JP2023049868A - Decorative sheet and decorative material - Google Patents

Abstract

To provide a decorative sheet and a decorative material having large brightness difference due to an excellent matting effect and a luminous pattern layer containing a luminous pigment.SOLUTION: There are provided a decorative sheet and a decorative material which have a luminous pattern layer containing a luminous pigment and a matte layer and has a winkle structure on at least a part of the uppermost surface of the matte layer.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to decorative sheets and decorative materials.

Conventionally, for example, interior members of buildings such as walls, ceilings, and floors; exterior members such as outer walls, eaves, roofs, fences, and fences; , fittings or fixtures such as malls, general furniture such as chests, shelves, desks; kitchen furniture such as dining tables and sinks; or surface decorative panels such as cabinets for home appliances and OA equipment; A so-called decorative sheet or decorative material is used as an article for decorating and protecting the surface of such as.

It is known that decorative materials used for these purposes are provided with a bright pigment-containing layer using a bright pigment for the purpose of expressing a metallic design (Patent Document 1).
Also, in order to improve the design, a method of improving texture by using a matting effect is widely used. As a decorative material using a matting effect, a decorative sheet having a pattern layer and a concealing layer on one side of a base sheet and a gloss adjusting layer such as a matte layer or a gloss layer on the other side has been proposed. (Patent Document 2). In the decorative sheet of Patent Document 2, the difference in gloss between the matte layer and the gloss layer of the gloss adjusting layer provides a design effect that enhances the pattern layer and the concealing layer. For the layer, a matte ink is used in which a total of 50 parts by weight of matting agent, ie, 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, is added to 100 parts by weight of resin.

Patent Document 2 proposes a decorative material having a printed layer and a transparent resin layer in this order on a substrate, and an embossed pattern on the outermost surface of the transparent resin layer.

JP 2014-184613 A JP-A-2000-062081

When a bright pigment-containing layer is provided as in Patent Document 1, external light is reflected by the bright pigment, and the design of the portion with the bright pigment-containing layer is the design of the portion without the bright pigment-containing layer. Compared to , it is visually recognized brightly. It is considered effective to provide a layer having a matte effect on the surface in order to express brightness and darkness by the intensity of the reflection of external light. As a method for improving the texture by the matting effect, a matting agent (also referred to as a "matting agent") is used as in Patent Document 2, and a method based on the light diffusion effect of the matting agent is used. Are known.

However, when the bright pigment-containing layer and the matte layer are combined, the external light reflected by the bright pigment-containing layer passes through the matte layer again and is diffused by the matting agent. For this reason, it becomes difficult to produce contrast depending on the presence or absence of the bright pigment-containing layer.

An object of the present invention is to provide a decorative sheet and a decorative material having an excellent matting effect and a bright pattern layer containing a bright pigment and having a large brightness difference.

In order to solve the above problems, the present invention provides the following decorative sheet and decorative material.
[1] A decorative sheet having a glitter pattern layer containing a glitter pigment and a matte layer, wherein at least part of the outermost surface of the matte layer has a wrinkled structure.
[2] The decorative sheet according to [1], wherein the wrinkled structure is a structure having an uneven shape composed of irregular wrinkles.
[3] According to [2], wherein the irregular wrinkles are composed of a plurality of projections formed by a plurality of filamentary projections and recesses formed by being surrounded by the plurality of filamentary projections. cosmetic sheet.

[4] The decorative sheet according to any one of [1] to [3], wherein the matte layer has an internal haze of 5.0% or less.
[5] The wrinkle structure according to any one of [1] to [4], wherein Rz (maximum height) defined in JIS B0601:2013 is 3.25 μm or more and 10.00 μm or less. cosmetic sheet.
[6] Any one of [1] to [5], wherein Ra (arithmetic mean roughness) of the wrinkled structure defined in JIS B0601:2013 is 0.10 μm or more and 2.00 μm or less. cosmetic sheet.

[7] The wrinkle structure has an Spc (arithmetic mean curvature of the apex of the projection) of 3000.00 mm ⁻¹ or more and 8000.00 mm ^{−1 or} less, as defined in JIS B0601:2013 [1] to [6 ] The decorative sheet according to any one of .
[8] Any one of [1] to [7], wherein the wrinkled structure has an Rsm (average length of curvilinear elements) of 10.00 μm or more and 30.00 μm or less as defined in JIS B0601:2013 The cosmetic sheet described in .
[9] The wrinkle structure according to any one of [1] to [8], wherein Sa (arithmetic mean height) defined in JIS B0601:2013 is 0.01 μm or more and 2.00 μm or less. cosmetic sheet.

[10] The decorative sheet according to any one of [1] to [9], wherein the wrinkled structure has an Ssk (skewness) defined in ISO25178-2:2012 of 0.01 or more and 1.50 or less. .
[11] The decorative sheet according to any one of [1] to [10], wherein the wrinkled structure has an Sku (kurtosis) of 2.00 or more and less than 4.00 as defined in ISO25178-2:2012. .
[12] The matte layer is composed of a cured resin composition containing a binder resin and a wrinkle-forming stabilizer, and the average particle size of the wrinkle-forming stabilizer is 100% or less of the thickness of the matte layer; [1] to [11], having an average particle size with an upper limit of whichever is smaller than 30 μm, and containing 0.5 parts by mass or more of the wrinkle-forming stabilizer with respect to 100 parts by mass of the resin. The decorative sheet according to any one of 1.

[13] The decorative sheet according to any one of [1] to [12], wherein the glitter pigment is a glitter inorganic pigment.
[14] The decorative sheet according to any one of [1] to [13], wherein the surface area ratio of the decorative sheet having the glitter pattern layer is 3% or more and 95% or less.
[15] The decorative sheet according to any one of [1] to [14], wherein the matte layer is provided over the entire surface of one side of the decorative sheet.

[16] The decorative sheet according to any one of [1] to [15], wherein the surface shape has a 60° gloss value of 10.0 or less.
[17] A decorative material having the decorative sheet according to any one of [1] to [16] on an adherend.

According to the present invention, it is possible to provide a decorative sheet and a decorative material having an excellent matting effect and a bright pattern layer containing a bright pigment and having a large brightness difference.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram for demonstrating the layer structure of the decorative sheet of this invention. 1 is an optical microscope image of the surface of the decorative sheet obtained in Example 1. FIG. FIG. 2 is a schematic diagram for explaining the wrinkled structure of the decorative sheet of the present invention;

[Decorative sheet]
Embodiments of the decorative sheet of the present disclosure will be described below. In the present disclosure, numerical values related to “more than” and “less than” regarding the description of numerical ranges are numerical values that can be arbitrarily combined, and the numerical values in the examples are numerical values that can be used for the upper and lower limits of the numerical ranges.

The decorative sheet of the present disclosure has a glitter pattern layer containing a glitter pigment and a matte layer, and is characterized by having a wrinkle structure on at least part of the outermost surface of the matte layer. is.
When the decorative material to be described later has a decorative sheet on the adherend, the matte layer is preferably provided so as to be the outermost surface opposite to the adherend, as shown in FIG. Moreover, when the decorative sheet has a base material, the matte layer is preferably provided on the outermost surface opposite to the base material, as shown in FIG. In other words, the matte layer is preferably provided so as to be the outermost surface of the decorative sheet (hereinafter also referred to as "the outermost surface of the decorative sheet") when the viewer visually recognizes the decorative sheet. A crease structure, which will be described later, is formed on the outermost surface 20 .
The glitter pattern layer is preferably provided on the opposite side of the matte layer to the viewer, and is preferably provided between the substrate and the matte layer or between the adherend and the matte layer. .

<Glitter pattern layer>
The glitter pattern layer of the present disclosure is a layer containing a glitter pigment, which will be described later. The glitter pattern layer may be a continuous layer or a patterned layer. Although the glitter pattern layer contains a glitter pigment, external light is reflected by the glitter pigment, and the viewer perceives the glitter pattern layer portion as a bright portion. For this reason, it is preferable that the glittering pattern portion is patterned rather than being provided on the entire surface of the decorative sheet so that there are areas on the decorative sheet with and without the glittering pattern layer. As a result, the area with the glittering pattern layer is visible as a bright area, and the area without the glittering pattern layer is visible as a dark area. preferable.

In the present disclosure, "lightness" means lightness (L ^* ) of color in CIE L ^* a ^* b ^* , which can be measured, for example, by the method described in the Examples. A "dark area" means an area with a relatively small L ^* value, and a "light area" means an area with a relatively large L ^* value. Since these values differ depending on the design expressed by the decorative sheet, it is preferable to appropriately adjust them according to the design.

In the case of a patterned layer, the preferable range of the area ratio of the glitter pattern layer to the entire surface of the decorative sheet when viewed in plan cannot be generalized because it can be appropriately selected according to the design expressed by the decorative sheet. In order to distinguish between bright and dark areas, the ratio of the area occupied by the glitter pattern layer to the area of one surface of the decorative sheet (area ratio) is preferably 95% or less, and is 90% or less. In order to recognize the bright part, it is preferably 3% or more, preferably 5% or more. The area ratio can be expressed by the following formula.
Area ratio = area of glitter pattern layer / area of decorative sheet in plan view x 100 (%)
In the present disclosure, “planar view” means visually recognizing the decorative material sheet of the present disclosure in a planar direction from the surface side, which is the surface side on which the glitter pattern layer is provided. For example, in the XYZ coordinate system shown in FIG. 1, the plane represented by the X-axis direction and the Y-axis direction coincides with the surface of the decorative sheet, and "planar view" means viewing the surface of the decorative material from the positive direction of the Z-axis. Equivalent to.

The patterning depends on the design expressed by the decorative sheet, and may be a pattern that is synchronized with the decorative layer described later, or may be randomly arranged. For example, when imparting a wood grain pattern to the entire decorative sheet, it is preferable to use a wood texture pattern (parts other than the vessel groove pattern and/or the knot pattern), and when imparting a stone pattern such as travertine to the entire decorative sheet is preferably a pattern other than the recessed portions, and when a tile pattern or brick pattern is given to the entire decorative sheet, it is preferably a tile portion or a brick portion. In order to express metallic luster over the entire decorative sheet, it is preferable that they are arranged at random without any regularity.

The bright pattern layer may contain a bright pigment described later, and in addition to the bright pigment, the binder resin may further include a pigment, a coloring agent such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent. It may also be a cured product of a glittering pattern layer-forming composition in which an agent, an ultraviolet absorber, a light stabilizer and the like are appropriately mixed.
The content of the bright pigment in the bright picture layer-forming composition is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 50 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of the binder resin. .

By setting the content of the bright pigment to 10 parts by mass or more, it is possible to easily achieve sufficient gloss in bright areas. Moreover, by setting the content of the glitter pigment to 90 parts by mass or less, it is possible to suppress deterioration of the visibility of the design when the glitter pattern layer-forming composition has a decorative layer as a lower layer.
The thickness of the glitter pattern layer is preferably 0.5 μm or more and 30 μm or less, more preferably 1 μm or more and 10 μm or less, in order to make the bright areas sufficiently glossy and to suppress deterioration of the visibility of the pattern. is more preferred. The binder resin of the glitter pattern layer forming composition includes thermoplastic resins, curable resins, and the like, and curable resins are preferable in order to improve durability.
Curable resins include thermosetting resins and ionizing radiation curable resins. A thermosetting resin is preferable in order to improve the adhesion between the layers above and below the glitter pattern layer (base material, decorative layer, primer layer, matte layer, etc.).

Thermosetting resins for the glitter pattern layer include polyester resins, epoxy resins, polyurethane resins, aminoalkyd resins, melamine resins, guanamine resins, urea resins and acrylic resins. These thermosetting resins are obtained by curing a composition of monomers and/or prepolymers constituting each resin and a curing agent or the like added as necessary.

As the ionizing radiation-curable resin for the glitter pattern layer, the same ionizing radiation-curable resin as that for the later-described matte layer can be used.
The glitter pattern layer can be formed, for example, by printing using a composition for forming a glitter pattern layer.

(Luminous pigment)
The bright pigment is not particularly limited as long as it reflects external light (incident light), and may be an inorganic pigment or an organic pigment. In order to improve the weather resistance, a bright inorganic pigment is preferable, a metallic scale or a pearl pigment is preferable, and a single substance or a mixture thereof is preferable.
Examples of materials for the metal flakes include metals and alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel-chromium, and stainless steel.

The metal flakes are obtained, for example, by peeling a metal thin film formed by vacuum-depositing the metal or alloy on a plastic film from the plastic film, pulverizing and stirring the peeled metal thin film; A product obtained by mixing a powder and a solvent and spreading and/or pulverizing the powder with a medium stirring mill, a ball mill, an attritor, etc.; etc.
The pearl pigment preferably contains at least one selected from pearl pigments and metal flakes as luster pigments. Since the pearl pigment can easily suppress a decrease in the light transmittance of the glitter ink layer, when a decoration layer exists under the glitter ink layer, the visibility of the decoration layer is less likely to be impaired. is.
Pearl pigments include, for example, white pearl pigments, interference pearl pigments, colored pearl pigments, and the like.

The white pearl pigment is obtained by covering a scale-like base such as mica, aluminum, glass, etc. with a coating layer made of a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is 0.1 μm or more. It is relatively small, on the order of 0.15 μm or less, and appears white or silver because it reflects almost all wavelengths of light.
The interference pearl pigment has a coating layer made of a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is greater than that of the white pearl pigment and exceeds 0.15 μm. This thickness changes the reflected and transmitted light, resulting in different interference colors. It is sometimes called an iris colored pearl.

The average particle size of the glitter pigment is preferably 1 μm or more and 500 μm or less, more preferably 5 μm or more and 100 μm or less, in order to impart glitter and prevent the glitter pigment from falling off.
In order to exhibit the same effect, the value of the ratio [average particle diameter of the glitter pigment/thickness of the glitter pattern layer] is preferably 0.01 or more and 15 or less, and is 0.5 or more and 10 or less. is more preferable.

<Matte layer>
The matte layer of the present disclosure is a layer having a wrinkled structure described later on at least a part of the outermost surface, and is the layer provided on the outermost surface of the decorative sheet as described above.
Since the matte layer has a wrinkle structure on at least part of the outermost surface, the wrinkle structure diffusely reflects external light (incident light), thereby exhibiting a matte effect.

The matte layer is composed of a cured product of a resin composition containing a resin and a wrinkle-forming stabilizer described later, and the wrinkle-forming stabilizer is 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. It preferably has an average particle size with an upper limit of 0.5 parts by mass or more of the wrinkle-forming stabilizer with respect to 100 parts by mass of the resin.

In order to form a stable wrinkle structure, the average particle size of the wrinkle-forming stabilizer is preferably 80% or less and 5% or more of the thickness of the matte layer, and is 70% or less and 10% or more. is more preferably 60% or less and 15% or more.
The thickness of the matte layer is preferably 0.1 μm or more and 40.0 μm or less in order to exhibit wrinkle stability, improve abrasion resistance, and improve visibility of the glitter pattern layer. , more preferably 1.0 μm or more and 30.0 μm or less, even more preferably 2.0 μm or more and 2.0 μm or less, and even more preferably 3.0 μm or more and 18.0 μm or less.
The thickness of the matte layer can be determined, for example, by the method described in the Examples.

In order to stably develop the wrinkle structure, the amount of the wrinkle-forming stabilizer is more preferably 1 part by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the resin. The upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less in order to allow the reflected light from the glitter pattern layer to pass therethrough. .

As the matte layer-forming composition for forming the matte layer, a resin composition containing a binder resin and a wrinkle-forming stabilizer is preferable because it can have an excellent matting effect. That is, in the present disclosure, the matte layer is preferably a layer containing a binder resin and a wrinkle-forming stabilizer.
The matte layer may be provided over the entire surface of the decorative sheet or may be provided in synchronism with the glitter pattern layer. is preferably provided over the entire surface of the

(Internal haze of matte layer)
The matte layer preferably has a low internal haze. When the decorative sheet is formed by combining the glitter pattern layer and the matte layer as described above, the external light (incident light) reflected by the glitter pattern layer passes through the mat layer again. When the light passes through the matte layer, if the internal haze of the matte layer is large, the lightness (L ^* ) of the bright portion decreases, resulting in a decrease in the lightness difference.
In order to reduce the internal haze of the matte layer, the difference in refractive index between the binder resin and the wrinkle-forming stabilizer in the matte layer should be approximately the same, and the sphericity of the wrinkle-forming stabilizer should be increased. , or both.

The internal haze can be appropriately selected according to the design expressed by the decorative sheet, but in order to increase the difference in brightness between the bright and dark areas of the decorative sheet, the upper limit is preferably 5.0% or less, and 4.0%. It is more preferably 3.6% or less, more preferably 3.6% or less. Although the lower limit is not particularly limited, it is preferably substantially 0% or more. Substantially means taking account of measurement errors.
The internal haze of the matting agent can be determined, for example, by separately preparing only the matting layer used in the decorative sheet and measuring it by the method described in Examples.

(binder resin)
As the binder resin for forming the matte layer, any resin that forms a matte layer-forming resin composition containing a predetermined amount of a wrinkle-forming stabilizer described later and cures to form a cured product that constitutes the matte layer can be used. good. It is preferable that the binder resin forms a wrinkle structure on its outermost surface and has approximately the same refractive index as the wrinkle-forming stabilizer described later.
The upper limit of the absolute value of the difference in the absolute value of the refractive index between the binder resin forming the matte layer and the wrinkle stabilizer described later is preferably 0.3 or less, more preferably 0.2 or less. It is more preferably 0.1 or less. Although the lower limit is not particularly limited, it is preferably substantially zero.

In the present disclosure, refractive index means the refractive index at a wavelength of 589 nm.
Such resins include ionizing radiation-curable resins. The matte layer is a layer that can be provided on the outermost surface of the decorative sheet of the present disclosure, as also shown in FIG. In addition, in order to improve usability as a decorative sheet, it is preferable to use a resin that easily exhibits surface properties such as processability, stain resistance, scratch resistance, weather resistance, etc. An ionizing radiation curable resin is a preferable resin. be. In the decorative sheet of the present disclosure, the content of the wrinkle-forming stabilizer contained in the matte layer is extremely low, so that the performance of the resin forming the matte layer is more directly exhibited as the surface properties. .

An ionizing radiation-curable resin is a resin having an ionizing radiation-curable functional group, and the ionizing radiation-curable functional group is a group that is cross-linked and cured by irradiation with ionizing radiation. For example, functional groups having an ethylenic double bond such as (meth)acryloyl group, vinyl group and allyl group are preferred. In addition, in this indication, a (meth)acryloyl group shows an acryloyl group or a methacryloyl group. Moreover, in this disclosure, (meth)acrylate indicates acrylate or methacrylate.
In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing and/or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used, In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.

Examples of ionizing radiation curable resins include electron beam curable resins and ultraviolet curable resins, which stabilize the formation of wrinkles by the wrinkle formation stabilizer, stably improve the matting effect, and the matting layer Ultraviolet curable resins are preferred for reducing internal haze.
Specifically, the ionizing radiation-curable resin can be appropriately selected and used from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation-curable resins.

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable.
Polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group.

In order to stabilize the formation of wrinkles, stably improve the matting effect, and further improve the surface properties such as post-processing properties, scratch resistance and weather resistance, the number of functional groups of the polyfunctional (meth)acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less. Moreover, when it is the number of functional groups, it becomes easy to obtain especially the wrinkled structure mentioned later.
These polyfunctional (meth)acrylates may be used alone or in combination.

Polymerizable oligomers include, for example, (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups as the functional groups. Examples thereof include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.
Furthermore, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. , aminoplast resins modified with aminoplast resins having many reactive groups in small molecules (meth)acrylate oligomers, novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers having cationic polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination.
To stabilize the formation of wrinkles and stably improve the matting effect, to reduce the internal haze of the matting layer, and to improve the surface properties such as post-processing properties, scratch resistance and weather resistance. , urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers are preferred, and urethane (meth)acrylate oligomers are preferred. More preferred are acrylate oligomers and polycarbonate (meth)acrylate oligomers, and even more preferred are urethane (meth)acrylate oligomers.

The functionality of these polymerizable oligomers stabilizes the formation of wrinkles, stably improves the matting effect, and reduces the internal haze of the matting layer. In order to improve surface properties such as toughness, the number is preferably 2 or more and 8 or less, and the upper limit is more preferably 6 or less, and even more preferably 4 or less.
For the same purpose, the weight average molecular weight of these polymerizable oligomers is preferably from 2,500 to 7,500, more preferably from 3,000 to 7,000, and more preferably from 3,500 to 6,500. 000 or less is more preferable. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

In the present disclosure, as the binder resin forming the matte layer, it is preferable to use a combination of the polymerizable oligomer and the polymerizable monomer. In this case, the polymerizable oligomer is preferably a polyfunctional urethane (meth)acrylate oligomer, more preferably a polyfunctional urethane acrylate oligomer, and the polymerizable monomer is preferably a polyfunctional polymerizable monomer. ) acrylate monomers are more preferred, and multifunctional acrylate monomers are even more preferred. It can also stabilize the formation of wrinkles, stably improve the matte effect, reduce the internal haze of the matte layer, and further improve surface properties such as processing properties, scratch resistance and weather resistance.

When used in combination, the content of the polymerizable oligomer with respect to the total 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 55 parts by mass. As described above, it is more preferably 60 parts by mass or more, and the upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less. Further, polymerizable oligomers can be used in combination, and it is preferable to use two kinds of polymerizable oligomers having different numbers of functional groups in combination. The content of the oligomer is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, still more preferably 60 parts by mass or more, and even more preferably 65 parts by mass or more.

(Wrinkle formation stabilizer)
The wrinkle formation stabilizer stabilizes the formation of wrinkles on at least one surface of the matte layer, thereby forming a wrinkle structure on at least a part of the surface of the decorative sheet. It preferably contains a formation stabilizer. A wrinkle structure can be formed in the matte layer without using a wrinkle-forming stabilizer, but by using a wrinkle-forming stabilizer, the formed wrinkle structure is stabilized and a stable matting effect can be visually recognized. (Hereinafter, expressions such as "stable matte effect visibility" and similar expressions may be used.), and the surface condition due to the stable formation of wrinkles over the entire surface of the matte layer. Uniformity (also referred to as “texture”) can be imparted.

In the present disclosure, "wrinkle formation stability" refers to the shape of wrinkles and their geometric characteristic values (the length and width of individual projections, and the ratio of the two), and their statistical indicators (Rz in this case, Ra, Spc, Rsm, Sm, Ssk, Sku, etc.), the in-plane distribution (dispersion σ) converges with the addition of the wrinkle-forming stabilizer as compared to the case without the additive. As a result, the in-plane distribution (dispersion σ) of the 60° gloss value of the surface shape, which will be described later, also converges. The wrinkle-forming stabilizer does not diffuse light for matting, but is added to stabilize the wrinkle structure.
Thus, the so-called "matting agents" in the prior art and the "wrinkling stabilizers" in the present disclosure, even if their constituents, average particle size, are the same or similar, the matting mechanism ( function), the structure for expressing mattness, and the relationship between the amount used and the degree of surface luster (gloss value).

In the prior art such as Patent Document 2, the matting agent that has been used for matte expression expresses the visibility of the matting effect itself due to the light diffusion effect caused by the physical shape. is. Specifically, what is generally called a matting agent generally has a refractive index difference between the matting agent particles and the surrounding resin and air, and the light reflection and refraction properties corresponding to the contour shape of the particles The visibility of the matte effect is expressed by the light diffusion effect of the interface. Therefore, if a matting agent is used in the matting layer combined with the glitter pattern layer as in the present disclosure, the external light (incident light) reflected by the glitter pigment is diffused by the matting agent. The brightness of the bright part is lowered.

On the other hand, the wrinkle-forming stabilizer causes wrinkles on the surface of the matte layer due to the wrinkle-forming stabilizer rather than light diffusion due to reflection and refraction of light rays by the particles themselves to express the visibility of the matting effect. By stabilizing the formation of , the decorative sheet is stably provided with the visibility of the matte effect and the texture due to the light diffusion effect at the refractive index difference interface between the surface and the air. Therefore, the wrinkle-forming stabilizer used in the present disclosure is different from the matting agent that itself expresses the visibility of the matting effect (assuming that the constituent substances and the average particle size of both are the same or similar). Also, the mechanism (action) of matting and the structure for expressing matting are different between the two.

Furthermore, the "wrinkle-forming stabilizer" and the "matting agent" also differ in the relationship between the content and surface gloss (gloss value). 60° gloss value G _60° ^AW (C) of the surface when the same substance A is used as a wrinkle-forming initiator AW (W: wrinkle) and this is contained in a specific amount C to form wrinkles on the surface is clearly lower than the ₆₀ ° gloss value ^G of the surface when wrinkles are not formed on the surface even when the same substance A is used as a mere matting agent AM and this is contained in the specific amount C (C). do. That is, the following relational expression holds.
G _60° ^AW (C) < G _60° ^AM (C)

The matting layer in the decorative sheet of the present disclosure may contain an agent that has been conventionally used as a matting agent, but it is preferable that it does not affect the internal haze of the matting layer. More preferably no. As described above, the decorative sheet of the present disclosure has extremely excellent visibility of the matting effect even if it does not substantially contain a matting agent that has been conventionally used to obtain the visibility of the matting effect. It can be said that there is. Here, "does not contain a matting agent" means not containing a matting agent at all, and even if it does contain a matting agent, it does not have the visibility of the matting effect based on the action and effect of the matting agent itself. Specifically, the content of the matting agent is less than 10.0 parts by mass, preferably 5.0 parts by mass or less, and more preferably 1.0 parts by mass or less per 100 parts by mass of the binder resin.

As described above, the wrinkle-forming stabilizer is not a matting agent, and is particularly limited as long as it has an average particle diameter of 100% or less of the matte layer thickness or 30 μm or less, whichever is smaller. can be used without
In the present disclosure, the average particle size of particles such as bright pigments and wrinkle-forming stabilizers refers to the cross section of each layer of the sheet in the thickness direction using a scanning electron microscope (SEM) at an acceleration voltage of 3.0 kV and an enlarged It is an average value (arithmetic mean diameter) of particle diameters of 100 randomly selected non-agglomerates of particles observed under conditions of a magnification of 50,000 times. The particle size was obtained by measuring the distance between two straight lines that maximizes the distance between the two straight lines when the cross section of the particle is sandwiched between two parallel straight lines. value.

As the wrinkle-forming stabilizer, for example, organic particles and inorganic particles can be used.
Organic substances constituting organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin and polyester-based resin. etc. Organic particles are preferably used in order to reduce the difference in refractive index between the binder resin of the matte layer and the wrinkle-forming stabilizer and reduce the internal haze of the matte layer.
Inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, barium sulfate, and the like. Among these, silica is preferred because of its excellent transparency. Inorganic particles are preferably used to improve the strength of the matte layer.

The shape of the wrinkle-forming stabilizer is not particularly limited, and may be, for example, spherical, polyhedral, scaly, amorphous, and the like. A spherical shape is preferred in order to reduce the internal haze of the matte layer. This is because the spherical shape suppresses the diffusion of the reflected light from the luster pigment due to the wrinkle-forming stabilizer, making it difficult for the lightness (L ^* ) of the bright area to decrease.
In order to reduce the internal haze of the matte layer, the upper limit of the sphericity of the wrinkle-forming stabilizer is preferably 10% or less, more preferably 8% or less, and 5% or less. is even more preferred. Although the lower limit is not particularly limited, it is preferably 0.1% or more, more preferably 0.5% or more, from the standpoint of availability.

The term “sphericity” as used in the present disclosure is a value obtained by averaging the degree of deviation of the outer shape of each of ten randomly selected particles from a perfect circle. Specifically, the maximum value of the radial distance between the minimum circumscribed circle and each point on the surface of the particle with respect to the radius of the minimum circumscribed circle (minimum circumscribed circle) in contact with the surface of each particle in the electron micrograph of each particle refers to the ratio (%) of
When silica is used as the wrinkle-forming stabilizer, it is preferable that the specific surface area by the BET method using the nitrogen adsorption method is small because light diffusion is suppressed. Therefore, the specific surface area is preferably 50 m ² /g or more and 800 m ² /g or less, more preferably 100 m ² /g or more and 500 m ² /g or less. Similarly, the smaller the oil absorption, the less the light diffusion, which is preferable. Therefore, the oil absorption is preferably 700 ml/100 g or less, more preferably 600 ml/100 g or less. The oil absorption was determined by the method described in JIS K6217-4 "Determination of oil absorption".

The surface of the wrinkle stabilizer may be coated with an organic compound to reduce light diffusion.
In order to reduce the matte effect and the internal haze of the matte layer, the average particle size of the wrinkle-forming stabilizer having an upper limit of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller, is It is preferred to use at least one of two types of wrinkling stabilizers distinguished by diameter. Specifically, the two types of wrinkle-forming stabilizers are wrinkle-forming stabilizer 1 having an average particle size of 1 μm or more and having an upper limit of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. and wrinkling stabilizer 2 having an average particle size of less than 1 μm. In the present disclosure, the use of at least one of the two wrinkle formation stabilizers stabilizes the formation of wrinkles, stably provides an excellent matting effect, and reduces the internal haze of the matte layer. can be done.

The upper limit of the average particle size of the wrinkle formation stabilizer 1 is 1 μm or more and the smaller one of 100% or less of the thickness of the matte layer and 30 μm or less. Since the matte effect can be stably improved and the internal haze of the matte layer can be reduced, the average particle diameter of the wrinkle formation stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, It is more preferably 1.8 μm or more, and the upper limit is preferably 90% or less of the thickness of the matte layer, more preferably 80% of the thickness of the matte layer. Below, it is more preferably 70% or less of the thickness of the matte layer. Any combination of the upper limit of the thickness of the erase layer and the upper limit of the absolute value may be set to the smaller one. For example, the upper limit may be 90% or less of the matte layer thickness or 20 μm or less, whichever is smaller, or the smaller one of 90% or less and 10 μm or less of the matte layer thickness may be the upper limit. can also The thickness of the matte layer will be described later.

Also, the average particle size of the wrinkle-forming stabilizer 2 is less than 1 μm. In order to stabilize the formation of wrinkles, stably improve the matting effect, and reduce the internal haze of the matte layer, the average particle size of the wrinkle formation stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more. , more preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm or less, and still more preferably 500 nm or less. It is preferable that the average particle diameter is near or below visible light because the internal haze of the matte layer against visible light is reduced.

In order to stabilize wrinkle formation by the wrinkle-forming stabilizer, stably improve the matting effect, and reduce the internal haze of the matte layer, the wrinkle-forming stabilizer (wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer The total content of these when used together with agent 2) is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass, relative to 100 parts by mass of the binder resin forming the matte layer parts or more, more preferably 1.0 parts by mass or more, and even more preferably 1.2 parts by mass or more, and the upper limit is for stable improvement of the matting effect and reduction of internal haze of the matting layer. Although there is no particular limitation, 25. is preferable in order to improve the productivity of the decorative material by, for example, the applicability of the resin composition for forming the matte layer, and to efficiently improve the visibility and texture of the matte effect. It is 0 parts by mass or less, more preferably 15.0 parts by mass or less, still more preferably 10.0 parts by mass or less, even more preferably 7.5 parts by mass or less, and particularly preferably 6.0 parts by mass or less.

When wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 are used in combination, the content of each of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 is not particularly limited as long as the total content is within the above range. However, the content of the wrinkle-forming stabilizer 2 is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1.0 parts by mass or more with respect to 100 parts by mass of the binder resin. The upper limit is preferably 10.0 parts by mass or less, more preferably 7.5 parts by mass or less, even more preferably 5.0 parts by mass or less, and even more preferably 3.5 parts by mass or less. Further, the blending ratio of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is preferably 0.0 parts by mass or more as the blending amount of the wrinkle-forming stabilizer 1 when the total amount of these is 100 parts by mass. 0.95 parts by mass or less, more preferably 0.10 parts by mass or more and 0.90 parts by mass or less, still more preferably 0.20 parts by mass or more and 0.80 parts by mass or less, still more preferably 0.30 parts by mass Above, it is 0.70 mass parts or less.

As the wrinkle-forming stabilizer, organic particles and inorganic particles can be used as described above. Matting agents such as spherical alumina and calcium carbonate are used in the matte layer of the decorative sheet described in 1 above. In order for matting agents such as spherical alumina and calcium carbonate to express the visibility of the matting effect themselves due to the light diffusion effect resulting from their physical shape, as described in Patent Document 1, It is necessary to use 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate in a total amount of about 50 parts by weight per 100 parts by weight of resin. However, in the present disclosure, even if the content is small as described above, that is, the content necessary for expressing the visibility of the matte effect itself due to the light diffusion effect caused by the physical shape Even with a smaller content, a very excellent matting effect is obtained compared to the effect obtained by the matting agent, and a soft touch feeling is also obtained. Therefore, although the decorative sheet of the present disclosure does not substantially contain a matting agent, wrinkles are stably formed on the surface, resulting in better matting than when a matting agent is used. It can be said that the visibility of the effect is stably obtained and at the same time the texture is obtained, and the internal haze of the matte layer can be reduced.

(Matte layer-forming composition)
The matte layer is preferably composed of a cured product of a resin composition containing a predetermined content of the wrinkle-forming stabilizer, and the resin composition preferably contains a predetermined content of the resin and the wrinkle-forming stabilizer. Quantity. The resin composition used in the present disclosure may contain other components in addition to the wrinkle stabilizer and resin, depending on desired performance and the like.
The resin composition for forming the matte layer may contain a monofunctional (meth)acrylate for the purpose of reducing its viscosity, for example. These monofunctional (meth)acrylates may be used alone or in combination.

Moreover, when the resin is an ultraviolet curable resin that is cured by ultraviolet rays, it is preferable that additives such as a photopolymerization initiator and a photopolymerization accelerator are included. By including these additives, the resin can be cured even with ultraviolet rays (without using ionizing radiation), and practical surface properties can be obtained.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like.

In addition, the photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. One or more selected types can be mentioned.

Since the matte layer is a layer that can be provided on the outermost surface of the decorative sheet of the present disclosure, it is preferably a layer having weather resistance, and may contain various weather resistance agents such as ultraviolet absorbers and light stabilizers. preferable.
As the UV absorber, any UV absorber that is commonly used for cosmetic materials, decorative sheets, etc. can be used without particular limitation. Examples include triazine-based ultraviolet absorbers. As the light stabilizer, any light stabilizer commonly used for decorative materials, decorative sheets, etc. can be used without particular limitation, and examples thereof include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers. Moreover, these ultraviolet absorbers and light stabilizers may have a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, vinyl group or allyl group in the molecule.
Weather resistance agents such as these ultraviolet absorbers and light stabilizers can be used alone or in combination.

<wrinkle structure>
The matte layer in the decorative material of the present disclosure is a layer composed of a cured resin composition for forming a matte layer containing the specific wrinkle-forming stabilizer in a specific content as necessary. As described above, by stabilizing the formation of wrinkles on the outermost surface of the matte layer, the layer stably expresses the visibility and texture of the matte effect due to the light diffusion effect caused by the shape of the wrinkles. FIG. 1 is a schematic cross-sectional view showing one embodiment of the decorative sheet of the present disclosure. FIG. 1 shows that the decorative sheet of the present disclosure has a wrinkled structure on its surface, ie, the outermost surface of the matte layer.

The wrinkle structure that appears on at least one surface of the matte layer is stabilized by the wrinkle-forming stabilizer and stably exhibits the visibility and texture of the matte effect. There is no particular limitation as long as it expresses the visibility and texture of Regarding the wrinkle structure, it is preferable that at least one surface of the matte layer has an uneven shape composed of irregular wrinkles. and a recess formed by being surrounded by the projections of , and the projections preferably have filamentous projections. In the present disclosure, the “line projection” (hereinafter also referred to as “line projection”) means that the ratio of the length and width of the projection (length / width) is 3 or more, preferably 5 More preferably, it means 10 or more, and the method for determining the length and width will be described later.
In the present disclosure, the more preferable irregular wrinkles are composed of a plurality of protrusions formed by the plurality of filamentary projections and recesses formed by being surrounded by the plurality of filamentary projections.

As aspects of these wrinkles, the surface of the decorative sheet, that is, the outermost surface of the matte layer as shown in FIG. It is configured by including a plurality of protrusions 2 formed by a plurality of curved filament protrusions and a recess 3 formed by being surrounded by the plurality of protrusions (plurality of protrusions 2). It is also shown that at least a part of the plurality of protrusions 2 are formed by meandering linear projections, and a meandering recess 3 is formed so as to be surrounded by the meandering linear projections. ing. The decorative material of the present disclosure stably expresses the visibility and texture of the matting effect due to the stable formation of wrinkles shown in FIG.

Here, “curved” means having one or more portions in which the extending direction of the continuous filamentary projections 2 is reversed from one side to the other side in plan view. As an example of the portion where the extending direction is reversed from one side to the other side, for example, when the width of the planar view shape of the protrusion 2 of the filament is ignored (when the width is considered to be 0), a continuous curve Examples of approximation include a form having an inflection point. In addition, when approximating with a straight line when the width of the planar view shape of the filamentary protrusion 2 is ignored, a form having a portion approximated by two sides sandwiching one vertex of a V-shaped broken line or triangle etc.

Further, the term "meandering" refers to a portion where the extending direction of the continuous filamentary protrusions 2 is reversed from one side to the other side (hereinafter also referred to as "reversed portion") in a plan view, at least two times. There are at least two portions where the extension direction of the filament projections 2 is alternately reversed at two locations adjacent to each other when the filament projections 2 are advanced in their extending direction. means to have For example, there is a form having a portion approximated by Roman letter "S" when approximating with a continuous curve when ignoring the width of the planar view shape of the projection 2 of the filaments. In addition, when the linear projections 2 are approximated by straight lines when the width of the projections 2 in plan view is ignored, there may be a form having a portion approximated by the Roman letter "W".

In the present disclosure, "irregular" means a shape having a certain rule, or a shape that is arranged according to a certain rule, which cannot be said to be patterned. A typical example of a non-irregular shape (regular shape) is a so-called "lenticular lens ( lenticular lens)”, which are arranged with a certain periodicity in a specific direction. Therefore, the irregular wrinkles in the present disclosure are that the shape of one protrusion itself is irregular rather than a shape formed according to a certain rule such as periodicity, and that a plurality of protrusions formed by a plurality of protrusions It includes that the shape of the part is not formed and arranged according to a certain rule but is irregular, and that the shape of the recess surrounded by such a plurality of protrusions is also irregular. .

In the matte decorative material of the present disclosure, the shape of one protrusion (one protrusion) itself, the shape and arrangement of each of the plurality of protrusions (plurality of protrusions), and the recesses surrounded by the plurality of protrusions If any of the shapes are irregular, the matte effect visibility and texture of having irregular wrinkles can be obtained, but both are preferably irregular. Since the decorative material of the present disclosure has irregular wrinkles, the visibility and texture of the matte effect are improved, and the visibility and texture of the matte effect are stably excellent.

As described above, the matte layer has wrinkles, ie, an irregular shape on at least one surface thereof. Protrusions and recesses in the uneven shape, for example, using the brightness difference of the image on the surface of the decorative material of the present disclosure, the darkest part in the density distribution image is set to gradation 255, and the lightest part in the density distribution image is set to gradation. Assuming 0 as 0 to 255, the gradations 0 to 127 can be classified as concave portions, and the gradations 128 to 255 can be classified as convex portions by binarization processing.

The surface of the decorative material of the present disclosure preferably has an irregular wrinkled structure at least partially, and more preferably has irregular wrinkles over the entire surface. The place where the wrinkles are formed is not particularly limited as long as it is on the surface of the decorative material, for example, it is not limited to only the place corresponding to the pattern described later (on the pattern), and if it is at least a part of the surface, wrinkles are formed. The visibility and texture of the matte effect by is expressed. For example, in the case of having a pattern layer, which will be described later, and irregular wrinkles are formed in part, if the wrinkles are formed in a portion corresponding to the pattern of the pattern layer (for example, on the pattern), the pattern will be more prominent than the surroundings. Since it is visually recognized as a matted portion, it is possible to improve the design.

Also, as shown in FIG. 2, it has a plurality of protrusions formed by a plurality of protrusions that are irregular but uniform to some extent, and recesses surrounded by the protrusions. is preferred. Therefore, a shape in which the width and height of one protrusion (protrusion) change drastically is not preferable for obtaining the visibility and texture of the matte effect. Concerning the shape of the protrusions (protrusions) forming irregular wrinkles and the shapes of the recesses, specific aspects that can be advantageous in stably improving the visibility and texture of the matte effect will be described below.

Regarding the shape of wrinkles formed on at least one surface of the matte layer, the height of the projections (the height of the protrusions) is preferably 0.5 µm or more, more preferably 1 µm or more, and still more preferably 2 µm or more. and the upper limit is about 10 μm or less. The width of the protrusion is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, and still more preferably 3 μm. It is below. When the height and width of the protrusions are within the above ranges, the visibility and texture of the matte effect are stably improved in relation to the recesses.
Here, the above dimensions of the protrusions are arbitrary 10 protrusions (protrusions) at arbitrary 10 locations (100 μm square area × 10 locations) of the decorative sheet of the present disclosure, that is, the average value of a total of 100 protrusions is. In addition, as shown in FIG. 2, since the width of one protrusion (projection) is not the same but varies, the width of one protrusion (projection) is ) shall be the average value of the widths of any five locations. The same applies to the height of the projection (protrusion).

The depth of the concave portion is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is about 10 μm or less. The width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more, and the upper limit is preferably 10 μm or less, more preferably 3 μm or less, and still more preferably 2 μm or less. is. When the depth and width of the concave portions are within the above ranges, the visibility and texture of the matte effect are stably improved in relation to the convex portions.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The distance from the top of the projection to the bottom of the recess (height difference between the projection and the recess) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 2 μm or more. It is preferably 8 μm or less, more preferably 7 μm or less. When the distance is within the above range, the visibility and texture of the matte effect are stably improved.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The occupancy ratio of the convex portion is preferably 15% or more, more preferably 20% or more, and still more preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, and further preferably 60% or less. is. When the occupancy ratio of the projections is within the above range, the visibility and texture of the matte effect are stably improved in relation to the occupancy ratio of the recesses surrounded by the projections.
Here, the occupancy ratio of the projections is the average value of the occupancy ratios of the projections at arbitrary 10 locations (100 μm square area×10 locations) of the decorative material of the present disclosure.

The protrusions and recesses may have portions of approximately the same direction and approximately the same width, but their lengths are preferably short in order to improve the visibility and texture of the matte effect. Specifically, the length of continuous protrusions and recesses having approximately the same direction and approximately the same width is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, and the lower limit is preferably 5 μm or more. It is more preferably 10 μm or more, still more preferably 15 μm or more. When the length is within the above range, wrinkles become more irregular, so that the visibility and texture of the matte effect are stably improved.

Here, 80% or more of any 10 convex portions and concave portions (that is, a total of 100 convex portions and concave portions) in any 10 locations (100 μm square area × 10 locations) of the decorative material of the present disclosure It preferably satisfies the conditions, more preferably 85% or more, still more preferably 90% or more, and even more preferably 95% or more. In addition, "substantially" in "substantially the same" in the present disclosure means that it is substantially the same, without branching, means a difference within ± 3 ° in the case of direction, ± 5% in the case of width Mean difference within.

In addition, the number of protrusions (protrusions) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more, and the upper limit is preferably 200 or less, more preferably 100 or less, and further. Preferably it is 70 or less. When the number of protrusions is within the above range, the visibility and texture of the matte effect are stably improved.
The number of protrusions is the average number of protrusions at 10 locations (100 μm square area×10 locations) of the decorative material of the present disclosure.

FIG. 3 is a cross-sectional view showing one embodiment of the decorative material of the present disclosure, and is a cross-sectional view of the decorative sheet 100 cut along a plane parallel to its thickness direction (the Z direction in the figure).
The shape of the recess may be, for example, an acute-angled one as shown in FIG. 3a, a semicircular or semielliptical shape as shown in 3b, or a combination thereof. Alternatively, a shape such as 3c in FIG. 3, in which one convex portion partially has a concave portion, may be used.
On the other hand, as for the shape of the convex portion, it exhibits a semi-circular or semi-elliptical shape as shown in 2a and 2b in FIG. 3, although the width varies widely.

The thickness of the matte layer is not particularly limited as long as it is a thickness capable of forming the above wrinkles to the extent that the visibility and texture of the matte effect can be stably expressed, but it is easy to produce. etc., it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more, and the upper limit is preferably 300 μm or less, more preferably 200 μm or less. It is more preferably 150 μm or less, still more preferably 100 μm or less.
In the present disclosure, the thickness of the matte layer is obtained by measuring the thickness at 20 points from an image of the cross section of the decorative material taken using a scanning electron microscope (SEM), and taking the average value of the 20 points. The acceleration voltage of the SEM is set to 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

The matte layer may be partially provided or may be provided over the entire surface. In order to improve the visibility and texture of the matte effect, the matte layer should be provided over the entire surface. is preferred.
When the matte layer is partially provided, the decorative material of the present disclosure preferably has a base material, which will be described later, substantially as a layer other than the matte layer.

In the present disclosure, the shape of the wrinkle structure and the statistical indices (Rz, Ra, Spc, Rsm, Sa, Ssk, and Sku) of its geometric characteristic values can be appropriately selected according to the design expressed by the decorative sheet. These Rz, Ra, Spc, Rsm, Sa, Ssk and Sku can be determined, for example, by the methods described in Examples.

(Rz (maximum height))
In the present disclosure, it is preferable that the outermost surface of the surface resin layer has Rz (maximum height), which is a lateral parameter of the contour curve defined in JIS B0601:2013, of 12.50 μm or less.
Rz (maximum height) is one of the peak and height parameters of the contour curve, and is the sum of the height of the highest peak and the depth of the deepest valley in the contour curve at the reference length. The larger the numerical value of Rz (maximum height) is, the larger (higher) the shape of the convex portion is when viewed from the valley (concave portion). Therefore, when the Rz (maximum height) is 10.00 μm or less, the unevenness of the height of the convex portions is reduced, and a uniform matting effect is exhibited, so that a decorative sheet having a large difference in brightness can be provided, which is preferable. .

The lower limit of Rz (maximum height) is preferably 3.25 µm or more, more preferably 3.50 µm or more, and still more preferably 4.00 µm or more, in order to develop a matting effect. The upper limit is preferably 10.00 μm or less, more preferably 7.00 μm or less, even more preferably 6.00 μm or less, and even more preferably 5.30 μm or less, in order to improve the visibility of the bright pigment layer. Note that the cutoff value is 0.8 mm for the measurement of Rz (maximum height) in the present disclosure.

(Ra (arithmetic mean roughness))
In the present disclosure, the outermost surface of the surface resin layer preferably has an Ra (arithmetic mean roughness) of 2.00 μm or less, which is a lateral parameter of the contour curve defined by JIS.
Ra (arithmetic mean roughness) is one of the parameters in the height direction of the profile curve, and is the average value of the difference in height from the average plane in the profile curve at the reference length. The smaller the numerical value of Ra (arithmetic mean roughness), the smaller the height difference between the convex portions and the concave portions formed accordingly in the surface shape. be. Therefore, when Ra (arithmetic average roughness) is 2.00 μm or less, the shape of the convex portions of the surface shape is more uniform and gentle, and a uniform matting effect is exhibited. Therefore, it is possible to provide a decorative sheet with a large difference in brightness, which is preferable.

The lower limit of Ra is preferably 0.10 μm or more, more preferably 0.50 μm or more, and still more preferably 0.70 μm or more, in order to improve the matting effect. The upper limit is preferably 1.50 µm or less, more preferably 1.20 µm or less, still more preferably 1.00 µm or less, in order to improve the visibility of the bright pigment layer.

(Spc (arithmetic mean curvature of protrusion vertex))
Spc (arithmetic mean curvature of vertices of protrusions) is one of the three-dimensional surface texture parameters specified by the JIS, and is the peak of a portion classified as a mountain (convex portion) in the feature image included in the reference area. It is the average curvature (average sharpness) of the tip of the peak obtained from the arithmetic average value of the curvature radii of (the peak of the protrusion). Therefore, Spc is the reciprocal (mm ⁻¹ ) of the radius (mm).

The larger the value of Spc, the larger the curvature of the tip of the peak (convex portion) (the reciprocal of the radius of curvature is smaller, and the shape of the tip is sharper). becomes smaller (its reciprocal has a larger radius of curvature, and the shape of the tip is duller).In other words, the smaller the Spc, the more rounded the protrusion, and the closer it is to the plane, the higher the gloss.Therefore, the value of Spc In order to suppress gloss by focusing only on , if a surface shape with a large Spc (a surface shape with a sharp apex of protrusions) is used, the diffusion of light on the surface becomes strong and the gloss is reduced.
The surface shape with a small Spc has rounded apexes of the projections, so the matting effect is inferior when viewed from the front by a viewer, but the matting effect is improved when the decorative sheet is viewed from an oblique direction. be. Therefore, when Spc is 8000.00 mm ⁻¹ or less, the shape of the convex portions of the surface shape is more gentle, and a uniform matting effect is exhibited, so makeup with a large difference in brightness It is preferable because the sheet can be provided.

Spc is preferably 3000.00 mm ⁻¹ or more, more preferably 3500.00 mm ⁻¹ or more, and more preferably 4000.00 mm ⁻ in order to provide a decorative sheet with a uniform matting effect and a large difference in brightness. ¹ or more, and the upper limit is preferably 7000.00 mm ⁻¹ or less, preferably 6500.00 mm ⁻¹ or less, more preferably 6200.00 mm ⁻¹ or less in order to increase the visibility of the bright pigment layer , and more preferably 6000.00 mm ⁻¹ or less. The cutoff value is 0.8 mm for the measurement of Spc in the present disclosure.

(Rsm (average length of curvilinear element))
Rsm (average length of curve element) is a lateral parameter of the contour curve among the three-dimensional surface texture parameters defined in the JIS, and is the average length of the contour curve elements in the reference length. The smaller Rsm is, the more convex portions are included in the reference length. Therefore, in a surface shape with a small Rsm, the apexes of the protrusions are densely present, so that the matting effect of the decorative sheet is enhanced.

The lower limit of Rsm is preferably 10.00 μm or more, more preferably 15.00 μm or more, and still more preferably 18.00 μm or more, in order to provide a decorative sheet with a uniform matting effect and a large brightness difference. The upper limit is preferably 30.00 μm or less, more preferably 25.00 μm or less, still more preferably 20.00 μm or less, in order to improve the visibility of the bright pigment layer. Note that the cutoff value is 0.8 mm for the measurement of Rsm in the present disclosure.

(Sa (arithmetic mean height))
Sa (arithmetic average height) is a numerical value representing the average of the absolute values of the heights of the recesses and protrusions from the average plane of the surface, among the three-dimensional surface texture parameters defined in the JIS. Sa is an index indicating the state of undulations on the entire surface of the decorative sheet, and when Sa is 0.01 μm or more, designability is improved mainly by the physical uneven shape and visual unevenness.
The lower limit of Sa is preferably 0.10 µm or more, more preferably 0.50 µm or more, and still more preferably 0.71 µm or more, in order to provide a decorative sheet with a uniform matting effect and a large difference in brightness. The upper limit is preferably 2.00 µm or less, more preferably 1.50 µm or less, still more preferably 1.00 µm or less, in order to improve the visibility of the bright pigment layer.

Rz, Ra, Spc, Rsm, ^Sa , Ssk and Sku are as described above. Light reflected by the pigment layer can easily pass through the matte layer. Therefore, it is possible to increase the difference in brightness due to the matting effect and the bright pattern layer containing the bright pigment, which is preferable.

(Ssk (skewness))
Ssk (skewness) is one of the three-dimensional surface texture parameters defined in ISO25178-2:2012, and is an index indicating the degree of deviation of height distribution from the average plane. When Ssk is 0, the surface shape is symmetrical (normal distribution) with respect to the average plane. , are measured values from which it can be grasped that the vicinity of the top of the convex portion tends to be sharp and thin. On the other hand, when Ssk is less than 0, the surface shape is biased toward the upper side, ie, the higher side, with respect to the average surface.

In order to improve the matting effect, the lower limit of Ssk is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.07 or more. The upper limit is preferably 1.50 or less, more preferably 1.00 or less, still more preferably 0.50 or less, and still more preferably 0.20, in order to improve the visibility of the bright pigment layer. It is below.
(Sku (Kurtosis))
Sku (kurtosis) is one of the three-dimensional surface texture parameters defined in ISO25178-2:2012, and is an index indicating the degree of sharpness of height distribution from the average surface. When Sku is 3, the surface shape is symmetrical (normal distribution) with respect to the average plane, when Sku exceeds 3, the height distribution has a sharp shape, and when Sku is less than 3, the height distribution is It is a measured value that can be grasped that there is a tendency to have a collapsed shape.

Sku is preferably 2.00 or more, more preferably 2.20 or more, still more preferably 2.50 or more, in order to improve the matting effect. The upper limit is preferably less than 4.00, more preferably less than 3.50, even more preferably less than 3.00, and even more preferably 2.80, in order to improve the visibility of the bright pigment layer. is less than

[Regarding layer structure]
The decorative sheet of the present disclosure has a glitter pattern layer containing a glitter pigment and a surface resin layer, and if at least part of the outermost surface of the surface resin layer has a wrinkle structure, the layer The structure is not particularly limited, and any layer structure may be adopted.
For example, the simplest layer structure of the decorative sheet of the present disclosure includes a structure having only two layers, a glitter pattern layer and a surface resin layer.

In addition, in order to respond flexibly to various demands such as the mechanical strength of the decorative sheet, suitability for post-processing, design appearance, etc., and to ensure suitability for manufacturing and handling, as shown in Fig. 1, A laminate formed by laminating a plurality of layers, for example, may have other layers such as a base material, a primer layer and a decorative layer.
A decorative sheet composed of a laminate, which is one of preferred embodiments of each layer constituting the decorative sheet of the present disclosure, will be described below.

〔Base material〕
The form (or shape) of the base material forming the decorative sheet of the present disclosure is not particularly limited, and is preferably selected from various shapes such as film, sheet or plate, polyhedron, polygonal prism, cylinder, sphere, and spheroid. can be adopted. Here, films, sheets and plates are referred to as films, sheets and plates according to their relatively thin thickness. Differences between sheets and plates shall not result in any difference in the interpretation of the rights of the present invention. Therefore, in the present disclosure, films, sheets, and plates may be collectively referred to as "sheets", "sheet-like", and the like.

When the decorative sheet of the present disclosure is composed of a laminate, the shape of the substrate is preferably sheet-like. When the substrate is in the form of a sheet, it is particularly easy to form a matte layer, which will be described later, so that production aptitude is improved.

The constituent material of the base material is not particularly limited, and various materials such as resins, metals, non-metallic inorganic materials, fibrous materials, and woody materials can be appropriately selected according to the application. A base material composed of these various materials can be used as a single layer, or a plurality of layers in which two or more layers of base materials composed of these various materials are combined. In the case of multiple layers, two or more layers of different materials can be laminated and integrated to complement each other's functions of the materials of each layer.

When a multi-layer substrate is employed, each layer constituting the multiple layers, for example, a layer made of material A and a layer made of material B are laminated to form a laminate "A / B". When notating;
(1) Resin/wood material (2) Resin/metal (3) Resin/fibrous material (4) Resin/non-metallic inorganic material (5) Resin 1/resin 2 (for example, "olefin resin/acrylic resin" etc. If you have multiple layers composed of different resins)

(6) Metal/wood-based materials (7) Metal/non-metallic inorganic materials (8) Metal/fibrous materials (9) Metal 1/metal 2 (for example, multiple metals composed of different metals such as "copper/chromium" layer)
(10) Preferred examples include non-metallic inorganic materials/fibrous materials.
When the substrate has multiple layers, an adhesive layer, a pressure-sensitive adhesive layer, a primer layer (both anchor layer and easy-adhesion layer) may be added between each layer to improve the adhesion of adjacent layers. ) may be further included.

Various synthetic resins, natural resins and the like can be used as resins that can be used for the base material. Synthetic resins include thermoplastic resins and curable resins, and thermoplastic resins are preferred in consideration of suitability for manufacturing, handling, and post-processing of the decorative sheet.

Thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymer; polyethylene Polyester resins such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester thermoplastic elastomer; poly(methyl) acrylate, poly(meth)ethyl acrylate, poly( acrylic resins such as butyl methacrylate and methyl (meth)acrylate-butyl (meth)acrylate copolymer; polyamide resins such as nylon 6 and nylon 66; cellulose triacetate, cellophane, celluloid and the like Resin; styrene resin such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, Polyarylate resins, polyimide resins and the like are preferred.

Preferred natural resins include natural rubber, pine resin, amber, and the like.
Moreover, as the curable resin, a thermosetting resin, an ionizing radiation curable resin, and the like, which are exemplified as constituent materials of the later-described matte layer, are preferably exemplified.

Metals that can be used for the substrate include, for example, aluminum or aluminum alloys such as duralumin; iron or iron alloys such as carbon steel and stainless steel; copper or copper alloys such as brass and bronze; gold, silver, chromium, nickel, and cobalt. , tin, and titanium are preferred. Moreover, as the base material composed of metal, those having the surface thereof coated with such metal by plating or the like are also preferably exemplified.

Examples of non-metallic inorganic materials that can be used for the base material include non-ceramic ceramic materials such as cement, ALC (light cellular concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramics such as ceramics, earthenware, glass, and enamel. Materials: Natural stones such as limestone (including marble), granite and andesite are preferred.

Examples of fibrous materials that can be used for the base material include thin paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, parchment paper, paraffin paper, parchment paper, glassine paper, backing paper for wallpaper, paperboard, and gypsum board. Paper such as base paper; woven fabrics or non-woven fabrics made of fibers such as polyester resin fibers, acrylic resin fibers, proteins such as silk, cotton and hemp, natural fibers such as cellulose, glass fibers and carbon fibers are preferred. Among these materials, in order to improve the interlaminar strength between the fibers of the paper base material composed of paper or with other base materials used in combination with the paper base material, and to prevent fluffing, acrylic resin , styrene-butadiene rubber, melamine resin, urethane resin, and the like (impregnated with these resins after papermaking or incorporated during papermaking). As the resin-added paper, for example, inter-paper reinforced paper, resin-impregnated paper, and the like are preferably used.

It is preferable to form a known permeation-preventing resin layer on the surface of the substrate of fibrous material on which the matting layer is formed by a method such as coating. As such a permeation-preventing resin layer-forming resin, for example, a two-liquid curable urethane resin can be used.
In addition, as a laminate obtained by laminating a layer composed of a fibrous material and a layer composed of a resin, a vinyl chloride resin layer and an olefin resin are added to the surface of wallpaper backing paper commonly used in the field of building materials. Preferred examples include wallpaper raw fabrics in which layers composed of various resins such as layers and acrylic resin layers are laminated.

Examples of woody materials that can be used as the base material include veneers, plywoods, laminated lumbers, and the like, which are composed of various types of wood such as cedar, cypress, pine, zelkova, oak, oak, walnut, lauan, teak, and rubber trees. Particle board, medium density fiber board (MDF), etc. are preferably mentioned.

As the base material, any base material composed of the materials described above can be used without limitation, and the material may be appropriately selected according to desired properties and the like.
Among resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferable, olefin resins, vinyl chloride resins, and polyester resins are more preferable, polyethylene and polypropylene are preferable as olefin resins, and polyvinyl chloride is preferable as vinyl chloride resins. Polyethylene terephthalate is preferred as the polyester resin. Moreover, among fibrous materials, paper is preferable. By using a substrate composed of these materials, it is particularly easy to obtain the surface shape described above, and it is easy to improve the soft touch feeling.

The shape and dimensions of the single-layer or laminate substrate are not particularly limited, and may be appropriately selected in consideration of the intended use, desired properties, post-processing suitability, and the like.
When adopting the shape of a film, a sheet or a plate, there is a thickness as a typical design dimension of the decorative sheet. In view of economy, etc., the thickness should preferably be selected from the range of 10 μm or more and 10 cm or less. When adopting the shape of a film or sheet, it is preferably selected from the range of 20 μm or more and 300 μm or less, and when adopting the shape of a plate, it is preferably selected from the range of 1 mm or more and 2 cm or less.

At least one of the substrates is used to improve adhesion with other layers such as the later-described matte layer constituting the decorative sheet and adhesion with adherends such as resin molded articles on which the decorative sheet is laminated. The surface can be subjected to a physical surface treatment such as an acid value method or a roughening method, or a surface treatment such as a chemical surface treatment for improving easy adhesion.
Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, and the like. Examples of roughening methods include sandblasting and solvent treatment. These surface treatments may be appropriately selected according to the type of base material, and corona discharge treatment is preferred from the viewpoint of the effect of improving easy adhesion by surface treatment, workability, and the like.

The substrate may be colored or may not be colored (it may be transparent), and when colored, the mode of coloring is not particularly limited, and may be transparently colored, Opaque coloring (concealing coloring) may be used, and these can be selected arbitrarily.

When the substrate is colored, examples of coloring agents include white pigments such as titanium white, inorganic pigments such as iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. , isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethine azo black pigments, perylene black pigments, and other organic pigments or dyes; metal pigments made of scale-like foil pieces such as aluminum and brass; titanium dioxide-coated mica, bases coloring agents such as pearl luster (pearl) pigments composed of scaly foil pieces such as organic lead carbonate. For example, when the surface hue of an adherend such as a resin molded article on which a decorative sheet is laminated varies, the surface hue is concealed, and the stability of the color tone of the decorative layer provided as desired is improved. , an inorganic pigment such as a white pigment may be used.

When coloring a base material with a resin, any means such as adding (kneading or kneading) a coloring agent into the resin, or forming a coating film of a paint containing a resin and a coloring agent, should be adopted. can be done. When a base material made of fibrous material such as paper, woven fabric, or non-woven fabric is to be colored, it can be carried out by any means such as mixing with pulp or fibrous material, forming a coating film, or the like, or a combination thereof.

When coloring a base material made of a wood-based material, it can be carried out by dyeing with a dye, coating film formation, or a combination of these methods. In the case of coloring a substrate made of metal, in addition to coating film formation, an electrolytic coloring method or the like can be employed in which a metal oxide film is formed on the surface using an anodizing method. In addition, when the base material is colored with a non-metallic inorganic material, it can be carried out by either means of forming a coating film or adding it to the base material, or a combination of these means.

Additives may be added to the base material, if necessary. Additives, mainly in the case of resins, include, for example, inorganics such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. etc. The amount of the additive compounded is not particularly limited as long as it does not impair the surface characteristics, processing characteristics, etc., and can be appropriately set according to the required characteristics.

In order to improve the weather resistance of the decorative sheet of the present disclosure, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers among the additives.
Examples of the ultraviolet absorber and light stabilizer include those exemplified as those that can be contained in the later-described matte layer.
These ultraviolet absorbers, weathering agents such as light stabilizers, and other various additives can be used alone or in combination.

In the present disclosure, the above substrates may be used singly or in combination. A combination of a plurality of paper substrates may be used, or a paper substrate and a fiber substrate, a paper substrate and a resin substrate, a fiber substrate and a resin substrate, a paper substrate, a fiber substrate and a resin substrate. It may be a combination of materials. In addition, the resin base material may be composed of a single layer of the resin base material, or a multiple layer structure of the same or different resin.

The thickness of the substrate is as described above. Considering physical strength, economic efficiency, etc., the thickness is more preferably 40 μm or more, and the upper limit is more preferably 200 μm or less, and further preferably 100 μm or less.
In order to exhibit the same effect as this, when the substrate is paper, the basis weight is usually preferably 20 g/m ² or more and 150 g/m ² or less, more preferably 30 g/m ² or more and 100 g/m ^{2 or} less.

(primer layer)
When the decorative sheet of the present disclosure is composed of multiple layers, it may have a primer layer in order to improve the interlayer adhesion of the multiple layers.

The primer layer is mainly composed of a binder resin, and may contain additives such as ultraviolet absorbers and light stabilizers, if necessary.

Binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and polycarbonate-based urethane-acrylic copolymers (carbonate bonds in the polymer main chain). urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the end and side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer Resins such as coalescent resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins are preferred, and these can be used alone or in combination.
The binder resin may be obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins, followed by cross-linking and curing. Among these, a polyol resin such as an acrylic polyol resin is preferably crosslinked and cured with an isocyanate curing agent, and more preferably an acrylic polyol resin is crosslinked and cured with an isocyanate curing agent.

The thickness of the primer layer is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and still more preferably 1.5 μm or more and 6 μm or less.

(Transparent resin layer)
The decorative sheet of the present disclosure may have a transparent resin layer in order to increase its strength and protect each layer. The transparent resin layer may be provided between the base material and the glittering pattern layer when it has a base material, and when it has a decorative layer, the decorative layer and the base material may be provided in order to protect the decorative layer. It should be provided between the material.

Examples of resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, and the like. Among these, polyolefin-based resins and vinyl chloride resins are preferable from the viewpoint of post-processing suitability. Also, two or more of these various resins may be laminated or mixed for use.

The transparent resin layer may be transparent to the extent that the base material side of the transparent resin layer is visible, and if it has a decorative layer, it may be transparent to the extent that the decorative layer can be visually recognized. In addition, it may be colored, transparent, or translucent. That is, in the present invention, "transparency" means not only colorless transparency but also colored transparency and semi-transparency.

The transparent resin layer may contain additives such as UV absorbers, light stabilizers and other weather resistance agents, and colorants and the like.
The thickness of the transparent resin layer is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and even more preferably 60 μm or more and 100 μm or less, in order to protect the decorative layer and in consideration of post-processing suitability.

(decorative layer)
The decorative sheet of the present disclosure may further have a decorative layer in addition to the glitter pattern layer in order to improve the design. The decorative layer may be provided on the opposite side of the glitter pattern layer to the matte layer, and when a substrate is provided, it may be provided between the substrate and the glitter pattern layer.

The decorative layer may be, for example, a colored layer covering the entire surface (a so-called solid colored layer, or a pattern layer formed by printing various patterns using ink and a printing machine). Moreover, it may have two or more decorative layers, and may be a combination of a solid colored layer and a pattern layer.

The pattern (pattern) of the pattern layer is not particularly limited, and any desired pattern may be adopted. Examples include texture patterns on the surface of fabric, grain patterns on the surface of leather, geometric patterns, characters, figures, and combinations thereof.
The glitter pattern layer may be synchronized with the pattern of the decoration layer as described above.

The ink used for the decorative layer is a mixture of a binder resin and a coloring agent such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. used.
The binder resin for the decorative layer is not particularly limited, and examples include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and vinyl chloride-vinyl acetate copolymers. Resins such as coalesced resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins can be used. Moreover, various types of resins can be used, such as a one-pack curable resin and a two-pack curable resin with a curing agent such as an isocyanate compound.

As the colorant, a pigment having excellent hiding properties and weather resistance is preferred. Pigments similar to those exemplified as pigments that can be used in the substrate can be used.
The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more, based on 100 parts by mass of the resin constituting the decorative layer. 70 parts by mass or less is more preferable.

The decorative layer may contain additives such as ultraviolet absorbers, weathering agents such as light stabilizers, and colorants.
The thickness of the decorative layer may be appropriately selected according to the desired pattern, but is preferably 0.5 μm or more and 20 μm or less, and 1 μm or more, in order to hide the background color of the adherend and improve the design. , 10 μm or less, and more preferably 2 μm or more and 5 μm or less.

(adhesive layer)
The decorative sheet of the present disclosure may have an adhesive layer to improve adhesion between layers.

The adhesive layer can be composed of, for example, an adhesive such as a urethane-based adhesive, an acrylic adhesive, an epoxy-based adhesive, or a rubber-based adhesive. Among these adhesives, urethane-based adhesives are preferable in terms of adhesive strength.
Urethane-based adhesives include, for example, adhesives using two-liquid curing urethane resins containing various polyol compounds such as polyether polyols, polyester polyols and acrylic polyols, and curing agents such as isocyanate compounds.

The thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less, in order to efficiently obtain the desired adhesive strength.

[60° gross value]
The decorative sheet of the present disclosure has excellent matte effect visibility. In the present disclosure, "matte" means that the gloss is difficult to see, and it cannot be said unconditionally because it varies depending on the color tone, pattern, etc. of the decorative sheet. If it is about 0.0 or less, it is generally treated as "matte".
Until now, for example, black or other dark colors ("dark colors" means low brightness, for example, CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* L in the color system measured in accordance with JIS Z8781-4:2013 ^* value (hereinafter sometimes simply referred to as "L ^* value") means that it is usually about 40 or less, preferably 30 or less. Although it is possible to obtain excellent visibility of the matting effect with a 60° gloss value of 20.0 or less, preferably 10.0 or less, since a large amount of matting agent is used, streaks, Due to the occurrence of unevenness, it was not easy to manufacture, and the surface characteristics were degraded. Further, for example, with regard to the decorative sheet exhibiting a color tone other than black or other dark colors, even if a matting agent is used, there is a lower limit to the numerical value of the 60° gloss value, which is the same as the decorative sheet exhibiting black. It has not been possible to easily obtain a decorative sheet which is excellent in both the visibility of the matte effect and the texture. Such a tendency becomes more remarkable as the 60° gloss value becomes smaller.

In the decorative sheet of the present disclosure, by suppressing the amount of the wrinkle-forming stabilizer used to an extremely small amount, it is possible to suppress a significant increase in the viscosity of the resin composition, thereby facilitating layer formation. It naturally has surface properties such as excellent stain resistance, scratch resistance, weather resistance, etc.

Although the decorative sheet of the present disclosure changes depending on the color tone as described above, it cannot be defined unconditionally. 0 or less, furthermore, 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, 2.0 or less, so that the visibility of the extremely excellent matting effect can be expressed.
Further, a decorative sheet exhibiting a color tone other than black or other dark colors may also have the 60° gloss value. The 60° gloss value of the matte layer side of the decorative sheet of the present disclosure is substantially the same as the 60° gloss value of the surface of the matte layer forming the outermost surface of the decorative sheet.
In the present disclosure, the 60° gloss value on the matte layer side is the 60° specular gloss measured in accordance with JIS K 5600-4-7: 1999, using a gloss meter or the like at arbitrary 10 points. It is the average value of the values that can be measured from the matte layer side.

[Other physical properties]
The L ^* value of the decorative sheet of the present disclosure is preferably 80.00 or more and 90.00 or less, because the decorative sheet has an excellent matting effect and a bright pattern layer containing a bright pigment and a large difference in brightness. It is preferably 0.00 or more and 98.00 or less.
The total light transmittance of JIS K7361-1:1997 in the entire range of incident light from the matte layer of the decorative sheet of the present disclosure is generally determined by the layer structure constituting the decorative sheet, the patterning of the glitter pattern layer, etc. However, it is preferably 30% or less, more preferably 20% or less, even more preferably 30% or less.

[Method for manufacturing decorative sheet]
The matte layer of the decorative sheet of the present disclosure has a wrinkled structure on its outermost surface.
If necessary, a primer layer is further formed on the glitter pattern layer formed using the glitter pattern layer-forming composition, and the matte layer-forming composition is applied.
In forming the matte layer, the matte layer is formed by irradiating a resin composition for forming a matte layer containing a wrinkle-forming stabilizer with ultraviolet light having a short wavelength of at least 100 nm or more and 380 nm or less. It is possible to form wrinkles on at least one surface of the decorative sheet (matte layer), thereby imparting a matte effect to the decorative sheet (matte layer).

The details of the mechanism by which wrinkles are formed on at least one surface of the matte layer and the matting effect is exhibited by irradiating the resin composition for forming the matte layer with such short-wavelength ultraviolet rays are unknown. However, it is presumed to be due to the following mechanism.

When a coating layer formed by applying a resin composition for forming a matte layer to a predetermined thickness is irradiated with ultraviolet light having a short wavelength, the energy of the ultraviolet light penetrates only the surface portion, and the energy does not reach the lower layers. As a result, only the surface portion of the resin composition begins to harden, and it is thought that wrinkles are formed due to curing shrinkage occurring only on the surface. Thus, the formation of wrinkles is thought to occur when the resin composition for forming the matte layer is cured only in a certain thickness direction from the surface by irradiation with short-wave ultraviolet rays.
In addition, from the comparison of the examples and comparative examples described later, the formation of wrinkles is unstable when the wrinkle-forming stabilizer is not included, and the visibility and texture of the matte effect are stable over the entire surface of the matte layer. The stable expression of the matte effect cannot be explained only by the curing of only the surface portion by short-wave ultraviolet rays, because the matting effect is not sufficiently exhibited and the soft touch feeling is not sufficiently exhibited. That is, in order for the decorative sheet of the present disclosure to stably have wrinkles and exhibit a matting effect, it is essential that the wrinkle formation stabilizer is included. Considering that a stable matting effect due to wrinkle formation is not obtained when the wrinkle formation stabilizer is not contained, the wrinkle formation stabilizer has a function like a nucleus that triggers wrinkle formation. , around the core, the resin on the surface of the resin composition gathers to form convex portions (projections) of wrinkles and concave portions along with the formation of the convex portions (projections), and as a result, the formation of wrinkles is stabilized. , it is considered that the matting effect and stably appear.

The resin composition for forming a matte layer containing a wrinkle-forming stabilizer and a wrinkle-forming stabilizer used in the production method of the present disclosure includes the wrinkle-forming stabilizer and the matte The contents are the same as those described for the layer-forming resin composition.

In the production method of the present disclosure, the resin composition for forming the matte layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. By this irradiation, as described above, the energy of the ultraviolet rays penetrates only the surface portion, and the energy does not reach the lower layer, so that only the surface portion of the resin composition starts to harden. Cure shrinkage stabilizes the formation of wrinkles, and the surface layer of the resin composition becomes a cured product and constitutes a matte layer. Then, after that, curing progresses from the near-surface portion where curing progresses slowly to the deep portion away from the depth direction, and the layer of the resin composition becomes a cured product, thereby covering the entire thickness of the resin composition. It hardens and constitutes a matte layer having wrinkles on the surface that exhibit a light diffusion effect. In order to accelerate the progress of curing to the deep portion, it is preferable to perform another irradiation treatment after irradiating with light having a wavelength of 100 nm or more and 380 nm or less, as will be described later.

The light having a wavelength of at least 100 nm or more and 380 nm or less includes, for example, rare gases such as Ar, Kr, Xe, and Ne, halogen halides of rare gases such as F, Cl, I, and Br, or mixed gases thereof. Preferred is "excimer light," which includes light in the ultraviolet wavelength region from excited dimers, or excimers, formed by the discharge. The wavelength of the excimer light and the excimer serving as the light source include, for example, light with a wavelength of 126 nm emitted from the excimer of Ar ₂ (hereinafter abbreviated as “126 nm (Ar ₂ )”), 146 nm (Kr ₂ ), and 157 nm. Wavelength light such as (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), 351 nm (XeF) can be preferably employed. As the excimer light, either spontaneous emission light or laser light with high coherence due to stimulated emission can be used, but the use of spontaneous emission light is usually sufficient. A discharge lamp that emits the light (ultraviolet rays) is also called an “excimer lamp”.
The excimer light has a single wavelength peak and is characterized by a narrow half width of the wavelength compared to ordinary ultraviolet rays (for example, ultraviolet rays emitted from metal halide lamps, mercury lamps, etc.). By using such excimer light, the formation of wrinkles is stabilized, and the matting effect is stably improved.

In order to stabilize the formation of wrinkles and stably improve the matting effect, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, and still more preferably 155 nm or more. It is preferably 320 nm or less, more preferably 300 nm or less, even more preferably 250 nm or less, still more preferably 200 nm or less, and most preferably 172 nm (Xe ₂ ). Thus, in the present disclosure, in order to stably improve the matting effect, it is preferable to use light with a shorter wavelength. below) is more preferable, and short-wave ultraviolet rays are even more preferable.

In the present disclosure, the integrated light amount of the wavelength light is preferably 1 mJ/cm ² or more, more preferably 3 mJ/cm 2 or more, and even more preferably 3 mJ/cm ² or more, in order to stabilize the formation of wrinkles and stably improve the matting effect. is 5 mJ/cm ² or more. The upper limit is not particularly limited, and the upper limit is preferably 1,000 mJ/cm ² or less, more preferably 500 mJ/cm ² in order to reduce the number of lamps required for irradiating wavelength light and improve production efficiency. 300 mJ/cm 2 or less, more preferably 300 mJ/cm ² or less. In order to exhibit the same effect, the ultraviolet power density is preferably 1 mW/cm or more, more preferably 10 mW/cm or more, and still more preferably 20 mW/cm, and the upper limit is preferably 100 mW/cm or less, more preferably. is 70 mW/cm or less, more preferably 50 mW/cm or less.
In addition, the oxygen concentration at the time of irradiation with the above-mentioned wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

In the matte layer forming step in the method for producing a decorative sheet of the present disclosure, in addition to irradiation with light having a wavelength of at least 100 nm or more and 380 nm or less, another treatment that contributes to curing of the composition for forming a matte layer is performed. good too.
For example, in order to stabilize the formation of wrinkles due to the difference in the degree of hardening progress between the surface portion and the deep portion distant from the surface in the depth direction, and to promote the progress of hardening to the deep portion, for example, the thickness exceeds 380 nm. Wavelength light, preferably wavelength light of about 385 nm or more and 400 nm or less may be irradiated in advance to pre-cure the entire resin composition for forming a matte layer, and then irradiation with wavelength light of 100 nm or more and 380 nm or less may be performed. Further, after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, post-curing may be performed to further cure the resin composition. Pre-curing and post-curing may be appropriately determined depending on desired properties (for example, surface properties such as workability and stain resistance) required for the matte layer. Moreover, although the wavelength light belongs to ultraviolet rays, it is possible to use not only ultraviolet rays but also other ionizing radiation such as electron beams. For example, in post-curing, an electron beam can be preferably used in order to improve the surface properties of the matte layer.

In the production method of the present disclosure, the matte layer is formed by applying a resin composition for forming a matte layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, comma coating, and the like. The applied layer (uncured resin layer) can be formed by irradiating with light having a wavelength of at least 100 nm or more and 380 nm or less.

In addition, the decorative sheet obtained by the manufacturing method of the present disclosure may have other layers such as a transparent resin layer in addition to the base material described as the layer that can be employed in the decorative sheet of the present disclosure.
For example, the decorative layer, the adhesive layer and the primer layer can be formed by applying a coating liquid containing the composition for forming each layer by the known method described above, and drying and curing as necessary. Moreover, when forming a transparent resin layer, a resin film forming the transparent resin layer can be formed by dry lamination or the like.

(Application)
The decorative sheet of the present disclosure can be used as a decorative material as described later.

The decorative sheet of the present disclosure can also be used as a shaping sheet. When used as an embossing sheet, it can be used as an embossing plate, embossing sheet, etc. used for embossing in the second manufacturing method and the third manufacturing method, thereby forming an article composed of the single layer. , a thermosetting resin decorative board is obtained.
The surface shape of the shaped object (article composed of a single layer, thermosetting resin decorative board, etc.) is opposite to the surface shape of the shaped sheet (decorative sheet of the present disclosure) as described above. It becomes a shape exhibiting a shape.

[Cosmetic material]
The decorative sheet of the present disclosure can be used as a decorative material as it is, or can be used as a decorative material by being laminated, combined, or combined with an adherend. It is preferable that the decorative material has the decorative sheet on the adherend, but any of them may be determined as desired. When the decorative sheet of the present disclosure is used as a decorative material, the decorative sheet preferably has a decorative layer.

In the case of having an adherend, the decorative material has the adherend and the above-described decorative sheet of the present disclosure. The surface opposite to the surface on which wrinkles are formed in the layer to exhibit the matte effect is laminated. Moreover, when it has an adherend, the decorative sheet of the present disclosure preferably has a film or sheet form in consideration of ease of lamination.

(Substrate)
Examples of the adherend include flat plates of various materials, plate materials such as curved plates, three-dimensional shaped articles such as cylinders and polygonal prisms, sheets (or films), and the like. For example, it is used as a plate material such as a wood veneer made of various woods such as cedar, cypress, pine, lauan, wood plywood, laminated lumber, particle board, and wood fiberboard such as MDF (medium density fiberboard), and as a three-dimensional article. Wood members used as plate materials, three-dimensional articles, or sheets made of metals such as iron, aluminum, copper, and alloys containing one or more of these metals; Glass, ceramics such as ceramics, gypsum, cement , ALC (lightweight cellular concrete), ceramic materials used as plate materials and three-dimensional articles made of non-ceramic ceramic materials such as calcium silicate; acrylic resins, polyester resins, polystyrene resins, polyolefin resins such as polypropylene, ABS (acrylonitrile -butadiene-styrene copolymer) resins, phenolic resins, vinyl chloride resins, cellulose resins, resin members used as resins such as rubber plates, three-dimensional articles, and sheets. Moreover, these members can be used individually or in combination of multiple types.

The adherend may be appropriately selected from the above depending on the application, and may be interior members of buildings such as walls, ceilings, and floors, or exterior members such as outer walls, roofs, eaves, fences, gates, and windows. When used as fittings or fixtures such as frames, doors, handrails, baseboards, rims, moldings, etc., it is preferably made of at least one member selected from wooden members, metal members and resin members, such as entrance doors. When it is used as fittings such as exterior members, window frames, and doors, it is preferably made of at least one member selected from metal members and resin members.

The thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 mm or more and 100 mm or less, more preferably 0.3 mm or more and 5 mm or less, and still more preferably 0.5 mm or more and 3 mm or less.

(adhesive layer)
The adherend and the decorative sheet are preferably attached via an adhesive layer in order to obtain excellent adhesiveness.

The adhesive used for the adhesive layer is not particularly limited, and known adhesives can be used, and may be appropriately selected according to the application. For example, adhesives such as moisture-curable adhesives, anaerobic-curable adhesives, dry-curable adhesives, UV-curable adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives are preferred. be done.

Examples of resins used for these adhesives include acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, Examples include cyanoacrylate resins and epoxy resins, and these can be used alone or in combination. In addition, a two-liquid curing type urethane-based adhesive or an ester-based adhesive using an isocyanate compound or the like as a curing agent can also be applied.
A pressure-sensitive adhesive can also be used for the adhesive layer. As the adhesive, various adhesives such as acrylic, urethane, silicone, and rubber can be appropriately selected and used.

Although the thickness of the adhesive layer is not particularly limited, it is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and still more preferably 10 μm or more and 30 μm or less, in order to obtain excellent adhesiveness.

(Manufacturing method of decorative material)
The decorative material can be produced through a process of laminating the decorative sheet of the present disclosure and an adherend.
This step is a step of laminating the adherend and the decorative sheet of the present disclosure, and wrinkles are formed on the surface of the adherend that requires decoration and the matte layer of the decorative sheet of the present disclosure to achieve a matte effect. The surface opposite to the one surface to be developed and, if the decorative sheet of the present disclosure has a substrate, the surface on the side of the substrate are laminated so as to face each other. As a method for laminating the adherend and the decorative sheet, for example, there is a lamination method in which the decorative sheet is laminated on the plate-like adherend by pressing with a pressure roller via an adhesive layer.

When a hot-melt adhesive (heat-sensitive adhesive) is used as the adhesive, the heating temperature is preferably 160° C. or higher and 200° C. or lower, although it depends on the type of resin that constitutes the adhesive. °C or higher and 130 °C or lower. Moreover, in the case of vacuum forming, it is common to carry out while heating, and the temperature is preferably 80° C. or higher and 130° C. or lower, more preferably 90° C. or higher and 120° C. or lower.

The decorative material obtained as described above can be arbitrarily cut, and the surface and the butt end portion can be arbitrarily decorated such as grooving and chamfering using a cutting machine such as a router and a cutter. And various uses, for example, interior members of buildings such as walls, ceilings and floors, exterior members such as outer walls, eaves, roofs, fences and fences, window frames, doors, door frames, handrails, baseboards, In addition to fittings or fixtures such as rims and malls, general furniture such as chests, shelves, desks, kitchen furniture such as dining tables and sinks, surface decorative panels such as cabinets such as home appliances and OA equipment, interior and exterior of vehicles It is suitably used as a member for use.
In addition to the decorative materials used for buildings and the like, the decorative sheet of the present disclosure can be used as a single unit, or in a form in which the decorative sheet is laminated, combined, or combined with another material (adherent material). Packaging materials, anti-glare films for displays, whiteboards or blackboards, credit cards, cash cards, telephone cards, various cards such as various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (windows glass, etc.), artificial leather, etc. In these applications, it is preferable that the decorative sheet of the present disclosure, which exhibits excellent symmetry and texture, is arranged on the outermost surface, but other usage forms may be used depending on the application, purpose of use, etc. Of course it is possible.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

(Measurement of wrinkle structure (surface shape of decorative sheet))
Rz (maximum height), Ra (arithmetic mean roughness), Spc (arithmetic mean curvature of projection apex), Rsm (average length of curvilinear element), Sa of the decorative sheets obtained in Examples and Comparative Examples (Arithmetic mean height), Ssk (Skewness) and Sku (Kurtosis) are measured by a shape analysis laser microscope ("VK-X150 (control unit) / VK-X160 (measurement unit) ”, manufactured by Keyence Corporation), objective lens: 50 times, laser wavelength: 658 nm, measurement mode: surface shape mode, measurement pitch: 0.13 μm, measurement quality: at high speed mode It was measured.
Moreover, the cutoff value was set to 0.8 mm.

(Evaluation method: 60° gloss value)
For the decorative sheets obtained in Examples and Comparative Examples, a gloss meter ("Microgloss (model name)", manufactured by BYK Gardner) was used to measure the 60° gloss value in accordance with K 5600-4-7: 1999. (specular gloss) was measured.

(internal haze)
A polypropylene sheet (thickness: 60 μm) subjected to corona discharge treatment was used as a base material, and a resin composition (resin A) for forming a matte layer described later was applied to the base material. was applied by the gravure method (application amount: 18 μm (dry)). The coated surface is irradiated with ultraviolet rays (wavelength: 395 nm, maximum illuminance: 0.6 W/cm ² , integrated light intensity: 30 to 100 mJ/cm ² ) using a UV irradiation device composed of LEDs, and then excimer. Ultraviolet rays are irradiated using a light irradiation device (wavelength: 172 nm (Xe ₂ ), maximum illuminance: 30 mW/cm ² , integrated light intensity: 5 mJ/cm ² or more and 100 mJ/cm ² or less, nitrogen atmosphere (oxygen concentration 200 ppm or less). ), and then irradiated with an electron beam (accelerating voltage: 100 to 150 kV, irradiation dose: 30 to 100 kGy) to form a wrinkled structure.
An 80 μm thick TAC film (manufactured by FUJIFILM Corporation, TD80UL) was attached to the surface of the wrinkled structure via a transparent adhesive (manufactured by Panac Co., Ltd., PD-S1, thickness 25 μm) to flatten the uneven shape. Thus, a sample for internal haze measurement was produced in which the influence of haze caused by the surface shape was eliminated. The haze of the produced sample was measured to obtain the internal haze of the matte layer. The light incident surface during haze measurement was on the substrate side. A haze meter (HM-150, manufactured by Murakami Color Research Laboratory) was used as a measuring device, and the haze was measured according to JIS K7136:2000.

(Measurement of L ^* value)
The L ^* value of the decorative sheet obtained in each example described later was measured by the following method.
When the decorative sheet was viewed from the matte layer side in plan, the L ^* value was measured at arbitrary 10 points, and the average value of the 10 points was taken as the L ^* value of each decorative sheet. A spectrocolorimeter/color difference meter (“CM-700d” (model number), manufactured by Konica Minolta, Inc.) was used as a measuring device. During the measurement, the surface of the decorative sheet was irradiated with light (D65 light source) at an incident angle of 10 degrees. The measurement conditions were a viewing angle of 2 degrees, a measurement diameter of 3 mmφ, and a measurement mode of total reflected light (specular reflected light + diffuse reflected light).

(Visibility of brightness difference)
Regarding the decorative sheets obtained in Examples and Comparative Examples, 20 random adults were asked to evaluate the visibility of the glitter pattern layer. When the visibility of the glitter pattern layer through the matte layer is excellent, the area where the glitter pattern layer is present is recognized as a bright area. As a result, a decorative sheet with a matte effect and a large difference in brightness due to the glitter pattern layer can be obtained.
The visibility of the glitter pattern layer was evaluated according to the following criteria.

A: 18 or more persons evaluated that the effect of the bright pattern layer and the difference in lightness due to the bright pattern layer could be visually recognized.
B: 10 or more and 17 or less persons evaluated that the bright pattern layer and the effect of the brightness difference due to the bright pattern layer could be visually recognized.
C: Nine or less people evaluated that the effect of the bright pattern layer and the difference in lightness due to the bright pattern layer could be visually recognized.

[Example 1]
(Preparation of composition for forming matte layer)
30 parts by mass of a polyfunctional urethane acrylate oligomer (number of functional groups: 3), 30 parts by mass of a polyfunctional acrylate monomer (bifunctional), and 40 parts by mass of a monofunctional acrylate monomer are mixed, and a wrinkle-forming stabilizer (silica particles, average particle size Diameter: 3 μm, specific surface area: 100 m ² /g, oil absorption: 40 ml/100 g) and 0.8 parts by mass of a photopolymerization initiator (benzophenone type) were added to form a matte layer forming composition (resin A ).

(Preparation of Composition for Forming Glittering Pattern Layer)
A glittering pigment (particle size: 10 to 60 μm) was added to a urethane resin to obtain a composition for forming a glittering picture layer (resin B).

(Manufacture of decorative sheet)
A polypropylene sheet (thickness: 60 μm) subjected to corona discharge treatment was used as a substrate, and the composition for forming a glittering pattern layer (resin B) was applied to one surface of the substrate by a gravure method (coating amount: 3 μm (when dry)) and dried to form a glitter pattern layer on 60% (area ratio) of the surface area of the substrate.
A resin composition for forming a primer layer (urethane resin, coating amount: 2 μm (when dried)) was applied to the glitter pattern layer and dried to form a primer layer.

On the primer layer, the composition for forming a matte layer (resin A) is applied by a gravure method (coating amount: 5 g/m ² ), and then irradiated with ultraviolet rays using a UV irradiation device composed of an LED. (wavelength: 395 nm, maximum illuminance: 0.6 W/cm ² , integrated light intensity: 30 to 100 mJ/cm ² ), then using an excimer light irradiation device, ultraviolet light is irradiated (wavelength: 172 nm (Xe ₂ ), ultraviolet light Output density: 30 mW/cm, integrated light intensity: 5 mJ/cm ² or more and 100 mJ/cm ² or less, nitrogen atmosphere (oxygen concentration: 200 ppm or less)), then electron beam (acceleration voltage: 100 to 150 kV, irradiation dose: 30 to 100 kGy). By irradiation, a matte layer having a wrinkled structure on at least a part of the outermost surface was formed on the base material to obtain a decorative sheet having a glittering pattern layer and a matte layer. As described above, it was confirmed that the surface of the decorative sheet obtained in Example 1 had a wrinkled structure as shown in the optical microscope image of FIG.

The thickness of the glitter pattern layer was 2.0 μm, the thickness of the primer layer was 1.0 μm, and the thickness of the matte layer was 5.0 μm. The thickness of each layer is measured by preparing the cross section of the decorative sheet shown in FIG. 1 and measuring the thickness of each layer at arbitrary 10 points with an optical microscope.
The average particle size of the wrinkle stabilizer calculated from this was 60% of the thickness of the matte layer.
Table 1 shows the measurement results of internal haze, 60° gloss value, L ^* value, brightness difference visibility, and wrinkle structure of the obtained decorative sheet.

[Example 2]
In Example 1,
A decorative sheet having a glossy pattern layer and a matte layer was obtained in the same manner, except that the wrinkle-forming stabilizer in the matte layer-forming composition was changed to 10 parts by mass.
Table 1 shows the measurement results of the internal haze, 60° gloss value, L ^* value, brightness difference visibility, and wrinkle structure of the decorative sheet obtained in Example 2.

[Comparative Example 1]
In Example 1, without performing ultraviolet irradiation using a UV irradiation device composed of LEDs and ultraviolet irradiation using an excimer light irradiation device, an electron beam (accelerating voltage: 100 to 150 kV, irradiation dose: 30 to 100 kGy ) was cured only by irradiation to obtain a decorative sheet.

[Comparative Example 2]
The procedure was the same as in Comparative Example 1, except that 20 parts by mass of a matting agent (silica particles, average particle size: 3 μm, oil absorption: 200 ml/100 g) was added in place of the wrinkle-forming stabilizer in the composition for forming a matte layer. I got a makeup sheet.

[Comparative Example 3]
In Example 1, a primer layer was formed on the substrate without forming a glitter pattern layer, and then a matte layer was formed on the primer layer in the same manner as in Example 1 to obtain a decorative sheet having a matte layer. rice field.

Table 1 shows the measurement results of internal haze, 60° gloss value, L ^* value, brightness difference visibility, and wrinkle structure of the decorative sheets obtained in Comparative Examples 1 to 3.

"○" in the composition in Table 1 means that it has a glittering pattern layer, "×" means that it does not have a glittering pattern layer, and the irradiation condition "◯" means that irradiation is not performed. means gone.
From the results in Table 1, it was confirmed that the decorative sheets of Examples 1 and 2 were extremely excellent in the visibility of the matte effect.

On the other hand, the decorative material of Comparative Example 1 was a decorative sheet that was not irradiated with excimer light and did not form a wrinkled structure. The decorative sheet contains a wrinkle-forming stabilizer, but does not have a wrinkle structure. Therefore, although the visibility of the glitter pattern layer is excellent, the 60° gloss value is large and the matting effect is not exhibited. Do you get it.

The decorative sheet of Comparative Example 2 is a decorative sheet exhibiting a matting effect with a matting agent. Since this decorative sheet has a matting agent on its surface, the Spc and Sku values are larger than those of the decorative sheets of Examples 1 and 2. Also, although the 60° gloss value is comparable to that of the decorative sheet of Example 1, the internal haze is increased due to the influence of the matting agent. Due to these factors, the reflected light from the glitter pigment is blocked, so that the L ^* value is smaller than that of the decorative sheet of Example 1, and the visibility of the glitter pattern layer is also inferior. It's closed.

Compared with the decorative sheet of Example 1, the decorative material of Comparative Example 3 does not have a glitter pattern layer. Although the internal haze and 60° gloss value are comparable to those of the decorative sheet of Example 1, the L ^* value is lowered.

Since the decorative sheet of the present disclosure has an excellent matte effect visibility and texture, it can be used in a variety of applications, including building interior materials such as walls, ceilings and floors, outer walls, eaves, roofs and fences. , Exterior materials such as fences, window frames, doors, door frames, handrails, baseboards, rims, malls and other fittings or fixtures, general furniture such as chests of drawers, shelves, desks, kitchens such as dining tables and sinks As a decorative material for various members such as furniture, home appliances, surface decorative boards such as cabinets such as OA equipment, interior and exterior members of vehicles, and decorative materials used in the above-mentioned buildings etc., the present disclosure The decorative sheet of is used as a single unit, or in the form of laminating, combining, or combining the decorative sheet with other materials (adherends), such as packaging materials, antiglare films for displays, whiteboards (whiteboards) or blackboards, It can be suitably used as various cards such as credit cards, cash cards, telephone cards, various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (window glass, etc.), artificial leather, and the like.

2: Convex portion 3: Concave portion 20: Outermost surface 21: Matte layer 22: Primer layer 23: Glittering pattern layer 24: Decorative layer 25: Substrate 31: Adhesive layer 30: Adherend 100: Decorative sheet

Claims (17)

A decorative sheet comprising a glitter pattern layer containing a glitter pigment and a matte layer, wherein at least a part of the outermost surface of the matte layer has a wrinkled structure. 2. The decorative sheet according to claim 1, wherein said wrinkled structure is a structure having an uneven shape composed of irregular wrinkles. 3. The decorative sheet according to claim 2, wherein the irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary protrusions and recesses formed by being surrounded by the plurality of filamentary protrusions. . The decorative sheet according to any one of claims 1 to 3, wherein the matte layer has an internal haze of 5.0% or less. The decorative sheet according to any one of claims 1 to 4, wherein the wrinkled structure has a Rz (maximum height) of 3.25 µm or more and 10.00 µm or less as defined in JIS B0601:2013. The decorative sheet according to any one of claims 1 to 5, wherein the wrinkled structure has an Ra (arithmetic mean roughness) defined in JIS B0601:2013 of 0.10 µm or more and 2.00 µm or less. Any one of claims 1 to 6, wherein the wrinkle structure has an Spc (arithmetic mean curvature of the apex of the projection) of 3000.00 mm ⁻¹ or more and 8000.00 mm ⁻¹ or less, as defined in JIS B0601:2013 The cosmetic sheet described in the paragraph. The makeup according to any one of claims 1 to 7, wherein the wrinkle structure has an Rsm (average length of curvilinear elements) of 10.00 μm or more and 30.00 μm or less as defined in JIS B0601:2013. sheet. The decorative sheet according to any one of claims 1 to 8, wherein Sa (arithmetic mean height) defined in JIS B0601:2013 of the wrinkled structure is 0.01 µm or more and 2.00 µm or less. The decorative sheet according to any one of claims 1 to 9, wherein the wrinkled structure has an Ssk (skewness) defined in ISO25178-2:2012 of 0.01 or more and 1.50 or less. The decorative sheet according to any one of claims 1 to 10, wherein the wrinkled structure has an Sku of 2.00 or more and less than 4.00 as defined in ISO25178-2:2012. The matte layer is composed of a cured resin composition containing a binder resin and a wrinkle-forming stabilizer, and the average particle size of the wrinkle-forming stabilizer is 100% or less of the thickness of the matte layer and 30 μm or less. 12. Any one of claims 1 to 11, which has an average particle size with an upper limit of whichever is smaller, and contains 0.5 parts by mass or more of the wrinkle-forming stabilizer with respect to 100 parts by mass of the resin. The cosmetic sheet described in . The decorative sheet according to any one of claims 1 to 12, wherein the glitter pigment is a glitter inorganic pigment. 14. The decorative sheet according to any one of claims 1 to 13, wherein the surface area ratio of the decorative sheet having the glitter pattern layer is 3% or more and 95% or less. The decorative sheet according to any one of Claims 1 to 14, wherein the matte layer is provided over the entire surface of one surface of the decorative sheet. The decorative sheet according to any one of claims 1 to 15, wherein the surface shape has a 60° gloss value of 10.0 or less. A decorative material having the decorative sheet according to any one of claims 1 to 16 on an adherend.

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