM or STEM, the acceleration voltage is preferably 10 to 30 kV and the magnification is preferably 50,000 to 300,000 times. The thickness of a design layer and a concealing layer, which will be described later, can be calculated in the same manner.

  The resin component of the uneven layer preferably includes a thermosetting resin composition or an ionizing radiation curable resin composition, and more preferably includes an ionizing radiation curable resin composition from the viewpoint of improving mechanical strength. Of these, it is more preferable to include an electron beam curable resin composition.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

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

Low-frequency rugged layer The low-frequency rugged layer serves as a lower layer when the rugged layer has a laminated structure of a low-frequency rugged layer and a high-frequency rugged layer, or a high-frequency component by means (a) described above on the low-frequency rugged layer. Has a role as a low-frequency uneven layer serving as a base.

The low-frequency uneven layer preferably contains a resin component and particles.
As long as the particle | grains of a low frequency uneven | corrugated layer can carry out surface unevenness | corrugation, both an organic particle and an inorganic particle can be used. Examples of the organic particles include particles made of polymethyl methacrylate, polyacryl-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine resin, and polyester resin. Can be mentioned. Examples of the inorganic particles include particles made of silica, alumina, zirconia, titania and the like. Among these particles, inorganic particles are preferable from the viewpoint that an excellent low gloss feeling is obtained, they can be easily procured and are inexpensive, and silica is preferable among the inorganic particles.
Further, from the viewpoint of facilitating the formation of low-frequency unevenness, it is preferable that the particles are appropriately aggregated in the low-frequency uneven layer. From the viewpoint of appropriately aggregating the particles, untreated silica or the like that has not been surface-treated is suitable as the particles.

  The content of the particles in the low frequency uneven layer is preferably 0.1 to 60% by mass, more preferably 1 to 50% by mass in the total solid content forming the layer, and 4 to 44. More preferably, it is mass%.

The average particle diameter of the particles in the low frequency uneven layer is preferably 0.2 to 50 μm, more preferably 0.5 to 30 μm, and further preferably 1.0 to 20 μm. In addition, it is preferable that the average particle diameter of the aggregated particles in which the primary particles are aggregated satisfies the above range from the viewpoint of easily forming the low-frequency irregularities.
The thickness of the low-frequency uneven layer is preferably 40 to 2000%, more preferably 100 to 1000% with respect to the average particle diameter of the particles in the low-frequency uneven layer.

In the present invention, the average particle diameter of the particles can be calculated by calculating the particle diameter of individual particles (aggregated particles in the case of aggregation) from the average of the major axis and minor axis of the particles, and averaging these. Specifically, two arbitrary particles are extracted from the surface image or cross-sectional image of the decorative sheet by SEM, TEM, or STEM. (In the case of a surface image, two particles can be selected randomly. Since it is unknown where it is cut, select two particles that are as large as possible), measure the long and short diameters of each particle, calculate the particle diameter of each particle, and display another screen of the same sample The same operation was performed 9 times in the above imaging, and the value obtained from the number average of the particle diameters of a total of 20 particles was defined as the average particle diameter of the particles. The major axis is the longest diameter on the particle screen. The minor axis is a distance between two points where a line segment perpendicular to the midpoint of the line segment constituting the major axis is drawn and the perpendicular line segment intersects the particle.
When calculating the average particle diameter of the particles, it is preferable to use SEM when the average particle diameter to be calculated is on the order of μm, and it is preferable to use TEM or STEM on the order of nm. In the case of SEM, the acceleration voltage is preferably 1 to 10 kV and the magnification is preferably 1000 to 7000 times. In the case of TEM or STEM, the acceleration voltage is preferably 10 to 30 kV and the magnification is preferably 50,000 to 300,000 times.

It is preferable that the low frequency uneven layer has a two-layer structure. Specifically, it is preferable to form a low frequency adjustment layer that smoothes the irregularities of the basic low frequency layer after forming the basic low frequency layer containing the resin component and particles. By forming the low-frequency uneven layer with a two-layer structure, the conditions relating to the low-frequency component can be easily set in the above-described range.
The low frequency adjusting layer contains a resin component, preferably does not substantially contain particles, and more preferably does not contain particles completely.

High-frequency concavo-convex layer The high-frequency concavo-convex layer serves as an upper layer when the concavo-convex layer is a laminated structure of a low-frequency concavo-convex layer and a high-frequency concavo-convex layer, or a low-frequency component is imparted to the high-frequency concavo-convex layer by means (a) described above In this case, it has a role as a base layer.

The high-frequency concavo-convex layer preferably contains a resin component and particles.
As the particles of the high-frequency concavo-convex layer, any of the machine particles and inorganic particles exemplified as the particles of the low-frequency concavo-convex layer can be used. Among these, inorganic particles are preferable from the viewpoint that an excellent low gloss feeling is obtained, they can be easily procured, and are inexpensive, and silica is preferable among the inorganic particles.
Further, from the viewpoint of facilitating the formation of high-frequency unevenness, it is preferable that the particles are dispersed without being aggregated in the high-frequency unevenness layer. From the viewpoint of dispersing the particles, silica having a hydrophobic surface is preferable as the particles.

The content of the particles in the high-frequency concavo-convex layer is preferably 0.1 to 60% by mass, more preferably 1 to 50% by mass, and more preferably 4 to 44% by mass in the total solid content forming the layer. % Is more preferable.
The average particle size of the particles in the high-frequency concavo-convex layer is preferably from 0.1 to 20 μm, more preferably from 0.3 to 10 μm, still more preferably from 0.3 to 5 μm. In addition, it is preferable that the average particle diameter of a primary particle satisfy | fills the said range from a viewpoint of making high frequency unevenness | corrugation easy to form.
The thickness of the high-frequency concavo-convex layer is preferably 150 to 700%, more preferably 400 to 700% with respect to the average particle diameter of the particles in the high-frequency concavo-convex layer.

The high-frequency concavo-convex layer preferably has a two-layer structure. Specifically, it is preferable to form a high frequency adjusting layer that smoothes the irregularities of the basic high frequency layer after forming the basic high frequency layer containing the resin component and the particles. By making the high-frequency concavo-convex layer into a two-layer structure, the conditions relating to the high-frequency component can be easily set in the above-described range.
The high-frequency adjusting layer contains a resin component, preferably does not substantially contain particles, and more preferably does not contain particles completely.

The design layer design layer is provided as necessary for the purpose of enhancing the design properties of the decorative sheet. The design layer is provided, for example, between the base material and the uneven layer.
Examples of the design layer include a colored layer and a pattern layer. These layers may be used in appropriate combination by stacking the same kind or different kinds of layers.

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 by printing or the like.
As the ink used for forming the colored layer, an ink obtained by appropriately mixing a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used.
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.
The colorant may be appropriately selected from the use of the decorative sheet and the color compatibility with the pattern layer. For example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, and petal , Inorganic pigments such as cadmium red, ultramarine, and cobalt blue, organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue, metal pigments made of scaly foil pieces such as aluminum and brass, titanium dioxide-coated mica, base And nacreous (pearl) pigments composed of scaly foil pieces such as conductive lead carbonate.

  The pattern layer is formed by printing or the like. Pattern patterns (pattern patterns) include wood grain patterns, marble patterns (for example, travertine marble patterns), stone patterns that simulate the surface of rocks, fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, There are brickwork patterns, etc., and there are also patterns such as marquetry and patchwork that combine these. In the present invention, a wood grain pattern is preferable from the viewpoint of a synergistic effect with the effect of the uneven surface. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done. As the ink using the pattern layer, the same ink as the colored layer can be used.

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

Thermoplastic resin layer thermoplastic resin layer, for protection of the substrate and decorative layer, if necessary, is provided between the substrate and the relief layer or between the design layer and the uneven layer.
Various thermoplastic resins can be used as the thermoplastic resin forming the thermoplastic resin layer, and polyolefin resins are preferable.
As polyolefin resin, polyolefin resin illustrated as a material which comprises a base material can be employ | adopted preferably. Of these polyolefin resins, polypropylene resins are preferable, and homopolypropylene resins are more preferable.

The thermoplastic resin layer may be constituted by a thermoplastic resin composition containing a colorant, if necessary, and may be translucent as long as the visibility of the design layer is ensured. Moreover, 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. .
The thickness of the thermoplastic resin layer is preferably 5 to 200 μm, more preferably 10 to 150 μm, and more preferably 10 to 100 μm from the viewpoints of protection of the base material and design layer, mechanical strength, handleability, and the like. More preferably.

Adhesive layer Adhesive layer is provided between the base material and the thermoplastic resin layer or between the design layer and the thermoplastic resin layer as necessary in order to improve the adhesion of the thermoplastic resin layer. It is done.
The adhesive used in the adhesive layer can be appropriately selected according to the materials constituting the base material, the design layer, and the thermoplastic resin layer. For example, α-polyolefin resin such as polyethylene and polypropylene elastomer, polyester resin, A urethane resin, an epoxy resin, etc. are mentioned. Among these, polyester resins are preferable from the viewpoint of adhesion and heat resistance, and among these, two-component curable polyurethane resins are preferable.
Although the thickness of an adhesive bond layer changes with kinds etc. of the adhesive agent to be used, it is usually preferable to set it as about 0.1-30 micrometers, and it is more preferable to set it as 1-15 micrometers.

Primer layer The primer layer is provided between the thermoplastic resin layer and the concavo-convex layer, between the base material and the concavo-convex layer, etc., as necessary, in order to improve the adhesion of the concavo-convex layer.
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 primer layer may contain a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent.
The thickness of a primer layer is about 0.5-20 micrometers normally, and 1-10 micrometers is preferable.

Back surface primer layer The back surface primer layer is a layer that is preferably provided for the purpose of improving the adhesion between the substrate and various adherends, and is the surface opposite to the uneven surface of the decorative sheet (for example, the uneven surface of the substrate). The surface opposite the layer).
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.
Moreover, it is preferable that the thickness of a back surface primer layer is 1-5 micrometers, and it is more preferable that it is 1-3 micrometers.

[Cosmetic materials]
The decorative material of the present invention is formed by laminating an adherend and a surface opposite to the uneven surface 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), etc .; gypsum board such as gypsum board, gypsum slag board; calcium silicate board, asbestos slate board, lightweight foam Cement boards such as concrete boards and hollow extruded cement boards; fiber cement boards such as pulp cement boards, asbestos cement boards, wood chip cement boards; ceramics boards such as ceramics, porcelain, earthenware, glass, glazing; iron plates, galvanized steel sheets, poly Metal plates such as steel plates coated with vinyl chloride sol, aluminum plates, copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates, polycarbonate plates; phenol resin plates, urea resin plates, unsaturated polyester resin plates, polyurethane resins Thermosetting resin plates such as plates, epoxy resin plates, melamine resin plates; phenol resins, urea resins, unsaturated polyester Examples include so-called FRP plates in which glass fiber nonwoven fabrics, fabrics, papers, and other various fibrous base materials are impregnated and cured with resins such as copper resin, polyurethane resin, epoxy resin, melamine resin, and diallyl phthalate resin. 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. Among them, it is preferable to use it as an interior material for buildings, and it is preferable to use it for floors.

  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 prepared in Examples and Comparative Examples. The results are shown in Table 1.
(1) Surface roughness measurement (cut-off value 2.5 mm)
Using a surface roughness measuring instrument (trade name: SURFCOM FLEX-50A, manufactured by Tokyo Seimitsu Co., Ltd.), Ra, Rz, and Sm of JIS B0601: 1994 on the outermost surface on the uneven layer side of the decorative sheet under the following measurement conditions. Was measured. In addition, about the decorative sheet (Example 1, comparative example 5) which embossed the grain conduit pattern, it measured in the direction perpendicular | vertical to the arrangement direction of a grain conduit pattern, and in other directions about the other decorative sheet It was measured.
[Surface probe for surface roughness detection]
Product name DM43801 manufactured by Tokyo Seimitsu Co., Ltd. (tip radius of curvature: 2 μm, apex angle: 60 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
Reference length (roughness curve cut-off value λc): 2.5 mm
Evaluation length (reference length (cutoff value λc) × 5): 12.5 mm
・ Feeding speed of stylus: 0.6mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 1000 times ・ Horizontal magnification: 20 times

(2) Surface roughness measurement (cut-off value 0.08 mm)
Using a surface roughness measuring instrument (trade name: SURFCOM FLEX-50A, manufactured by Tokyo Seimitsu Co., Ltd.) under the following measurement conditions, JIS B0601: on the outermost surface of the decorative sheet prepared in Examples and Comparative Examples 1994 Ra and Rz were measured. In addition, about the decorative sheet (Example 1, comparative example 5) which embossed the grain conduit pattern, it measured in the direction perpendicular | vertical to the arrangement direction of a grain conduit pattern, and in other directions about the other decorative sheet It was measured.
[Surface probe for surface roughness detection]
Product name DM43801 manufactured by Tokyo Seimitsu Co., Ltd. (tip radius of curvature: 2 μm, apex angle: 60 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
Reference length (roughness curve cut-off value λc): 0.08 mm
Evaluation length (reference length (cutoff value λc) × 5): 0.4 mm
・ Feeding speed of stylus: 0.6mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 5000 times ・ Horizontal magnification: 500 times

(3) Gloss and whitening The decorative sheet was placed on a horizontal base so that the concave and convex surface faced upward, and the concave and convex surface of the decorative sheet was irradiated with a fluorescent lamp from an angle of 45 degrees. The gloss of the decorative sheet and the degree of whitening were observed from the position in the specular reflection direction of the fluorescent light. Table 1 shows how each decorative sheet looks glossy and whitened.

2. Preparation of decorative sheet [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, a pattern layer with a grain pattern (thickness: 3 μm) and an adhesive layer (polyester resin, thickness: 5 μm) are sequentially formed on the surface opposite to the surface provided with the back primer layer by gravure coating. did. Next, a thermoplastic resin layer (transparent polypropylene resin sheet, thickness: 80 μm) was laminated on the adhesive layer by extrusion lamination.
Next, 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), a back primer layer, a colored polypropylene sheet, A laminate A having a pattern layer, an adhesive layer, and a transparent polypropylene resin sheet / primer layer in this order was obtained.

Next, on the primer layer of the laminate A, a high-frequency uneven layer coating solution 1 having the following formulation was applied by a roll coating method, and using an electron beam irradiation apparatus, oxygen concentration: 200 ppm, acceleration voltage: 175 keV, irradiation amount: 5 Mrad. The uneven layer (thickness: 15 μm) was formed by curing the uncured resin layer of the ionizing radiation curable resin composition by irradiating an electron beam under the above conditions. Subsequently, embossing was performed using an embossing roll having a wood grain conduit pattern (sheet temperature: 120 to 160 ° C., pressure: 10 to 40 kg / cm ² ) to obtain a decorative sheet. The shape of the recess formed by embossing is such that 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 width s of the front edge in the long side direction of the recess, and the average value of the measurement values obtained by measuring each of the 10 recesses at a measurement length of 10 mm, the area ratio of the recess: 50%, width It was a grain pattern having b ₂ / depth h: 9.2, width b ₂ / width b ₁ : 0.24, depth h: 10 μm, width b ₁ / width s: 1.8 × 10 ⁻² .

<High-frequency uneven layer coating solution 1>
-Bifunctional urethane acrylate oligomer 80 parts (weight average molecular weight: 1500, glass transition temperature: -55 ° C)
-Hexafunctional aliphatic urethane acrylate oligomer 20 parts (weight average molecular weight: 1500, glass transition temperature: 200 ° C. or higher)
("UA306H (trade name)", manufactured by Kyoeisha Chemical Co., Ltd.)
14 parts of inorganic particles (hydrophobized silica, average particle size: 3 μm, pore volume: 5 ml / g or more)

[Example 2]
A mold with irregularities was produced by laser micromachining technology. The uneven layer coating solution 2 (excluding inorganic particles from the high frequency uneven layer coating solution 1) was poured into the mold, and then the surface of the laminate A on the primer layer side was overlaid on the mold.
Next, after 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, irradiation amount: 5 Mrad, using an electron beam irradiation apparatus. The laminate A and the concavo-convex layer were taken out of the mold, and a decorative sheet having a concavo-convex layer (thickness: 15 μm) on the laminate A was obtained.

[Comparative Example 1]
A decorative sheet was obtained in the same manner as in Example 1 except that the embossing of Example 1 was not performed.

[Comparative Example 2]
A decorative sheet was obtained in the same manner as in Comparative Example 1 except that the inorganic particles in the high-frequency uneven layer coating solution of Comparative Example 1 were changed to the following.
Inorganic particles (untreated silica, average particle size: 9 μm, pore volume: 5 ml / g or more)

[Comparative Example 3]
A decorative sheet was obtained in the same manner as in Example 1 except that the embossing roll of Example 1 was changed to a grain pattern. The shape of the recess formed by embossing is such that 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 width s of the front edge in the long side direction of the recess, and the average value of the measurement values obtained by measuring each of the 10 recesses at a measurement length of 10 mm, the area ratio of the recess: 50%, width It has a grain pattern having b ₂ / depth h: 8.4, width b ₂ / width b ₁ : 0.29, depth h: 15 μm, width b ₁ / width s: 0.5 × 10 ⁻² It was.

[Comparative Example 4]
A decorative sheet was obtained in the same manner as in Example 1 except that the inorganic particles in the high-frequency uneven layer coating solution of Example 1 were changed to the following and the embossing roll was changed to a grain pattern different from Comparative Example 3. It was. The shape of the recess formed by embossing is such that 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 width s of the front edge in the long side direction of the recess, and the average value of the measurement values obtained by measuring each of the 10 recesses at a measurement length of 10 mm, the area ratio of the recess: 50%, width It is a grain pattern having b ₂ / depth h: 7.5, width b ₂ / width b ₁ : 0.26, depth h: 16 μm, width b ₁ / width s: 0.6 × 10 ⁻² It was.
Inorganic particles (untreated silica, average particle size: 11 μm, pore volume: 1 ml / g)

[Comparative Example 5]
A decorative sheet was obtained in the same manner as in Example 1 except that the embossing roll of Example 1 was changed to a wood grain pattern different from that of Example 1. The shape of the recess formed by embossing is such that 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 width s of the front edge in the long side direction of the recess, and the average value of the measurement values obtained by measuring each of the 10 recesses at a measurement length of 10 mm, the area ratio of the recess: 50%, width The grain pattern was b ₂ / depth h: 2.4, width b ₂ / width b ₁ : 0.13, depth h: 21 μm, width b ₁ / width s: 2.1 × 10 ⁻² .

  From the results of Table 1, it can be seen that the decorative sheets of Examples 1 and 2 have a high-class feeling due to moderate luster and do not give discomfort to the viewer due to the intensity of regular reflection light being too strong. I understand. Furthermore, it turns out that the decorative sheet of Example 1 and 2 can suppress the fall of the gradation level and clarity of a pattern by whitening, and does not impair the visibility of a pattern.

  The decorative sheet of the present invention is useful in that it has a high-class feeling due to luster, the intensity of regular reflection light is suppressed, and whitening does not occur.

1: Base material 2: Design layer 3: Adhesive layer 4: Thermoplastic resin layer 5: Concavity and convexity layer 51: Low frequency concavity and convexity layer 52: High frequency concavity and convexity layer 10: Cosmetic sheet

Claims (10)

A decorative sheet having at least one surface of a concavo-convex surface, the arithmetic average roughness (Ra _2.5 ) of JIS B0601: 1994 when the cut-off value is 2.5 mm in any direction of the concavo-convex surface, and A decorative sheet in which the arithmetic average roughness (Ra _0.08 ) of JIS B0601: 1994 when the cutoff value is 0.08 mm satisfies the following conditions (1) and (2).
0.82 μm ≦ Ra _2.5 ≦ 3.80 μm (1)
Ra _0.08 ≦ 0.39 μm (2) The decorative sheet according to claim 1, further satisfying the following condition (3) in an arbitrary direction of the uneven surface.
0.05 ≦ Ra _0.08 / [Ra _2.5 −Ra _0.08 ] ≦ 0.50 (3) The 10-point average roughness (Rz _2.5 ) of JIS B0601: 1994 when the cut-off value is 2.5 mm for any direction of the uneven surface satisfies the following condition (4). Makeup sheet.
Rz _2.5 ≦ 15.00μm (4) The arbitrary point of the concavo-convex surface, the ten-point average roughness (Rz _0.08 ) of JIS B0601: 1994 when the cut-off value is 0.08 mm satisfies the following condition (5): The decorative sheet according to claim 1.
Rz _0.08 ≦ 1.80μm (5) For any direction of the uneven surface, the cut-off time of the 2.5mm the value JIS B0601: average distance 1994 of the unevenness (Sm _2.5) is one of claims 1 to 4 satisfy the following condition (6) The decorative sheet according to item 1.
350μm ≦ Sm _2.5 (6)   The decorative sheet according to any one of claims 1 to 5, comprising an uneven layer on a substrate, wherein the surface of the uneven layer is the uneven surface.   The decorative sheet according to claim 6, comprising a design layer between the base material and the uneven layer.   The decorative sheet according to claim 7, wherein the design layer includes a wood grain pattern.   A decorative material obtained by laminating and integrating an adherend and a surface opposite to the uneven surface of the decorative sheet according to any one of claims 1 to 8.   The decorative material according to claim 9, which is used as a decorative material for floors.