Decorative sheets and decorative materials

Abstract

The present invention provides decorative sheets and decorative materials that offer excellent matte finish and a large difference in brightness due to a lustrous pattern layer containing lustrous pigments. [Solution] A decorative sheet and a decorative material having the decorative sheet, comprising a lustrous pattern layer containing a lustrous pigment and a matte layer, wherein at least a portion of the outermost surface of the matte layer has a wrinkled structure.

Description

Technical Field

[0001] The present disclosure relates to a cosmetic sheet and a cosmetic material.

Background Art

[0002] Conventionally, for example, interior members of buildings such as walls, ceilings, and floors; exterior members such as outer walls, eaves, roofs, fences, and gates; fittings or architectural members such as window frames, doors, door frames, handrails, baseboards, moldings, and trims; general furniture such as wardrobes, shelves, and desks; kitchen furniture such as dining tables and sinks; or surface decorative panels for cabinets of home appliances, OA equipment, etc.; and interior or exterior members of vehicles, so-called cosmetic sheets or cosmetic materials are used as articles for decorating and protecting the surfaces.

[0003] It is known that a decorative pigment-containing layer using a glitter pigment is provided on a cosmetic material used for these applications for the purpose of expressing a metallic design (Patent Document 1). In addition, a technique of improving the texture using a matte effect to improve the design property is widely used. As a cosmetic material using a matte effect, a cosmetic sheet having a pattern layer and a concealment layer on one side of a base sheet and a matte adjustment layer such as a matte layer or a gloss layer on the other side has been proposed (Patent Document 2). In the cosmetic sheet of Patent Document 2, a design effect of enhancing the pattern layer and the concealment layer is obtained by the difference in gloss between the matte layer and the gloss layer of the matte adjustment layer. In its example, a matte ink containing a total of 50 parts by weight of spherical alumina 10 parts by weight and calcium carbonate 40 parts by weight per 100 parts by weight of the resin component is used for the matte layer provided on the entire surface.

[0004] Further, Patent Document 2 proposes a cosmetic material having a printing layer and a transparent resin layer in this order on a base material, and an embossed pattern is provided on the outermost surface of the transparent resin layer.

Prior Art Documents

Patent Documents

Patent Document 1

[0006] When having a phosphorescent pigment-containing layer as in Patent Document 1, external light is reflected by the phosphorescent pigment, and the design of the part with the phosphorescent pigment-containing layer is visually recognized brighter than the design of the part without the phosphorescent pigment-containing layer. Thus, in order to express light and shade depending on the strength of reflection of external light, it is considered effective to provide a layer having a matte effect on the surface. As a method for improving the texture by the matte effect, a method using a matting agent (also referred to as a "mat agent") as in Patent Document 2 and having a light diffusion effect of the matting agent is known.

[0007] However, when combining a phosphorescent pigment-containing layer and a matte layer, the external light reflected by the phosphorescent pigment-containing layer passes through the matte layer again, so that it is diffused by the matting agent. For this reason, it becomes difficult to generate light and shade depending on the presence or absence of the phosphorescent pigment-containing layer.

[0008] An object of the present invention is to provide a decorative sheet and a decorative material having an excellent matte effect and a large difference in lightness due to a phosphorescent pattern layer containing a phosphorescent pigment. [Means for Solving the Problems]

[0009] In order to solve the above problems, the present invention provides the following decorative sheet and decorative material. [1] A decorative sheet having a phosphorescent pattern layer containing a phosphorescent pigment and a matte layer, and having a wrinkle structure on at least a part of the outermost surface of the matte layer. [2] The decorative sheet according to [1], wherein the wrinkle structure has an uneven shape formed by irregular wrinkles. [3] The decorative sheet according to [2], wherein the irregular wrinkles are composed of a plurality of protrusions formed by a plurality of linear protrusions and a recess formed by being surrounded by the plurality of linear protrusions.

[0010] [4] The decorative sheet according to any one of [1] to [3], wherein the internal haze of the matte layer is 5.0% or less. [5] The decorative sheet according to any one of [1] to [4], wherein the wrinkle structure has a maximum height Rz of 3.25 μm or more and 10.00 μm or less, as defined in JIS B0601:2013. [6] The decorative sheet according to any one of [1] to [5], wherein the wrinkled structure has an arithmetic mean roughness (Ra) of 0.10 μm or more and 2.00 μm or less, as defined in JIS B0601:2013.

[0011] [7] The wrinkle structure has an Spc (arithmetic mean curvature of the projection vertices) of 3000.00 mm as defined in JIS B0601:2013. -1 8000.00mm -1 The decorative sheet described in any one of the following [1] to [6]. [8] The decorative sheet according to any one of [1] to [7], wherein the Rsm (average length of curved elements) of the wrinkled structure, as defined in JIS B0601:2013, is 10.00 μm or more and 30.00 μm or less. [9] The decorative sheet according to any one of [1] to [8], wherein the arithmetic mean height (Sa) of the wrinkled structure, as defined in JIS B0601:2013, is 0.01 μm or more and 2.00 μm or less.

[0012]

[10] The decorative sheet according to any one of [1] to [9], wherein the wrinkle structure has an Ssk (skewness) of 0.01 or more and 1.50 or less as defined in ISO 25178-2:2012.

[11] The decorative sheet according to any one of [1] to

[10] , wherein the wrinkle structure has a Sku (kurtosis) of 2.00 or more and less than 4.00 as defined in ISO 25178-2:2012.

[12] The decorative sheet according to any one of [1] to

[11] , wherein the matte layer is composed of a cured product of a resin composition containing a binder resin and a wrinkle-forming stabilizer, the average particle size of the wrinkle-forming stabilizer has an upper limit of the smaller of 100% or less of the thickness of the matte layer and 30 μm or less, and the wrinkle-forming stabilizer is contained in an amount of 0.5 parts by mass or more per 100 parts by mass of the resin.

[0013]

[13] The decorative sheet according to any one of [1] to

[12] , wherein the luminous pigment is a luminous inorganic pigment.

[14] The decorative sheet according to any one of [1] to

[13] , wherein the area ratio having a glossy pattern layer within the surface of the decorative sheet 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.

[0014]

[16] The decorative sheet according to any one of [1] to

[15] , wherein the 60° gloss value of the surface shape is 10.0 or less.

[17] A decorative material having a decorative sheet according to any one of [1] to

[16] on a substrate. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide decorative sheets and decorative materials that have an excellent matte effect and a large difference in brightness due to a lustrous pattern layer containing lustrous pigments. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic diagram illustrating the layer structure of the decorative sheet of the present invention. [Figure 2] This is an optical microscope image of the surface of the decorative sheet obtained in Example 1. [Figure 3] This is a schematic diagram illustrating the wrinkle structure of the decorative sheet of the present invention. [Modes for carrying out the invention]

[0017] [Decorative sheet] The embodiments of the decorative sheet described herein will be explained below. In this disclosure, the numerical values ​​related to "greater than or equal to" and "less than or equal to" in numerical range descriptions are arbitrary combinations, and the numerical values ​​in the examples are numerical values ​​that can be used as the upper and lower limits of the numerical range.

[0018] The decorative sheet of this disclosure comprises a lustrous pattern layer containing a lustrous pigment and a matte layer, and is characterized in that at least a portion of the outermost surface of the matte layer has a wrinkled structure. When the decorative material 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 Figure 1. Also, when the decorative sheet has a base material, the matte layer is preferably provided so as to be the outermost surface opposite to the base material, as shown in Figure 1. In other words, when a viewer sees the decorative sheet, the matte layer is preferably provided so as to be the outermost surface (hereinafter also referred to as the "outermost surface of the decorative sheet"). The wrinkle structure described later is formed on this outermost surface 20. The glossy pattern layer is preferably provided on the side opposite to the viewer of the matte layer, and is preferably provided between the substrate and the matte layer or between the adherend and the matte layer.

[0019] <Luminous pattern layer> The lustrous pattern layer in this disclosure is a layer containing the lustrous pigment described below. The lustrous pattern layer may be a continuous layer or a patterned layer. The lustrous pattern layer contains the lustrous pigment, and external light is reflected by the lustrous pigment, causing the viewer to perceive the lustrous pattern layer portion as a bright area. For this reason, it is preferable that the lustrous pattern portion is patterned, with areas on the decorative sheet having a lustrous pattern layer and areas without it, rather than being provided across the entire surface of the decorative sheet. This is preferable because the areas with the lustrous pattern layer are perceived as bright areas, and the areas without the lustrous pattern layer are perceived as dark areas, resulting in a decorative sheet with a high difference in brightness (difference in brightness between dark and bright areas).

[0020] In this disclosure, "brightness" refers to CIE L * a * b * Color brightness (L * ) means, and can be measured, for example, by the method described in the examples. "Dark area" is relatively L * This means that the value is small in the region, and the "bright area" is relatively L * This represents a region where the value is large. Since these values ​​vary depending on the design expressed by the decorative sheet, it is preferable to adjust them appropriately to match the design.

[0021] In the case of a patterned layer, the preferred range for the area ratio of the glossy pattern layer relative to the entire surface of the decorative sheet when viewed from above cannot be generalized, as it can be appropriately selected depending on the design expressed by the decorative sheet. However, in order to distinguish between light and dark areas, the ratio of the area occupied by the glossy pattern layer to the area of ​​one side of the decorative sheet (area ratio) is preferably 95% or less, preferably 90% or less, and in order to recognize the light areas, it is preferably 3% or more, preferably 5% or more. The area ratio can be expressed by the following formula. Area ratio = Area of ​​the glossy pattern layer ÷ Area of ​​the decorative sheet in plan view × 100 (%) In this disclosure, "plan view" means viewing the decorative material sheet of this disclosure in a planar direction from the surface side, which is the side on which the lustrous pattern layer is provided. For example, in the XYZ coordinate system shown in Figure 1, the planes represented by the X-axis and Y-axis coincide with the surface of the decorative sheet, and "plan view" corresponds to viewing the surface of the decorative material from the positive Z-axis direction.

[0022] The patterning depends on the design expressed by the decorative sheet, and may be a harmonious pattern in combination with the decorative layer described later, or it may be randomly arranged. For example, when applying a wood grain pattern to the entire decorative sheet, it is preferable to use a wood texture pattern (parts other than the pore groove pattern and / or knot pattern), when applying a stone pattern such as travertine to the entire decorative sheet, it is preferable to use a pattern other than the recessed areas, and when applying a tile pattern or brick pattern to the entire decorative sheet, it is preferable to use a pattern on the tile or brick parts. When expressing a metallic luster to the entire decorative sheet, it is preferable to arrange it randomly without any regularity.

[0023] The lustrous pattern layer may contain the lustrous pigments described below, but it may also be a cured product of a lustrous pattern layer forming composition obtained by further mixing a binder resin with appropriate amounts of pigments, dyes and other colorants, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers, etc., in addition to the lustrous pigments. The amount of lustrous pigment in the lustrous pattern layer forming composition is preferably 10 to 90 parts by mass, more preferably 50 to 80 parts by mass, per 100 parts by mass of binder resin.

[0024] By including 10 parts by mass or more of the luminous pigment, it is possible to easily achieve sufficient gloss in the bright areas. Furthermore, by including 90 parts by mass or less of the luminous pigment, it is possible to suppress the impairment of the visibility of the pattern when a decorative layer is present beneath the luminous pattern-forming composition. To ensure sufficient gloss in the bright areas and prevent impairment of the visibility of the pattern, the thickness of the lustrous pattern layer is preferably 0.5 μm to 30 μm, and more preferably 1 μm to 10 μm. Examples of binder resins for the lustrous pattern layer forming composition include thermoplastic resins and curable resins, and curable resins are preferred to improve durability. Examples of curable resins include thermosetting resins and ionizing radiation-curable resins. Thermosetting resins are preferred in order to improve adhesion between the glossy pattern layer and the layers above and below it (substrate, decorative layer, primer layer, matte layer, etc.).

[0025] Examples of thermosetting resins for the glossy 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, along with a curing agent added as needed.

[0026] As the ionizing radiation-curable resin for the glossy pattern layer, the same type as the ionizing radiation-curable resin for the matte layer described later can be used. The glossy pattern layer can be formed, for example, by printing using a glossy pattern layer forming composition.

[0027] (Luminous pigment) The aforementioned lustrous pigment is not particularly limited as long as it is a pigment that reflects ambient light (incident light), and may be an inorganic pigment or an organic pigment. To improve weather resistance, lustrous inorganic pigments are preferred, and metallic flakes or pearl pigments are preferred, and these individually or in mixtures are preferred. Examples of materials for the aforementioned metal flakes include metals and alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel-chromium, and stainless steel.

[0028] Examples of the metal flakes include those obtained by vacuum-depositing the metal or alloy onto a plastic film, peeling off the thin metal film from the plastic film, and then crushing and stirring the peeled thin metal film; those obtained by mixing the powder of the metal or alloy with a solvent and spreading and / or crushing the powder using a medium stirring mill, ball mill, attritor, etc.; and those obtained by having the surface of the aforementioned material coated with resin. The pearl pigment preferably includes one or more selected from pearl pigments and metal flakes as the luminous pigment. The pearl pigment is preferable because it can easily suppress the decrease in light transmittance of the luminous ink layer, and therefore does not impair the visibility of the decorative layer when a decorative layer exists beneath the luminous ink layer. Examples of pearl pigments include white pearl pigments, interference pearl pigments, and colored pearl pigments.

[0029] The aforementioned white pearl pigment consists of a scale-like matrix made of mica, aluminum, glass, etc., covered with a coating layer made of a colorless, high refractive index material such as titanium dioxide. The thickness of the coating layer is relatively small, approximately 0.1 μm to 0.15 μm, and it reflects almost all wavelengths of light, so it appears white or silver. The aforementioned 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 white pearl pigment, exceeding 0.15 μm. This thickness alters the reflected and transmitted light, producing various interference colors. It is sometimes called iridescent pearl.

[0030] The average particle size of the lustrous pigment is preferably 1 μm to 500 μm, and more preferably 5 μm to 100 μm, in order to impart lustrousness and suppress the shedding of the lustrous pigment. To achieve a similar effect, the ratio of [average particle size of the lustrous pigment / thickness of the lustrous pattern layer] is preferably 0.01 or more and 15 or less, and more preferably 0.5 or more and 10 or less.

[0031] <Matte finish> The matte layer of this disclosure is a layer having the wrinkled structure described below in at least a portion of its outermost surface, and is a layer provided on the outermost surface of the decorative sheet as described above. The matte layer has a wrinkled structure on at least a portion of its outermost surface, and this wrinkled structure causes ambient light (incident light) to be diffusely reflected, resulting in a matte finish.

[0032] Preferably, the matte layer is composed of a cured product of a resin composition containing a resin and a wrinkle-forming stabilizer described below, wherein the wrinkle-forming stabilizer has an average particle size that is limited to the smaller of 100% or less of the thickness of the matte layer and 30 μm or less, and the wrinkle-forming stabilizer is present in an amount of 0.5 parts by mass or more per 100 parts by mass of the resin.

[0033] The average particle size of the wrinkle-forming stabilizer is preferably 5% or more of 80% or less of the thickness of the matte layer, more preferably 10% or more of 70% or less, and even more preferably 15% or more of 60% or less, in order to form a stable wrinkle structure. The thickness of the matte layer is preferably 0.1 μm to 40.0 μm, more preferably 1.0 μm to 30.0 μm, even more preferably 2.0 μm to 2.0 μm, and even more preferably 3.0 μm to 18.0 μm, in order to exhibit wrinkle stability, improve abrasion resistance, and improve the visibility of the glossy pattern layer. The thickness of the matte layer can be determined, for example, by the method described in the examples.

[0034] To stably form a wrinkle structure, the wrinkle-forming stabilizer is more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of the resin. As an upper limit, in order to transmit reflected light from the lustrous pattern layer, it 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.

[0035] As the matte layer forming composition, a resin composition containing a binder resin and a wrinkle-forming stabilizer is preferred because it can have an excellent matte effect. That is, in this 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 in coordination with the glossy pattern layer, but it is preferable that it be provided over the entire surface of one side of the decorative sheet in order to uniformly exhibit a matte effect.

[0036] (Internal haze in the matte finish layer) It is preferable that the matte layer has low internal haze. As mentioned above, when a decorative sheet is made by combining a glossy pattern layer and a matte layer, the external light (incident light) reflected by the glossy pattern layer will pass through the matte layer again. If the internal haze of the matte layer is large when this light passes through, the brightness of the bright areas (L) will be reduced.* ) decreases, resulting in a decrease in the brightness difference. In order to reduce the internal haze of the matting layer, it is preferable to perform at least one or both of making the refractive index difference between the binder resin and the wrinkle formation stabilizer in the matting layer the same and increasing the sphericity of the wrinkle formation stabilizer.

[0037] The internal haze can be appropriately selected according to the design expressed by the decorative sheet. However, in order to increase the brightness difference between the bright part and the dark part of the decorative sheet, the upper limit value is preferably 5.0% or less, more preferably 4.0% or less, and even more preferably 3.6% or less. The lower limit value is not particularly limited, but it is preferably substantially 0% or more. Substantially means considering measurement errors. The internal haze of the matting agent can be determined by, for example, separately preparing only the matting layer used in the decorative sheet and measuring it by the method described in the examples.

[0038] (Binder resin) As the binder resin for forming the matting layer, any resin that can form a cured product by forming a matting layer forming resin composition containing a predetermined amount of the wrinkle formation stabilizer described below and curing it to constitute the matting layer may be used. The binder resin preferably forms a wrinkle structure on its outermost surface and has a refractive index similar to that of the wrinkle formation stabilizer described below. The upper limit value of the absolute value of the difference in the absolute value of the refractive index between the binder resin for forming the matting layer and the wrinkle stabilizer described below is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less. The lower limit value is not particularly limited, but it is preferably substantially 0.

[0039] In the present disclosure, the refractive index means the refractive index at a wavelength of 589 nm. Examples of such resins include ionizing radiation-curable resins. As shown in Figure 1, the matte layer is a layer that can be provided on the outermost surface of the decorative sheet of this disclosure. Therefore, it is preferable that the resin is one that can easily form wrinkles with a wrinkle-forming stabilizer and maintain that shape, and also one that readily exhibits surface properties such as processing properties, stain resistance, scratch resistance, and weather resistance in order to improve the usability of the decorative sheet. Ionizing radiation-curable resins are therefore preferred resins. Because the decorative sheet of this disclosure contains an extremely small amount of wrinkle-forming stabilizer in the matte layer, the performance of the resin forming the matte layer is more directly expressed as a surface property.

[0040] Ionizing radiation-curable resins are resins having ionizing radiation-curable functional groups, which are groups that crosslink and harden upon irradiation with ionizing radiation. Preferred examples include functional groups having ethylenic double bonds, such as (meth)acryloyl groups, vinyl groups, and allyl groups. In this disclosure, (meth)acryloyl group refers to either an acryloyl group or a metacloyl group. Furthermore, in this disclosure, (meth)acrylate refers to either an acrylate or a methacrylate. Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing and / or bridging molecules. While ultraviolet (UV) or electron beams (EB) are commonly used, the term also includes other electromagnetic waves such as X-rays and gamma rays, as well as charged particle beams such as alpha rays and ion beams.

[0041] Examples of ionizing radiation-curable resins include electron beam-curable resins and ultraviolet-curable resins. Ultraviolet-curable resins are preferred in order to stabilize wrinkle formation by wrinkle-forming stabilizers, thereby stably improving the matte effect, and to reduce internal haze in the matte layer. Specifically, the ionizing radiation-curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation-curable resins.

[0042] As polymerizable monomers, (meth)acrylate monomers having a radical polymerizable unsaturated group in the molecule are preferred, and among these, polyfunctional (meth)acrylate monomers are preferred. Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least one (meth)acryloyl group as such functional group.

[0043] To stabilize wrinkle formation and stably improve the matte effect, and further improve surface properties such as post-processing characteristics, scratch resistance, and weather resistance, the number of functional groups in the polyfunctional (meth)acrylate monomer is preferably 2 to 8, and more preferably 2 to 6. Furthermore, with the aforementioned number of functional groups, the wrinkle structure described later is particularly easily obtained. These polyfunctional (meth)acrylates may be used individually or in combination of multiple types.

[0044] Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least one (meth)acryloyl group as such functional group. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, and the like. Furthermore, polymerizable oligomers include other highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins that have many reactive groups in a small molecule, and oligomers having cationic polymerizable functional groups in the molecules of novolac-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc.

[0045] These polymerizable oligomers may be used individually or in combination of multiple types. To stabilize wrinkle formation and stably improve the matte effect, and to reduce internal haze in the matte layer, and further to improve surface properties such as post-processing properties, scratch resistance and weather resistance, urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, and acrylic (meth)acrylate oligomer are preferred, urethane (meth)acrylate oligomer and polycarbonate (meth)acrylate oligomer are more preferred, and urethane (meth)acrylate oligomer is even more preferred.

[0046] The number of functional groups in these polymerizable oligomers is preferably between 2 and 8, with a more preferable upper limit of 6 or less, and even more preferable of 4 or less, in order to stabilize wrinkle formation, stably improve the matting effect, reduce internal haze in the matting layer, and further improve surface properties such as processing characteristics, scratch resistance, and weather resistance. Furthermore, for similar purposes, the weight-average molecular weight of these polymerizable oligomers is preferably 2,500 to 7,500, more preferably 3,000 to 7,000, and even more preferably 3,500 to 6,000. Here, the weight-average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

[0047] In this disclosure, it is preferable to use a combination of the polymerizable oligomer and polymerizable monomer as the binder resin for forming the matte layer. In this case, a polyfunctional urethane (meth)acrylate oligomer is preferred as the polymerizable oligomer, and a polyfunctional urethane acrylate oligomer is more preferred. The polymerizable monomer is preferably a polyfunctional polymerizable monomer, more preferably a polyfunctional (meth)acrylate monomer, and even more preferably a polyfunctional acrylate monomer. This can stabilize wrinkle formation, stably improve the matte effect, reduce internal haze in the matte layer, and further improve surface properties such as processing properties, scratch resistance, and weather resistance.

[0048] When used in combination, the content of polymerizable oligomers per 100 parts by mass of the total amount of polymerizable oligomers and polymerizable monomers is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, and even more preferably 60 parts by mass or more, with an upper limit of 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. Polymerizable oligomers can also be used in combination, and it is preferable to use two polymerizable oligomers with different numbers of functional groups in combination. In this case, the content of the polymerizable oligomer with a larger number of functional groups per 100 parts by mass of the total amount of polymerizable oligomers is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 65 parts by mass or more.

[0049] (Wrinkle-forming stabilizer) The wrinkle-forming stabilizer stabilizes wrinkle formation on at least one surface of the matte layer, thereby forming a wrinkled structure on at least a portion of the surface of the decorative sheet. Therefore, it is preferable that the matte layer contains a wrinkle-forming stabilizer. Although a wrinkled structure can be formed in the matte layer without using a wrinkle-forming stabilizer, using a wrinkle-forming stabilizer stabilizes the formed wrinkled structure, providing stable visibility of the matte effect (hereinafter, expressions such as "stable visibility of the matte effect" or similar expressions may be used), and uniformity of the surface condition (also referred to as "texture") due to the stable formation of wrinkles across the entire surface of the matte layer.

[0050] In this disclosure, "wrinkle formation stabilization" means that the in-plane distribution (variance σ) of the wrinkle shape and its geometric characteristic values ​​(length, width, and ratio of individual protrusions), and their statistical indicators (Rz, Ra, Spc, Rsm, Sm, Ssk, Sku, etc. in this case), converges compared to the case without the addition of the wrinkle formation stabilizer. As a result, the in-plane distribution (variance σ) of the 60° gloss value of the surface shape, as described later, also converges. The wrinkle formation stabilizer is added not to diffuse light and create a matte finish, but to stabilize the wrinkle structure. Therefore, even if the constituent materials and average particle size of the so-called "matting agents" in the prior art and the "wrinkle-forming stabilizers" in this disclosure are the same or similar, they will differ in their matting mechanisms (actions), the structure for producing the matting effect, and the relationship between the amount used and the degree of surface gloss (gloss value).

[0051] In the prior art described in Patent Document 2 and other documents, the matting agents used for matte finishes exhibit a matte effect through a light diffusion effect caused by their physical shape. Specifically, what is generally referred to as a matting agent generally has a refractive index difference between the matting agent particles and the surrounding resin and air, and exhibits a matte effect through the reflection of light rays corresponding to the contour shape of the particles and the light diffusion effect due to the refractive interface. For this reason, if a matting agent is used in a matte layer combined with a glossy pattern layer as in this disclosure, the ambient light (incident light) reflected by the glossy pigment is diffused by the matting agent, and the brightness of the bright areas decreases.

[0052] On the other hand, the wrinkle-forming stabilizer does not produce the visibility of the matte effect through light diffusion due to the reflection and refraction of light rays by the particles themselves, but rather stabilizes the formation of wrinkles on the surface of the matte layer due to the wrinkle-forming stabilizer, thereby stably imparting a matte effect and texture to the decorative sheet through the light diffusion effect at the refractive index difference interface between the surface and the air. Therefore, the wrinkle-forming stabilizer used in this disclosure differs from a matting agent that produces the visibility of the matte effect itself (even if the constituent materials and average particle size of both are the same or similar), in terms of the mechanism (action) of matting and the structure for producing the matte effect.

[0053] Furthermore, "wrinkle-forming stabilizers" and "matting agents" differ in their relationship to the amount contained and the surface gloss value. When the same substance A is used as a wrinkle-forming initiator AW (W: wrinkle) and is included in a specific amount C to form wrinkles on the surface, the 60° gloss value G of the surface is... 60° AW (C) is the 60° gloss value G of the surface when substance A is used as a simple matting agent AM and is included in the specified amount C, but no wrinkles are formed on the surface. 60° AM This is clearly lower than (C). In other words, the following relationship holds: G 60° AW (C) <G 60° AM (C)

[0054] The matte layer in the decorative sheet of this disclosure may contain agents that have been conventionally used as matting agents, but preferably to an extent that does not affect the internal haze of the matte layer, and more preferably without any matting agents. Thus, the decorative sheet of this disclosure can be said to have extremely excellent visibility of the matte effect even without substantially containing the matting agents that were conventionally used to obtain visibility of the matte effect. Here, "without matting agents" means not only that it does not contain any matting agents at all, but also that even if it contains matting agents, it does not have visibility of the matte effect based on the action of the matting agent itself. Specifically, the content of the matting agent is less than 10.0 parts by mass per 100 parts by mass of binder resin, preferably 5.0 parts by mass or less, and more preferably 1.0 part by mass or less.

[0055] As mentioned above, any wrinkle-forming stabilizer that is not a matting agent and whose average particle size is limited to the smaller of 100% or less of the thickness of the matting layer or 30 μm or less can be used without particular restrictions. In this disclosure, the average particle size of particles such as luminous pigments and wrinkle-forming stabilizers is the average particle size (arithmetic mean diameter) measured for 100 randomly selected non-aggregated particles when observing the cross-section in the thickness direction of each layer of the sheet using a scanning electron microscope (SEM) under conditions of an acceleration voltage of 3.0 kV and a magnification of 50,000 times. The particle size is the value measured by the distance between two parallel lines that maximize the distance between the two lines when the cross-section of the particle is sandwiched between them.

[0056] For example, organic particles and inorganic particles can be used as wrinkle-forming stabilizers. Examples of organic materials constituting the organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, and polyester resin. It is preferable to use organic particles to reduce the refractive index difference between the binder resin and the wrinkle-forming stabilizer of the matte layer and to reduce internal haze in the matte layer. Inorganic materials that make up inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate, among which silica is preferred due to its excellent transparency. In order to improve the strength of the matte layer, it is preferable to use inorganic particles.

[0057] There are no particular restrictions on the shape of the wrinkle-forming stabilizer, but examples include spherical, polyhedral, flaky, and irregular shapes. However, a spherical shape is preferable in order to reduce internal haze in the matte layer. By being spherical, the diffusion of reflected light from the lustrous pigment by the wrinkle-forming stabilizer is suppressed, and the brightness of the bright areas (L) is reduced. * This is because it is thought that a decrease in ) will become less likely. To reduce internal haze in 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 even more preferably 5% or less. There is no particular limit on the lower limit, but for ease of availability, it is preferably 0.1% or more, and more preferably 0.5% or more.

[0058] In this disclosure, "sphericity" refers to the average value of the degree of deviation of the outer shape of 10 arbitrarily selected particles from a perfect circle. Specifically, it refers to the ratio (%) of the maximum value of the radial distance between the smallest circumscribed circle (minimum circumscribed circle) and each point on the particle surface to the radius of the smallest circumscribed circle (minimum circumscribed circle) that touches the surface of each particle, as seen in electron microscope images of each particle. When silica is used as a wrinkle-forming stabilizer, a smaller specific surface area obtained by the nitrogen adsorption method and the BET method is preferable because it suppresses light diffusion. For this reason, the specific surface area is 50 m². 2 / g or more 800m 2 It is preferable that it be less than or equal to / g, and 100m 2 / g or more 500m 2 It is more preferable that the amount is less than or equal to / g. Similarly, a smaller oil absorption amount is preferable because it suppresses light diffusion. For this reason, the oil absorption amount is preferably 700 ml / 100 g or less, and more preferably 600 ml / 100 g or less. The oil absorption amount was determined by the method described in JIS K6217-4 "Method for determining oil absorption amount".

[0059] The surface of the wrinkle-forming stabilizer may be coated with an organic compound to suppress light diffusion. To achieve a matte finish and reduce internal haze in the matte layer, it is preferable to use at least one of two types of wrinkle-forming stabilizers, distinguished by their average particle size, where the average particle size is limited to the smaller of either 100% or less of the thickness of the matte layer or 30 μm or less. Specifically, the two types of wrinkle-forming stabilizers are wrinkle-forming stabilizer 1, which has an average particle size of 1 μm or more and is limited to the smaller of either 100% or less of the thickness of the matte layer or 30 μm or less, and wrinkle-forming stabilizer 2, which has an average particle size of less than 1 μm. In this disclosure, by using at least one of the two types of wrinkle-forming stabilizers, wrinkle formation is stabilized, a stable and excellent matte finish can be obtained, and internal haze in the matte layer can be reduced.

[0060] The average particle size of the wrinkle-forming stabilizer 1 is 1 μm or more, and is limited to the smaller of 100% or less of the thickness of the matte layer and 30 μm or less. In order to stably improve the matte effect and reduce internal haze in the matte layer, the average particle size of the wrinkle-forming stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.8 μm or more. As an upper limit, with respect to the thickness of the matte layer, it is preferably 90% or less of the thickness of the matte layer, more preferably 80% or less, and even more preferably 70% or less. As for the absolute value, it is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and even more preferably 7 μm or less. The smaller of the upper limit with respect to the thickness of the matte layer and the upper limit of the absolute value can be used. For example, the upper limit may be set to the smaller of 90% or less of the thickness of the matte layer and 20 μm or less, or it may also be set to the smaller of 90% or less of the thickness of the matte layer and 10 μm or less. The thickness of the matte layer will be discussed later.

[0061] Furthermore, the average particle size of the wrinkle-forming stabilizer 2 is less than 1 μm. In order to stabilize wrinkle formation, stably improve the matte effect, and reduce internal haze in the matte layer, the average particle size of the wrinkle-forming stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, even more preferably 5 nm or more, with an upper limit of preferably 900 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less. An average particle size near or below the visible light range is preferable because it reduces internal haze in the matte layer relative to visible light.

[0062] In order to stabilize wrinkle formation by the wrinkle-forming stabilizer, stably improve the matte effect, and reduce internal haze in the matte layer, the content of the wrinkle-forming stabilizer (the total content of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 when used in combination) is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, even more preferably 1.0 part by mass or more, and even more preferably 1.2 parts by mass or more, per 100 parts by mass of the binder resin forming the matte layer. As for the upper limit, there is no particular limit in order to stably improve the matte effect and reduce internal haze in the matte layer, but in order to improve the productivity of the cosmetic material due to 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 preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, even more preferably 10.0 parts by mass or less, even more preferably 7.5 parts by mass or less, and especially preferably 6.0 parts by mass or less.

[0063] When wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 are used in combination, there are no particular restrictions on the content of each wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 as long as the total content is within the above range. However, the content of wrinkle-forming stabilizer 2 is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 part by mass or more, per 100 parts by mass of binder resin, with an upper limit of 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. Furthermore, the blending ratio of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 is preferably 0.0 parts by mass or more and 0.95 parts by mass or less, more preferably 0.10 parts by mass or more and 0.90 parts by mass or less, even more preferably 0.20 parts by mass or more and 0.80 parts by mass or less, and even more preferably 0.30 parts by mass or more and 0.70 parts by mass or less, based on the total amount of these two ingredients being 100 parts by mass.

[0064] As previously described, organic and inorganic particles can be used as wrinkle-forming stabilizers. However, the types of particles themselves include those conventionally used as matting agents. For example, the matte layer of the decorative sheet described in Patent Document 1 uses matting agents such as spherical alumina and calcium carbonate. For matting agents such as spherical alumina and calcium carbonate to exhibit a visible matting effect due to the light diffusion effect caused by their physical shape, they need to be used in an amount of approximately 50 parts by weight in total, consisting of 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of resin, as described in Patent Document 1. However, in this disclosure, even with a small amount of content, as previously described, that is, even with a content less than the amount necessary to exhibit a visible matting effect due to the light diffusion effect caused by their physical shape, an extremely superior matting effect is obtained compared to the effect obtained by matting agents, and a soft touch feeling is also obtained. Therefore, even though the decorative sheet of this disclosure substantially does not contain a matting agent, it can be said that, by stably forming wrinkles on the surface, it can stably obtain a more superior matting effect and texture compared to when a matting agent is used, and can reduce internal haze in the matting layer.

[0065] (Matte finish forming composition) The matte layer is preferably composed of a cured product of a resin composition containing the wrinkle-forming stabilizer in a predetermined amount, and the resin composition preferably contains the resin and the wrinkle-forming stabilizer in a predetermined amount. In addition to the wrinkle-forming stabilizer and the resin, the resin composition used in this disclosure may also contain other components depending on the desired performance, etc. The resin composition for forming the matte layer may contain monofunctional (meth)acrylates, for example, to reduce its viscosity. These monofunctional (meth)acrylates may be used individually or in combination of multiple types.

[0066] Furthermore, if the resin is an ultraviolet-curable resin that hardens when exposed to ultraviolet light, it is preferable to include additives such as photopolymerization initiators and photopolymerization accelerators. By including these additives, the resin can be cured using ultraviolet light (without using ionizing radiation), and surface properties that are useful for practical applications can be obtained. Examples of photopolymerization initiators include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, etc.

[0067] Furthermore, photopolymerization accelerators can reduce polymerization inhibition by air during curing and accelerate the curing speed. Examples include one or more selected from p-dimethylaminobenzoate isoamyl ester, p-dimethylaminobenzoate ethyl ester, etc.

[0068] Since the matte layer is a layer that can be provided on the outermost surface of the decorative sheet of this disclosure, it is preferable that it is a weather-resistant layer, and preferably contains various weather-resistant agents such as ultraviolet absorbers and light stabilizers. As UV absorbers, any UV absorbers commonly used in cosmetic materials, decorative sheets, etc., can be used without particular limitations, such as benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, and hydroxyphenyltriazine-based UV absorbers. Similarly, as light stabilizers, any light stabilizers commonly used in cosmetic materials, decorative sheets, etc., can be used without particular limitations, such as hindered amine-based light stabilizers like piperidinyl sebacate-based light stabilizers. Furthermore, these UV absorbers and light stabilizers may have reactive functional groups with ethylenic double bonds in their molecules, such as (meth)acryloyl groups, vinyl groups, and allyl groups. These weather-resistant agents, such as UV absorbers and light stabilizers, can be used individually or in combination.

[0069] <Wrinkle structure> The matte layer in the decorative material of this disclosure is a layer composed of a cured product of a resin composition for forming a matte layer, which contains the aforementioned specific wrinkle-forming stabilizer in a specific amount as needed. As described above, the formation of wrinkles is stable on the outermost surface of the matte layer, and the visibility and texture of the matte effect are stably expressed due to the light diffusion effect caused by the shape of the wrinkles. Figure 1 is a schematic cross-sectional view showing one embodiment of the decorative sheet of this disclosure. Figure 1 shows that the decorative sheet of this disclosure has a wrinkle structure formed on its surface, i.e., on the outermost surface of the matte layer.

[0070] The wrinkle structure that appears on at least one surface of the matte layer is not particularly limited as long as its formation is stabilized by a wrinkle-forming stabilizer and it stably exhibits the visibility and texture of the matte effect, that is, as long as it exhibits the visibility and texture of the matte effect on the decorative sheet of this disclosure. With regard to the wrinkle structure, it is preferable that at least one surface of the matte layer has an uneven shape composed of irregular wrinkles, and the irregular wrinkles are preferably composed of a plurality of protrusions formed by a plurality of projections and a recess formed by being surrounded by a plurality of projections, and it is preferable that the projections have linear projections. In this disclosure, "linear projections" (hereinafter also referred to as "linear projections") means that the ratio of the length to the width of the projection (length / width) is 3 or more, preferably 5 or more, and more preferably 10 or more, and the method for determining the length and width is as described below. In this disclosure, a more preferred irregular wrinkle is one which is composed of a plurality of protrusions formed by a plurality of linear projections and a recess formed by being surrounded by the plurality of linear projections.

[0071] Regarding these wrinkles, the surface of the decorative sheet, i.e., the outermost surface of the matte layer as shown in Figure 2, has irregular wrinkles in a plan view. Furthermore, the irregular wrinkles are composed of multiple protrusions 2 formed by multiple curved linear protrusions and recesses 3 formed by being surrounded by multiple protrusions (multiple protrusions 2). It is also shown that at least a portion of the multiple curved protrusions 2 are each formed by meandering linear protrusions, and meandering recesses 3 are formed surrounded by these meandering linear protrusions. The decorative material of this disclosure exhibits stable visibility and texture of the matte effect due to the stable formation of the wrinkles shown in Figure 2.

[0072] Here, "curvature" means that, in a plan view, the convex portion 2 of a continuous line has one or more points where its extension direction reverses from one side to the other. Examples of points where the extension direction reverses from one side to the other include, for example, a form that has an inflection point when the plan view shape of the convex portion 2 of the line is approximated by a continuous curve when the width of the shape is ignored (when the width is considered to be 0). Also, examples include a form that has a portion that is approximated by a V-shaped polyline or two sides enclosing one vertex of a triangle when the plan view shape of the convex portion 2 of the line is approximated by a straight line when the width of the shape is ignored.

[0073] Furthermore, "serpentine" means that, in a plan view, there are at least two places where the direction of extension of the convex portion 2 of a continuous line reverses from one side to the other (hereinafter also referred to as the "reversed portion"), and when the convex portion 2 of the line is advanced in its direction of extension, there are portions where the direction of extension of the convex portion 2 of the line alternately reverses in the opposite direction at two adjacent locations. For example, when the width of the plan view shape of the convex portion 2 of the line is ignored and it is approximated by a continuous curve, there are forms that have portions approximated by the Roman letter "S". Another example is when the width of the plan view shape of the convex portion 2 of the line is ignored and it is approximated by a straight line, there are forms that have portions approximated by the Roman letter "W".

[0074] In this disclosure, "irregular" means that the shape does not follow a certain rule, nor is it arranged according to a certain rule, in other words, it is not patterned. Typical examples of non-irregular shapes (regular shapes) include shapes arranged with a certain periodicity in a specific direction, such as a so-called "lenticular lens," in which multiple cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to their longitudinal direction. Therefore, irregular wrinkles in this disclosure include the fact that the shape of a single protrusion itself is not formed according to a certain rule such as periodicity, that the shapes of multiple convex parts formed by multiple protrusions are not formed and arranged according to a certain rule, but are irregular, and that the shape of the concave part surrounded by such multiple protrusions is also irregular.

[0075] In the matte finish decorative material of this disclosure, if the shape of a single protrusion (single convex part), the shape and arrangement of each of the multiple protrusions (multiple convex parts), or the shape of the recess surrounded by the multiple protrusions is irregular, the visibility and texture of the matte finish due to the presence of irregular wrinkles can be obtained, but it is preferable that all of them be irregular. The decorative material of this disclosure, by having irregular wrinkles, improves the visibility and texture of its matte finish, and stably exhibits an extremely excellent visibility and texture of the matte finish.

[0076] As previously described, the matte layer has wrinkles, i.e., an uneven surface, on at least one of its surfaces. The convex and concave parts of the uneven surface can be distinguished, for example, by utilizing the brightness difference of the image of the surface of the decorative material of this disclosure. In the density distribution image, the darkest part is set to 255 and the lightest part is set to 0. For the range from 0 to 255, the range from 0 to 127 is set to concave parts and the range from 128 to 255 is set to convex parts by binarization.

[0077] The surface of the decorative material of this disclosure preferably has a structure having an uneven shape composed of irregular wrinkles in at least a part thereof, and more preferably irregular wrinkles are formed over the entire surface. The location where the wrinkles are formed is not particularly limited as long as it is on the surface of the decorative material, and is not limited to, for example, areas corresponding to the pattern described later (on the pattern), but at least a part of the surface will exhibit the visibility and texture of the matte effect due to the formation of wrinkles. For example, if there is a pattern layer described later and irregular wrinkles are formed in a part thereof, if the wrinkles are formed in areas corresponding to the pattern of the pattern layer (for example, on the pattern), the pattern will be visible as an area that is more matte than the surrounding area, thereby improving the design.

[0078] As also shown in Figure 2, it is preferable to have multiple protrusions formed by multiple irregular but somewhat homogeneous protrusions, and recesses surrounded by these protrusions. Therefore, in the protrusions (projections), shapes in which the width or height changes drastically are not desirable in terms of obtaining the visibility and texture of the matte effect. The following describes specific embodiments of the shapes of the protrusions (projections) and recesses that form irregular wrinkles, which can be advantageous in stably improving the visibility and texture of the matte effect.

[0079] Regarding the shape of the wrinkles formed on at least one surface of the matte layer, the height of the protrusions (height of the projections) is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, with an upper limit of approximately 10 μm or less. The width of the protrusions is preferably 0.1 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, with an upper limit of preferably 10 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. 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 the average value of 10 arbitrary protrusions (projections) in any 10 locations (100 μm square areas × 10 locations) of the decorative sheet of this disclosure, i.e., a total of 100 protrusions. Furthermore, as shown in Figure 2, the width of a single protrusion (projection) is not uniform but varies; therefore, the width of a single protrusion (projection) is the average value of the widths of any 5 locations within that single protrusion (projection). The same applies to the height of the protrusions (projections).

[0080] The depth of the recess is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with an upper limit of approximately 10 μm or less. The width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, with an upper limit of preferably 10 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. When the depth and width of the recess are within the above range, the visibility and texture of the matte effect are stably improved in relation to the convex portion. Here, the dimensions of the recess are determined in the same way as the dimensions of the protrusion described above.

[0081] The distance from the top of the convex portion to the bottom of the concave portion (the height difference between the convex portion and the concave portion) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, with an upper limit of preferably 20 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less. When this distance is within the above range, the visibility and texture of the matte effect are stably improved. Here, the dimensions of the recess are determined in the same way as the dimensions of the protrusion described above.

[0082] The proportion of the protrusions is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more, with an upper limit of preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less. When the proportion of the protrusions is within the above range, the visibility and texture of the matte effect are stably improved in relation to the proportion of the recesses surrounded by the protrusions. Here, the occupancy rate of the protrusions is the average value of the occupancy rate of the protrusions in any 10 locations (100 μm square area × 10 locations) of the decorative material of this disclosure.

[0083] The convex and concave portions may be located in substantially the same direction and of substantially the same width, but their length is preferably short in order to improve the visibility and texture of the matte effect. Specifically, the length of continuous convex and concave portions in substantially the same direction and of substantially the same width is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, with a lower limit of preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, which stably improves the visibility and texture of the matte effect.

[0084] Here, it is preferable that 80% or more of any 10 protrusions and recesses (i.e., a total of 100 protrusions and recesses) in any 10 locations (100 μm square areas × 10 locations) of the decorative material of this disclosure satisfy the above conditions, more preferably 85% or more, even more preferably 90% or more, and even more preferably 95% or more. Furthermore, in this disclosure, "approximately identical" means that they are roughly the same, without branching, with differences of ±3° in the case of direction and differences of ±5% in the case of width.

[0085] Furthermore, the number of protrusions (projections) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, with an upper limit of preferably 200 or less, more preferably 100 or less, and even more preferably 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 in 10 locations (100 μm square area × 10 locations) of the decorative material of this disclosure.

[0086] Figure 3 is a cross-sectional view showing one embodiment of the decorative material of the present disclosure, and is a cross-sectional view obtained by cutting the decorative sheet 100 with a plane parallel to its thickness direction (the Z direction in the figure). The shape of the recess may be acute, as shown in 3a of Figure 3, or it may be semicircular or semi-elliptical, as shown in 3b, or a combination of these. Alternatively, it may be a shape like 3c of Figure 3, where one convex part has a recess in part. On the other hand, the shape of the convex portion is semicircular or semielliptical, although there are variations in width, as shown in Figures 3, 2a and 2b.

[0087] The thickness of the matte layer is not particularly limited as long as it is thick enough to form the wrinkles described above to a degree that allows for stable visibility and texture of the matte effect. However, considering ease of manufacture, 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. The upper limit is preferably 300 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, and even more preferably 100 μm or less. In this disclosure, the thickness of the matte layer is determined by measuring the thickness at 20 points on a cross-section of the decorative material using a scanning electron microscope (SEM), and taking the average of the 20 values. The SEM acceleration voltage is set to 3kV, and the magnification is set according to the thickness. The same procedure is followed for the thickness of other layers.

[0088] The matte layer may be applied partially or over the entire surface, but it is preferable to apply it over the entire surface in order to improve the visibility and texture of the matte effect. When the matte layer is partially provided, the decorative material of this disclosure preferably has a base material, described later, as a layer substantially other than the matte layer.

[0089] In this disclosure, the shape of the wrinkle structure and the statistical indices of its geometric characteristic values ​​(Rz, Ra, Spc, Rsm, Sa, Ssk, Sku) can be appropriately selected depending on the design expressed by the decorative sheet. These Rz, Ra, Spc, Rsm, Sa, Ssk, and Sku can be determined, for example, by the method described in the examples.

[0090] (Rz (maximum height)) In this disclosure, it is preferable that the outermost surface of the surface resin layer has a lateral parameter Rz (maximum height) of 12.50 μm or less, as defined in JIS B0601:2013. 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 a given length. A larger Rz (maximum height) value indicates the presence of larger (higher) convex areas relative to the valleys (concave areas), and a tendency for there to be many such convex areas. This serves as an indicator. Therefore, it is preferable that Rz (maximum height) is 10.00 μm or less, as this reduces the variation in the height of the protrusions and results in a uniform matte effect, thus providing a decorative sheet with a large difference in brightness.

[0091] The lower limit of Rz (maximum height) is preferably 3.25 μm or more, more preferably 3.50 μm or more, and even more preferably 4.00 μm or more, in order to exhibit a matte 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 enhance the visibility of the glossy pigment layer. In this disclosure, the cutoff value for measuring Rz (maximum height) is 0.8 mm.

[0092] (Ra (Arithmetic Mean Roughness)) In this disclosure, it is preferable that the outermost surface of the surface resin layer has an arithmetic mean roughness (Ra), which is a lateral parameter of the contour curve as defined in the JIS standard, of 2.00 μm or less. Ra (arithmetic mean roughness) is one of the parameters in the height direction of the contour curve, and is the average value of the height difference from the average surface in the contour curve over a reference length. The smaller the Ra (arithmetic mean roughness) value, the smaller the height difference between the convex parts and the corresponding concave parts formed in the surface shape, indicating a tendency towards a smoother and more uniform shape. Therefore, an Ra (arithmetic mean roughness) of 2.00 μm or less is preferable because it results in a surface shape with more uniform and gentle convex parts, leading to a uniform matte effect and providing a decorative sheet with a large difference in brightness.

[0093] The lower limit of Ra is preferably 0.10 μm or more, more preferably 0.50 μm or more, and even more preferably 0.70 μm or more, in order to improve the matte effect. The upper limit is preferably 1.50 μm or less, more preferably 1.20 μm or less, and even more preferably 1.00 μm or less, in order to improve the visibility of the lustrous pigment layer.

[0094] (Spc (arithmetic mean curvature of the vertices of the protrusions)) Spc (arithmetic mean curvature of projection vertices) is one of the three-dimensional surface texture parameters defined in the aforementioned JIS standard. It is the mean curvature (average sharpness) of the tip of a peak, obtained from the arithmetic mean of the curvature radii of the peaks (projection vertices) of areas classified as peaks (convex parts) in the shape image included in the reference region. Therefore, Spc is the reciprocal of the radius (mm) (mm -1 )

[0095] The larger the value of Spc, the greater the curvature of the tip of the peak (convex part) (the reciprocal radius of curvature is small, and the shape of the tip is sharp). On the other hand, the smaller the value of Spc, the smaller the curvature of the apex of the protrusion (the reciprocal radius of curvature is large, and the shape of the tip is blunt). In other words, the smaller the Spc, the more rounded the protrusion is and the closer it is to a flat surface, resulting in greater gloss. Therefore, to reduce gloss by focusing only on the value of Spc, a surface shape with a large Spc (a surface shape with a sharp apex of the protrusion) will increase the diffusion of light on the surface, reducing gloss. A surface shape with small Spcs has rounded protrusions, resulting in a less matte finish when viewed from the front, but an improved matte finish when the decorative sheet is viewed from an oblique angle. Therefore, an Spc of 8000.00 mm -1 The following is preferable because it results in a surface shape with more gently shaped protrusions, which leads to a uniform matte finish and provides a decorative sheet with a large difference in brightness.

[0096] Spc provides a decorative sheet that exhibits a uniform matte effect and a large difference in brightness, therefore preferably 3000.00 mm -1 More preferably 3500.00 mm -1The above, and more preferably 4000.00 mm -1 The above is true, and the upper limit is preferably 7000.00 mm in order to improve the visibility of the luminous pigment layer. -1 The following, preferably 6500.00 mm -1 More preferably, 6200.00 mm -1 More preferably, 6000.00 mm -1 The following applies: In measuring Spc in this disclosure, the cutoff value is 0.8 mm.

[0097] (Rsm(average length of curve elements)) Rsm (average length of curve elements) is a parameter of the lateral direction of the contour curve among the three-dimensional surface texture parameters specified in the JIS standard, and is the average length of the contour curve elements in the reference length. The smaller the Rsm, the more protrusions are included in the reference length. Therefore, surface shapes with a small Rsm have a denser distribution of protrusion vertices, resulting in a greater matte effect on the decorative sheet.

[0098] Rsm provides a decorative sheet with a uniform matte effect and a large difference in brightness, so the lower limit is preferably 10.00 μm or more, more preferably 15.00 μm or more, and even more preferably 18.00 μm or more. The upper limit is preferably 30.00 μm or less, more preferably 25.00 μm or less, and even more preferably 20.00 μm or less, in order to improve the visibility of the glossy pigment layer. In this disclosure, the cutoff value for measuring Rsm is 0.8 mm.

[0099] (Sa (Arithmetic Mean Height)) Sa (arithmetic mean height) is a numerical value representing the average of the absolute values ​​of the heights of recesses and protrusions from the average surface of the surface, among the three-dimensional surface texture parameters specified in the JIS. Sa is an indicator of the state of unevenness across the entire surface of a decorative sheet, and when Sa is 0.01 μm or higher, the design quality is improved mainly by the physical uneven shape and the visual sense of unevenness. Sa provides a decorative sheet that exhibits a uniform matte effect and a large difference in brightness, so the lower limit is preferably 0.10 μm or more, more preferably 0.50 μm or more, and even more preferably 0.71 μm or more. The upper limit is preferably 2.00 μm or less, more preferably 1.50 μm or less, and even more preferably 1.00 μm or less, in order to improve the visibility of the lustrous pigment layer.

[0100] Rz, Ra, Spc, Rsm, Sa, Ssk, and Sku are as described above, but Spc is 8000.00 mm -1 By setting the following and the Sku to less than 3, the apex of the convex portion becomes rounded, which makes it easier for light reflected by the lustrous pigment layer to pass through the matte layer. Therefore, the matte effect and the brightness difference due to the lustrous pattern layer containing the lustrous pigment can be greatly increased, which is preferable.

[0101] (Ssk (Skewness)) Ssk (skewness) is one of the three-dimensional surface texture parameters defined in ISO 25178-2:2012, and is an index that indicates the degree of bias in the height distribution from the mean plane. When Ssk is 0, the surface shape is symmetrical (normally distributed) with respect to the mean plane. When Ssk is greater than 0, the surface shape is biased downwards from the mean plane, i.e., towards the lower height side, and the vicinity of the tops of convex parts tends to be sharp and thin. On the other hand, when Ssk is less than 0, the surface shape is biased upwards from the mean plane, i.e., towards the higher height side, and the vicinity of the tops of convex parts tends to be blunt and thick.

[0102] To improve the matte effect, the lower limit of Ssk is preferably 0.01 or higher, more preferably 0.05 or higher, and even more preferably 0.07 or higher. The upper limit is preferably 1.50 or lower, more preferably 1.00 or lower, even more preferably 0.50 or lower, and even more preferably 0.20 or lower, in order to enhance the visibility of the glossy pigment layer. (Sku (Kurtosis)) Sku (Curtosis) is one of the three-dimensional surface texture parameters defined in ISO 25178-2:2012, and is an index that indicates the degree of sharpness of the height distribution from the mean plane. When Sku is 3, the surface shape is symmetrical (normally distributed) with respect to the mean plane, when Sku exceeds 3, the height distribution has a sharp shape, and when Sku is less than 3, the height distribution tends to have a flattened shape.

[0103] The Sku value is preferably 2.00 or higher, more preferably 2.20 or higher, and even more preferably 2.50 or higher, in order to improve the matte 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 less than 2.80, in order to improve the visibility of the glossy pigment layer.

[0104] [Regarding the layer structure] The decorative sheet of this disclosure comprises a lustrous pattern layer containing a lustrous pigment and a surface resin layer, and the layer configuration is not particularly limited as long as at least a portion of the outermost surface of the surface resin layer has a wrinkled structure, and any layer configuration may be adopted. For example, the simplest layer configuration of the decorative sheet of this disclosure is one in which only two layers are present: a glossy pattern layer and a surface resin layer.

[0105] Furthermore, in order to flexibly respond to various performance requirements according to various needs such as the mechanical strength, post-processing suitability, and design appearance of the decorative sheet, and to ensure suitability for manufacturing, use, and handling, the laminate may have multiple layers stacked together as shown in Figure 1, for example, a base material, a primer layer, and other layers such as a decorative layer. Hereinafter, a decorative sheet composed of a laminate, which is one preferred embodiment, will be described for each layer constituting the decorative sheet of this disclosure.

[0106] [Base material] The base material used to form the decorative sheet in this disclosure is not particularly limited in form (or shape), and can preferably be selected from various shapes such as films, sheets or plates, polyhedra, polygonal prisms, cylinders, spheres, and ellipsoids. Here, films, sheets, and plates are referred to as films, sheets, and plates in order of their relative thickness, but in this disclosure, there is no particular significance in strictly distinguishing these three, and differences between films, sheets, and plates will not result in differences in the interpretation of the rights of the present invention. Therefore, in this disclosure, films, sheets, and plates may be collectively referred to as "sheets," "sheet-like," etc.

[0107] When the decorative sheet of this disclosure is composed of a laminate, the shape of the base material is preferably sheet-like. When the base material is sheet-like, it is easier to provide a matte layer, as described later, which improves manufacturability, and it is also easier to integrate it with resin molded products, for example by bonding, which improves post-processing suitability.

[0108] The constituent materials of the base material are not particularly limited, and various materials such as resins, metals, non-metallic inorganic materials, fibrous materials, and wood-based materials can be appropriately selected depending on the application. The base material composed of these various materials can be used as a single layer, or as multiple layers by combining two or more base materials composed of these various materials. When multiple layers are used, two or more layers of different materials can be laminated and integrated, and the various functions of the materials in each layer can be complemented by each other.

[0109] When using a multi-layer substrate, if the laminate consisting of, for example, a layer made of material A and a layer made of material B is laminated together, it may be referred to as "A / B"; (1) Resin / wood material (2) Resin / Metal (3) Resin / Fibrous materials (4) Resin / nonmetallic inorganic materials (5) Resin 1 / Resin 2 (for example, when there are multiple layers composed of different resins such as "olefin resin / acrylic resin")

[0110] (6) Metal / wood materials (7) Metal / non-metal inorganic materials (8) Metals / Fibrous materials (9) Metal 1 / Metal 2 (for example, when there are multiple layers composed of different metals such as "copper / chromium") (10) Nonmetallic inorganic materials / fibrous materials These are some examples of preferred embodiments. Furthermore, if the substrate consists of multiple layers, it may also include adhesive layers, tack layers, and primer layers (also referred to as anchor layers or easy-adhesion layers) between each of the multiple layers to improve the adhesion between adjacent layers.

[0111] Examples of resins that can be used as a base material include various synthetic resins and natural resins. Examples of synthetic resins include thermoplastic resins and curable resins, and thermoplastic resins are preferred when considering suitability for manufacturing decorative sheets, handling suitability, and post-processing suitability.

[0112] Preferred 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 copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate-(meth)acrylate copolymers; polyamide resins represented by nylon 6 and nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer (ABS resin); and polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, and polyimide resin.

[0113] Preferred natural resins include natural rubber, pine resin, and amber. Furthermore, preferred curable resins include thermosetting resins and ionizing radiation-curable resins, which will be exemplified later as constituent materials for the matte layer.

[0114] Suitable metals for the base material 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; and gold, silver, chromium, nickel, cobalt, tin, and titanium. Furthermore, base materials composed of these metals may also include those with a surface coating applied by plating or other means.

[0115] Examples of non-metallic inorganic materials that can be used as a base material include non-ceramic ceramic materials such as cement, ALC (autoclaved lightweight concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as pottery, earthenware, glass, and enamel; and natural stones such as limestone (including marble), granite, andesite.

[0116] Examples of fibrous materials that can be used as a base material include paper such as tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, sulfuric acid paper, paraffin paper, parchment paper, glassine paper, wallpaper backing paper, cardboard, and gypsum board base paper; and woven or nonwoven fabrics made of polyester resin fibers, acrylic resin fibers, natural fibers of proteins or cellulose such as silk, cotton, and hemp, glass fibers, and carbon fibers. Among these materials, in order to improve the inter-fiber strength of a paper base material made of paper or the inter-layer strength with other base materials used in combination with the paper base material, and to prevent fuzzing, various resins such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin may be added (impregnated with these resins after papermaking or filled during papermaking). Examples of papers with added resin include inter-paper reinforced paper and resin-impregnated paper.

[0117] It is preferable to form a known penetration-preventing resin layer on the matte-finish side surface of the fibrous material substrate by coating or other methods. Examples of resins used for forming such a penetration-preventing resin layer include two-component curing urethane resins. Furthermore, as a laminate formed by laminating a layer composed of fibrous material and a layer composed of resin, a wallpaper base roll is preferred, which is made by laminating layers composed of various resins such as a polyvinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer onto the surface of wallpaper backing paper commonly used in the building materials field.

[0118] Suitable wood-based materials that can be used as a base material include, for example, veneers, plywood, laminated wood, particleboard, and medium-density fiberboard (MDF) made from various types of wood such as cedar, cypress, pine, zelkova, oak, walnut, lauan, teak, and rubber tree.

[0119] As the base material, any base material composed of the aforementioned materials can be used without limitation, and can be appropriately selected according to the desired properties, etc. Among resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferred, with olefin resins, vinyl chloride resins, and polyester resins being more preferred. Polyethylene and polypropylene are preferred as olefin resins, polyvinyl chloride as vinyl chloride resins, and polyethylene terephthalate as polyester resins. Among fibrous materials, paper is preferred. Using a substrate made of these materials makes it particularly easy to obtain the aforementioned surface shape and improve the soft-touch feel.

[0120] The shape and dimensions of the substrate, whether single-layer or laminated, are not particularly limited and should be selected as appropriate, taking into consideration the application, desired performance, and suitability for post-processing. When adopting the form of a film, sheet, or plate, the thickness is a typical design dimension for decorative sheets. However, there are no particular restrictions on this thickness. Considering suitability for manufacturing, handling, post-processing, mechanical strength, and economics, it is preferable to select a thickness from the range of 10 μm to 10 cm. When adopting the form of a film or sheet, it is preferable to select a thickness from the range of 20 μm to 300 μm, and when adopting the form of a plate, it is preferable to select a thickness from the range of 1 mm to 2 cm.

[0121] To improve adhesion between the base material and other layers, such as the matte layer described later, which constitute the decorative sheet, and to adhesion between the base material and the adherend, such as a resin molded product on which the decorative sheet is laminated, at least one of its surfaces may be subjected to a surface treatment to improve ease of adhesion, such as a physical surface treatment, such as an acid value method or an embossing method, or a chemical surface treatment. Oxidation methods include, for example, corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment, while surface texture creation methods include, for example, sandblasting and solvent treatment. These surface treatments can be appropriately selected depending on the type of substrate, but corona discharge treatment is preferred in terms of its effect on improving adhesion and ease of workability.

[0122] The substrate may or may not be colored (it may be transparent), and if it is colored, there are no particular restrictions on the manner of coloring; it may be transparently colored or opaquely colored (concealing colored), and these can be chosen arbitrarily.

[0123] If the substrate is colored, examples of colorants include white pigments such as titanium white, inorganic pigments such as iron black, lead yellow, titanium yellow, reddish-brown, cadmium red, ultramarine, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethine azo-based black pigments, and perylene-based black pigments; metallic pigments consisting of flaky foil pieces such as aluminum and brass; and pearlescent pigments consisting of flaky foil pieces such as titanium dioxide-coated mica and basic lead carbonate. For example, if the surface hue of the substrate, such as a resin molded product on which a decorative sheet is laminated, varies, and it is desired to conceal the surface hue and improve the stability of the color tone of the decorative layer provided as desired, an inorganic pigment such as a white pigment may be used.

[0124] When coloring a resin-based substrate, any of the following methods can be employed: adding a coloring agent to the resin (kneading, mixing), or forming a coating film containing the resin and coloring agent. When coloring a fibrous material substrate such as paper, woven fabric, or nonwoven fabric, this can be done by mixing it with pulp or fibrous material, forming a coating film, or a combination of these methods.

[0125] When coloring a substrate made of wood-based material, this can be done by dyeing with dyes, forming a coating film, or a combination of both. When coloring a substrate made of metal, in addition to forming a coating film, electrolytic coloring methods such as forming a metal oxide film on the surface using anodic oxidation can be employed. Furthermore, when coloring a substrate made of non-metallic inorganic material, this can be done by forming a coating film, adding it to the substrate, or a combination of both.

[0126] Additives may be added to the base material as needed. Examples of additives, mainly in the case of resins, include inorganic materials such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, UV absorbers, and light stabilizers. The amount of additives added is not particularly limited as long as it does not impair surface properties, processing properties, etc., and can be appropriately set according to the required properties.

[0127] In order to improve the weather resistance of the decorative sheet of this disclosure, it is preferable to use weather-resistant agents such as ultraviolet absorbers and light stabilizers among the additives. Examples of UV absorbers and light stabilizers include those that may be included in the matte layer described later. These UV absorbers, light stabilizers, and other weather-resistant agents, as well as various other additives, can be used individually or in combination.

[0128] In this disclosure, the aforementioned substrates may be used individually or in combination of multiple types. Multiple paper substrates may be combined, or paper substrates may be combined with fiber substrates, paper substrates with resin substrates, fiber substrates with resin substrates, or paper substrates, fiber substrates, and resin substrates. Furthermore, the resin substrate may consist of a single layer of the resin substrate or multiple layers of the same or different resins.

[0129] The thickness of the base material is as described above, but when the base material is a film or sheet of the resin, it is preferably 20 μm or more, and preferably 300 μm or less as the upper limit. Considering the suitability for manufacturing, handling, post-processing, mechanical strength, economy, etc., it is more preferably 40 μm or more, preferably 200 μm or less as the upper limit, and even more preferably 100 μm or less. To achieve a similar effect, if the base material is paper, the basis weight is typically 20 g / m². 2 More than 150g / m 2 The following is preferable: 30 g / m 2 More than 100g / m 2 The following are preferable.

[0130] (Primer layer) If the decorative sheet of this disclosure is composed of multiple layers, it may have a primer layer in order to improve the interlayer adhesion between the multiple layers.

[0131] The primer layer is mainly composed of a binder resin and may contain additives such as UV absorbers and light stabilizers as needed.

[0132] Preferred binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer main chain and two or more hydroxyl groups in the terminals and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrified cotton), and cellulose acetate resins. These can be used individually or in combination. Furthermore, 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 and then cross-linking and curing them. Among these, a polyol-based resin such as an acrylic polyol resin cross-linked and cured with an isocyanate-based curing agent is preferred, and an acrylic polyol resin cross-linked and cured with an isocyanate-based curing agent is more preferred.

[0133] 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 even more preferably 1.5 μm or more and 6 μm or less.

[0134] (Transparent resin layer) The decorative sheet of this disclosure may have a transparent resin layer to increase its strength and to protect each layer. If there is a substrate, the transparent resin layer may be provided between the substrate and the glossy pattern layer, and if there is a decorative layer, it may be provided between the decorative layer and the substrate to protect the decorative layer.

[0135] Examples of resins that make up the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resin"), acrylic resins, and vinyl chloride resins. Among these, polyolefin resins and vinyl chloride resins are preferred due to their suitability for post-processing. Furthermore, two or more of these resins may be laminated or mixed for use.

[0136] The transparent resin layer only needs to be transparent enough that the substrate side is visible from the transparent resin layer, and if there is a decorative layer, it only needs to be transparent enough that the decorative layer is visible. It may be colorless and transparent, as well as colored and translucent. In other words, in the present invention, "transparency" means not only colorless and transparent, but also colored and translucent.

[0137] The transparent resin layer may contain weather-resistant agents such as UV absorbers and light stabilizers, as well as additives such as colorants. The thickness of the transparent resin layer is preferably 20 μm to 150 μm, more preferably 40 μm to 120 μm, and even more preferably 60 μm to 100 μm, considering protection of the decorative layer and suitability for post-processing.

[0138] (Decorative layer) The decorative sheet of this disclosure may have a decorative layer in addition to the glossy pattern layer in order to improve its design. The decorative layer may be provided on the side opposite to the matte layer of the glossy pattern layer, and if there is a base material, it may be provided between the base material and the glossy pattern layer.

[0139] The decorative layer may be, for example, a colored layer that covers the entire surface (a so-called solid colored layer), or a patterned layer formed by printing various patterns using ink and a printing press. Alternatively, it may have two or more decorative layers, combining a solid colored layer and a patterned layer.

[0140] There are no particular restrictions on the patterns (designs) of the design layer; any desired design can be used. Examples include wood grain patterns such as annual rings and vessel grooves on the surface of wooden boards, stone patterns on the surface of stone slabs such as marble and granite, fabric patterns on the surface of cloth, leather grain patterns on the surface of leather, geometric patterns, letters, figures, and combinations thereof. The luminous pattern layer may be synchronized with the pattern of the decorative layer as described above.

[0141] The ink used for the decorative layer is a mixture of a binder resin with appropriate amounts of colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, UV absorbers, and light stabilizers. There are no particular restrictions on the binder resin for the decorative layer. Examples include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins accompanied by curing agents such as isocyanate compounds.

[0142] As a coloring agent, pigments with excellent opacity and weather resistance are preferred. The pigments used can be the same as those exemplified as pigments that can be used in the substrate. The coloring agent content 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 even more preferably 30 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the resin constituting the decorative layer.

[0143] The decorative layer may contain additives such as UV absorbers, weather stabilizers, and colorants. The thickness of the decorative layer can be appropriately selected according to the desired pattern, but in order to conceal the base color of the adherend and improve the aesthetic appeal, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0144] (adhesive layer) The decorative sheet in this disclosure may have an adhesive layer to improve the adhesion between each layer.

[0145] The adhesive layer can be composed of adhesives such as urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, and rubber-based adhesives. Among these adhesives, urethane-based adhesives are preferred in terms of adhesive strength. Examples of urethane-based adhesives include adhesives that utilize a two-component curing urethane resin containing various polyol compounds such as polyether polyols, polyester polyols, and acrylic polyols, and a curing agent such as an isocyanate compound.

[0146] To efficiently obtain the desired adhesive strength, 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.

[0147] [60° Gross Value] The decorative sheet disclosed herein has excellent visibility of its matte finish. In this disclosure, "matte" means that gloss is difficult to see, and this varies depending on the color tone, pattern, etc. of the decorative sheet, so it cannot be stated in general terms, but for example, if the 60° gloss value is 20.0 or less, preferably 10.0 or less, it will generally be treated as "matte". Until now, for example, black and other dark colors ("dark colors" means colors with low brightness, for example, measured in accordance with JIS Z8781-4:2013 CIE (International Commission on Illumination) L * a * b * L in color systems * Value (hereinafter simply referred to as "L") *Sometimes referred to as the "value," this means that the 60° gloss value is usually around 40 or less, preferably 30 or less. In decorative sheets exhibiting this, even with the use of a matting agent, 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. However, because a large amount of matting agent is used, streaks and unevenness occur during layer formation, making it difficult to manufacture, and the surface properties deteriorate. Furthermore, for decorative sheets exhibiting colors other than black or other dark colors, even with the use of a matting agent, there is a lower limit to the 60° gloss value, similar to decorative sheets exhibiting black. In any case, it was not easy to obtain decorative sheets with excellent surface properties, as well as excellent visibility of the matting effect and texture. This tendency becomes more pronounced as the 60° gloss value decreases.

[0148] In the decorative sheet disclosed herein, by minimizing the amount of wrinkle-forming stabilizer used, a significant increase in the viscosity of the resin composition can be suppressed, making layer formation easier and naturally resulting in excellent surface properties such as stain resistance, scratch resistance, and weather resistance, depending on the properties of the resin used in the matte layer.

[0149] As previously described, the decorative sheet of this disclosure varies depending on the color tone and therefore cannot be defined in general terms. However, for example, when exhibiting black or other dark colors, the 60° gloss value on the matte layer side can be 10.0 or less, and further, 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, and 2.0 or less, exhibiting extremely excellent visibility of the matte effect. Furthermore, decorative sheets exhibiting colors other than black or other dark colors may also have the aforementioned 60° gloss value. The 60° gloss value on the matte layer side of the decorative sheet of this 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 this disclosure, the 60° gloss value on the matte layer side refers to the 60° specular gloss measured in accordance with JIS K 5600-4-7:1999, and is the average value of values ​​that can be measured from the matte layer side using a gloss meter or the like at any 10 locations.

[0150] [Other physical properties] L of the decorative sheet in this disclosure * The value is preferably 80.00 to 90.00, and preferably 83.00 to 98.00, as this results in a decorative sheet with excellent matte effect and a large difference in brightness due to the lustrous pattern layer containing lustrous pigments. The total light transmittance of the decorative sheet according to JIS K7361-1:1997 over the entire range of incident light from the matte layer of the decorative sheet can not be generalized, as it depends on the layer composition of the decorative sheet and the patterning of the glossy pattern layer, but it is preferably 30% or less, more preferably 20% or less, and even more preferably 30% or less.

[0151] [Manufacturing method for decorative sheets] The matte layer of the decorative sheet of this disclosure has a wrinkled structure on its outermost surface. A primer layer is formed on the glossy pattern layer formed using the aforementioned glossy pattern layer forming composition, and if necessary, a matte layer forming composition is applied. In forming the matte layer, by irradiating a resin composition for matte formation, which contains a wrinkle-forming stabilizer for forming the matte layer, with short-wavelength ultraviolet light of at least 100 nm to 380 nm, wrinkles can be formed on at least one surface of the matte layer, thereby imparting a matte effect to the decorative sheet (matte layer).

[0152] The details of the mechanism by which wrinkles form on at least one surface of the matte layer and a matte effect is produced when such short-wavelength ultraviolet light is irradiated onto a resin composition for forming a matte layer are unknown, but it is presumed to be due to the following mechanism.

[0153] When a coating layer of a resin composition for forming a matte finish is applied to a predetermined thickness and then irradiated with short-wavelength ultraviolet light, the energy of the ultraviolet light penetrates only the surface portion, and does not reach the layers below. As a result, only the surface portion of the resin composition begins to harden, causing hardening shrinkage only on the surface, which is thought to form wrinkles. Thus, it is believed that wrinkle formation occurs when the resin composition for forming a matte finish hardens only in a certain thickness direction from the surface due to irradiation with short-wavelength ultraviolet light. Furthermore, a comparison of the examples and comparative examples described later shows that when the wrinkle-forming stabilizer is not included, wrinkle formation becomes unstable, the visibility and texture of the matte effect do not appear stably and sufficiently across the entire matte layer, and the soft-touch feel is not fully expressed. Therefore, the stable expression of the matte effect cannot be explained solely by hardening of the surface portion by short-wavelength ultraviolet light. In other words, for the decorative sheet of this disclosure to exhibit a matte effect by stably having wrinkles, the inclusion of a wrinkle-forming stabilizer is essential. Considering that a stable matte effect due to wrinkle formation is not obtained when the wrinkle-forming stabilizer is not included, it is thought that the wrinkle-forming stabilizer functions as a nucleus that triggers wrinkle formation, and around this nucleus, the resin on the surface portion of the resin composition gathers to form convex (protrusion) parts of the wrinkles, and along with the formation of convex (protrusion) parts, concave parts are formed, resulting in stable wrinkle formation and the stable expression of the matte effect.

[0154] The wrinkle-forming stabilizer and the resin composition for forming a matte layer containing the wrinkle-forming stabilizer used in the manufacturing method of the present disclosure are the same as those described above as the wrinkle-forming stabilizer and the resin composition for forming a matte layer that can be used in the matte cosmetic material of the present disclosure.

[0155] In the manufacturing method of this disclosure, a resin composition for forming a matte layer is irradiated with light of a wavelength of at least 100 nm to 380 nm. As described above, this irradiation causes the energy of the ultraviolet light to penetrate only to the surface portion, and the energy does not reach the layers below it. As a result, only the surface portion of the resin composition begins to harden, and the hardening shrinkage occurs only on the surface, stabilizing the formation of wrinkles. The surface layer of the resin composition becomes a hardened product and forms a matte layer. After this, hardening progresses from the slower hardening near the surface to the deeper parts, and the layer of the resin composition becomes a hardened product. Thus, the resin composition hardens throughout its entire thickness and forms a matte layer with wrinkles that exhibit a light-diffusing effect on the surface. To promote the hardening to the deeper parts, it is preferable to perform further irradiation treatment after irradiating with light of a wavelength of 100 nm to 380 nm, as described later.

[0156] As light with a wavelength of at least 100 nm to 380 nm, "excimer light" is preferred, which includes light in the ultraviolet wavelength range from gases such as noble gases like Ar, Kr, Xe, and Ne, halides of noble gases such as F, Cl, I, and Br, or dimers of excited states formed by the discharge of mixed gases thereon, i.e., excimers. As for the wavelength of the excimer light and the excimer that serves as the light source, for example, light with a wavelength of 126 nm radiated from an Ar2 excimer (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), and 351 nm (XeF) can be preferably used. For excimer light, either spontaneous emission light or highly coherent laser light produced by stimulated emission can be used, but usually spontaneous emission light is sufficient. The discharge lamp that emits this light (ultraviolet light) is also called an "excimer lamp." Excimer light is characterized by a single wavelength peak and a narrower full width at half maximum compared to ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). By using such excimer light, wrinkle formation is stabilized, and the matting effect is steadily improved.

[0157] To stabilize wrinkle formation and stably improve the matting effect, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, and even more preferably 155 nm or more. The upper limit is preferably 320 nm or less, more preferably 300 nm or less, even more preferably 250 nm or less, and even more preferably 200 nm or less, with the most preferred being 172 nm (Xe2). Thus, in this disclosure, it is preferable to use shorter wavelength light to stably improve the matting effect, with medium-wavelength ultraviolet light (wavelength: 280 nm or more and 320 nm or less) and short-wavelength ultraviolet light (wavelength: 280 nm or less) being more preferable, and short-wavelength ultraviolet light being even more preferable.

[0158] In this disclosure, the integrated amount of light of the wavelength is preferably 1 mJ / cm² in order to stabilize wrinkle formation and stably improve the matte effect. 2 More than 3 mJ / cm² 2 More preferably 5 mJ / cm 2 That concludes the explanation. There is no particular upper limit, but in order to reduce the number of lamps required for irradiation with wavelength light and to improve production efficiency, the upper limit is preferably 1,000 mJ / cm². 2 More specifically, 500 mJ / cm² 2 More preferably, 300 mJ / cm² 2 The following applies. To achieve a similar effect, the ultraviolet output density is preferably 1 mW / cm or more, more preferably 10 mW / cm or more, even more preferably 20 mW / cm, with an upper limit of preferably 100 mW / cm or less, more preferably 70 mW / cm or less, and even more preferably 50 mW / cm or less. Furthermore, the oxygen concentration when irradiating with the aforementioned 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.

[0159] In the matte layer formation step of the method for manufacturing decorative sheets according to this disclosure, in addition to irradiation with light of a wavelength of at least 100 nm to 380 nm as described above, other treatments that contribute to the curing of the matte layer formation composition may be performed. For example, in order to stabilize the formation of wrinkles caused by the difference in the degree of hardening between the surface and the deeper parts away from the surface, and to promote the progression of hardening to the deeper parts, the resin composition for forming the matte layer may be pre-cured overall by irradiating it with light with a wavelength greater than 380 nm, preferably light with a wavelength of about 385 nm to 400 nm, and then irradiated with light with a wavelength of 100 nm to 380 nm, or post-curing may be performed to further harden the resin composition after irradiation with light with a wavelength of 100 nm to 380 nm. The necessity of pre-curing and post-curing should be appropriately determined according to the desired properties required for the matte layer (e.g., surface properties such as processing characteristics and stain resistance). In addition, although the above wavelength light belongs to ultraviolet light, it is also possible to use other ionizing radiation, such as electron beams, not limited to ultraviolet light. For example, in post-curing, electron beams may be preferably used to improve the surface characteristics of the matte layer.

[0160] In the manufacturing method of the present disclosure, the matte layer can be formed by irradiating a coated layer (uncured resin layer) obtained by applying a resin composition for forming a matte layer using a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating with light of a wavelength of at least 100 nm to 380 nm.

[0161] Furthermore, the decorative sheet obtained by the manufacturing method of this disclosure may have other layers, such as a transparent resin layer, in addition to the substrate described above as a layer that can be used in the decorative sheet of this disclosure. For example, decorative layers, adhesive layers, and primer layers can be formed by applying a coating solution containing the composition for each layer using the known method described above, and drying and curing as necessary. Furthermore, when forming a transparent resin layer, the resin film for the transparent resin layer can be formed by dry lamination or the like.

[0162] (Application) The decorative sheet of this disclosure can be used as a decorative material, as described later.

[0163] Furthermore, the decorative sheet of this disclosure can also be used as a molding sheet. When used as a molding sheet, it can be used as an embossing plate, molding sheet, etc., used in the embossing process in the second manufacturing method and the third manufacturing method, thereby obtaining an article composed of the single layer described above, a thermosetting resin decorative panel. The surface shape of the molded object (an article composed of a single layer, a thermosetting resin decorative panel, etc.) will be the opposite of the surface shape of the molded sheet (the decorative sheet of this disclosure), as described above.

[0164] [Decorative materials] The decorative sheet of this disclosure can be used as a decorative material as is, or it can be laminated, composited, or combined with an adherend and used as a decorative material. It is preferable that the decorative material has the decorative sheet on the adherend, but the choice of which to use may be determined as desired. When the decorative sheet of this disclosure is used as a decorative material, it is preferable that the decorative sheet has a decorative layer.

[0165] When a substrate is present, the decorative material comprises the substrate and the decorative sheet of this disclosure, specifically, the surface of the substrate requiring decoration and the surface of the decorative sheet opposite to the surface where wrinkles are formed in the matte layer and a matte effect is exhibited are laminated facing each other. Furthermore, when a substrate is present, considering the ease of lamination, it is preferable that the decorative sheet of this disclosure is in the form of a film or a sheet.

[0166] (adherent material) Examples of adherends include flat plates, curved plates, and other sheet materials made from various materials; three-dimensional shaped articles such as cylinders and polygonal prisms; and sheets (or films). For example, these include wood components used as sheet materials or three-dimensional shaped articles, such as wood veneers, wood plywood, laminated wood, particleboard, and wood fiberboards such as MDF (medium-density fiberboard) made from various types of wood such as cedar, cypress, pine, and lauan; metal components used as sheet materials, three-dimensional shaped articles, or sheets, made from metals such as iron, aluminum, copper, and alloys containing one or more of these metals; ceramic components used as sheet materials or three-dimensional shaped articles, made from non-ceramic ceramic materials such as glass, ceramics, gypsum, cement, ALC (autoclaved lightweight concrete), and calcium silicate; and resin components used as sheet materials, three-dimensional shaped articles, and sheets, made from resins such as acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride resin, cellulose resin, and rubber. Furthermore, these components can be used individually or in combination of multiple types.

[0167] The adherend can be appropriately selected from the above-mentioned options depending on the application. When used for interior components of buildings such as walls, ceilings, and floors, or exterior components such as exterior walls, roofs, eaves, fences, and gates, or joinery or construction components such as window frames, doors, handrails, baseboards, moldings, etc., it is preferable to use a material consisting of at least one component selected from wood, metal, and resin. When used for exterior components such as entrance doors, or joinery such as window frames and doors, it is preferable to use a material consisting of at least one component selected from metal and resin.

[0168] The thickness of the adherend can be appropriately selected depending on the application and material, preferably 0.1 mm to 100 mm, more preferably 0.3 mm to 5 mm, and even more preferably 0.5 mm to 3 mm.

[0169] (adhesive layer) To obtain excellent adhesion between the adherend and the decorative sheet, it is preferable that an adhesive layer be used for bonding.

[0170] The adhesive used in the adhesive layer is not particularly limited, and any known adhesive can be used, and should be appropriately selected according to the application. For example, moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives are preferred.

[0171] Examples of resins used in 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, cyanoacrylate resins, and epoxy resins, which can be used individually or in combination. Two-component curing type urethane adhesives and ester adhesives using isocyanate compounds as curing agents can also be used. Furthermore, an adhesive can be used in the adhesive layer. Various adhesives such as acrylic, urethane, silicone, and rubber-based adhesives can be appropriately selected and used.

[0172] There are no particular restrictions on the thickness of the adhesive layer, but to obtain excellent adhesion, it is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 10 μm to 30 μm.

[0173] (Method of manufacturing decorative materials) The decorative material can be manufactured by laminating the decorative sheet and the adherend of the present disclosure. This process involves laminating a substrate with the decorative sheet of the present disclosure, with the surface of the substrate requiring decoration facing the surface of the decorative sheet opposite to the surface where wrinkles are formed in the matte layer and a matte effect is exhibited, and, if the decorative sheet of the present disclosure has a base material, facing the surface on the base material side. As a method for laminating the substrate and the decorative sheet, for example, there is a lamination method in which the decorative sheet is laminated onto a plate-shaped substrate by applying pressure with a pressure roller via an adhesive layer.

[0174] When using a hot-melt adhesive (thermosensitive adhesive) as the adhesive, the heating temperature is preferably 160°C to 200°C, depending on the type of resin that makes up the adhesive, and preferably 100°C to 130°C for reactive hot-melt adhesives. In the case of vacuum forming, it is common to perform the process while heating, and the temperature is preferably 80°C to 130°C, and more preferably 90°C to 120°C.

[0175] The decorative material obtained as described above can be cut as desired, and the surface and end grain can be decorated with grooves, chamfers, and other decorative processes using cutting machines such as routers and cutters. It is suitable for a variety of uses, such as interior building components for walls, ceilings, and floors; exterior components for exterior walls, eaves, roofs, fences, and railings; joinery or construction components for window frames, doors, door frames, handrails, baseboards, moldings, and other fixtures; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; or surface decorative panels for cabinets of home appliances and office equipment; and interior and exterior components for vehicles. In addition to the decorative materials used in the aforementioned buildings, the decorative sheet of this disclosure can be used as is, or laminated, composite, or combined with other materials (adhering materials) in packaging materials, anti-glare films for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, and various identification documents, keyboard keys, transparent panels such as windows, doors, and partitions (window glass, etc.), artificial leather, etc. In these applications, it is preferable that the decorative sheet of this disclosure be placed on the outermost surface to exhibit excellent symmetry and texture, but other forms of use are of course possible depending on the application and purpose. [Examples]

[0176] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited in any way by these examples.

[0177] (Measurement of wrinkle structure (surface shape of decorative sheet)) For the decorative sheets obtained in the examples and comparative examples, Rz (maximum height), Ra (arithmetic mean roughness), Spc (arithmetic mean curvature of projection vertices), Rsm (average length of curved elements), Sa (arithmetic mean height), Ssk (skewness), and Sku (curtsis) were measured on a rectangular area (1024 μm × 768 μm) at any point on the surface shape of the decorative sheet using a shape analysis laser microscope ("VK-X150 (control unit) / VK-X160 (measurement unit)", manufactured by Keyence Corporation), with an objective lens of 50x, laser wavelength of 658 nm, measurement mode: surface shape mode, measurement pitch: 0.13 μm, and measurement quality: high-speed mode. The cutoff value was set to 0.8 mm.

[0178] (Evaluation method: 60° gross value) The 60° gloss value (specular gloss) of the decorative sheets obtained in the examples and comparative examples was measured using a gloss meter ("Microgloss (model name)", manufactured by BYK Gardner) in accordance with K 5600-4-7:1999.

[0179] (Internal haze) The matte layer-forming composition described below was applied to a polypropylene sheet (thickness: 60 μm) that had undergone corona discharge treatment as a substrate. The resin composition for matte layer-forming (resin A), described below, was applied to the substrate by gravure printing (application amount: 18 μm (when dry)). The coated surface was then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, maximum illuminance: 0.6 W / cm²). 2 Total luminous intensity: 30-100 mJ / cm² 2 Next, ultraviolet light is irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe2), maximum irradiance: 30 mW / cm²). 2 Total luminous intensity: 5 mJ / cm 2 More than 100mJ / cm 2 The following steps involved irradiating the material in a nitrogen atmosphere (oxygen concentration 200 ppm or less) with an electron beam (acceleration voltage: 100-150 kV, irradiation dose: 30-100 kGy) to form a wrinkled structure. A sample for measuring internal haze was prepared by flattening the surface of a wrinkled structure by attaching an 80 μm thick TAC film (Fujifilm Corporation, TD80UL) via a transparent adhesive (Panac Corporation, PD-S1, 25 μm thick) to eliminate the influence of haze caused by the surface shape. The haze of the prepared sample was measured to determine the internal haze of the matte layer. The light incident surface during haze measurement was the substrate side. A haze meter (HM-150, Murakami Color Technology Laboratory) was used for measurement, and measurements were performed in accordance with JIS K7136:2000.

[0180] (L * (Measurement of values) Regarding the decorative sheets obtained in each of the examples described below, L * The values ​​were measured using the following method. When viewing the decorative sheet from the matte layer side, any 10 L-shaped points * The values ​​were measured, and the average of 10 points was used for each decorative sheet. * The values ​​were determined using a spectrophotometer / color difference meter (model number "CM-700d", manufactured by Konica Minolta, Inc.). During measurement, light (D65 light source) was shone onto the surface of the decorative sheet at an incident angle of 10 degrees. The measurement conditions were a field of view of 2 degrees, a measurement diameter of 3 mmφ, and the measurement mode was total ray reflected light (specular reflection + diffuse reflection).

[0181] (Visibility of differences in brightness) The decorative sheets obtained in the examples and comparative examples were evaluated by 20 randomly selected adults regarding the visibility of the glossy pattern layer. When the visibility of the glossy pattern layer is excellent through the matte layer, the area containing the glossy pattern layer is perceived as a bright area. This results in a decorative sheet with a large difference in brightness due to the matte effect and the glossy pattern layer. The visibility of the luminous pattern layer was evaluated according to the following criteria.

[0182] A: More than 18 people evaluated that they were able to visually perceive the luminous pattern layer and the effect of the brightness difference caused by the luminous pattern layer. B: Between 10 and 17 people evaluated that they were able to visually perceive the luminous pattern layer and the effect of the brightness difference caused by the luminous pattern layer. C: Nine or fewer people evaluated that they were able to visually perceive the luminous pattern layer and the effect of the brightness difference caused by the luminous pattern layer.

[0183] [Example 1] (Preparation of composition for forming a matte finish) A mixture of 30 parts by mass of polyfunctional urethane acrylate oligomer (number of functional groups: 3), 30 parts by mass of polyfunctional acrylate monomer (2-functional), and 40 parts by mass of monofunctional acrylate monomer is prepared, and a wrinkle-forming stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m²) is added. 2 Three parts by mass of (g, oil absorption rate: 40 ml / 100 g) and 0.8 parts by mass of a photopolymerization initiator (benzophenone-based) were added to obtain a matte layer forming composition (resin A).

[0184] (Preparation of composition for forming a lustrous pattern layer) A lustrous pigment (particle size 10-60 μm) was added to a urethane resin to obtain a composition for forming a lustrous pattern layer (resin B).

[0185] (Manufacturing of decorative sheets) A polypropylene sheet (thickness: 60 μm) treated with corona discharge was used as the base material. The glossy pattern layer forming composition (resin B) was applied to one side of the base material by gravure printing (application amount: 3 μm (when dry)), and after drying, a glossy pattern layer was formed on 60% (area ratio) of the surface area of ​​the base material. A resin composition for forming a primer layer (urethane resin, application amount: 2 μm (when dry)) was applied to the glossy pattern layer and dried to form a primer layer.

[0186] The matte layer forming composition (resin A) is applied onto the primer layer by gravure printing (application amount: 5g / m²). 2 Next, ultraviolet light is irradiated using a UV irradiation device consisting of LEDs (wavelength: 395nm, maximum illuminance: 0.6W / cm²). 2 Total luminous intensity: 30-100 mJ / cm² 2 Next, ultraviolet light is irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe2), ultraviolet power density: 30 mW / cm, integrated light amount: 5 mJ / cm). 2 More than 100mJ / cm2 Next, the substrate was irradiated with a nitrogen atmosphere (oxygen concentration of 200 ppm or less), followed by an electron beam (acceleration voltage: 100-150 kV, irradiation dose: 30-100 kGy) to form a matte layer having a wrinkled structure on at least a portion of the outermost surface of the substrate, thereby obtaining a decorative sheet having a glossy pattern layer and a matte layer. As described above, it was confirmed that the surface of the decorative sheet obtained in Example 1 has a wrinkled structure, as shown in the optical microscope image in Figure 2.

[0187] The thickness of the glossy pattern layer was 2.0 μm, the primer layer was 1.0 μm, and the matte layer was 5.0 μm. The thickness of each layer was measured by creating a cross-section of the decorative sheet as shown in Figure 1, and taking the average of the thicknesses measured at 10 arbitrary points in each layer using an optical microscope. The average particle size of the wrinkle-forming stabilizer calculated from this was 60% of the thickness of the matte layer. Regarding the obtained decorative sheet, internal haze, 60° gloss value, L * Table 1 shows the measurement results for the values, visibility of brightness differences, and wrinkle structure.

[0188] [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 10 parts by mass. The internal haze, 60° gloss value, and L of the decorative sheet obtained in Example 2 * Table 1 shows the measurement results for the values, visibility of brightness differences, and wrinkle structure.

[0189] [Comparative Example 1] In Example 1, a decorative sheet was obtained by curing using only electron beam irradiation (acceleration voltage: 100-150kV, irradiation dose: 30-100kGy), without using ultraviolet irradiation with an LED-based UV irradiation device or an excimer light irradiation device.

[0190] [Comparative Example 2] In Comparative Example 1, a decorative sheet was obtained in the same manner as in Comparative Example 1, except that 20 parts by mass of a matting agent (silica particles, average particle size: 3 μm, oil absorption rate: 200 ml / 100 g) was added instead of the wrinkle-forming stabilizer in the matting layer-forming composition.

[0191] [Comparative Example 3] In Example 1, a primer layer was formed on the substrate without forming a glossy pattern layer, and then a matte layer was provided on the primer layer in the same manner as in Example 1 to obtain a decorative sheet having a matte layer.

[0192] The internal haze, 60° gloss value, and L of the decorative sheets obtained in Comparative Examples 1-3 * Table 1 shows the measurement results for the values, visibility of brightness differences, and wrinkle structure.

[0193] [Table 1]

[0194] In Table 1, "〇" indicates the presence of a glossy pattern layer, "×" indicates the absence of a glossy pattern layer, and "〇" indicates irradiation was performed. From the results in Table 1, it was confirmed that the decorative sheets of Examples 1 and 2 are decorative sheets with extremely excellent visibility of the matte effect.

[0195] On the other hand, the decorative material of Comparative Example 1 was a decorative sheet that was not subjected to excimer light irradiation and did not form a wrinkle structure. Although this decorative sheet contained a wrinkle-forming stabilizer, it was found that because no wrinkle structure was generated, the visibility of the glossy pattern layer was excellent, but the 60° gloss value was large and the matte effect was not achieved.

[0196] The decorative sheet of Comparative Example 2 is a decorative sheet that exhibits a matte effect due to the presence of a matting agent. Because the matting agent is present on the surface of this decorative sheet, the Spc and Sku values ​​are larger compared to the decorative sheets of Examples 1 and 2. In addition, although the 60° gloss value is similar to that of the decorative sheet of Example 1, the internal haze is larger due to the effect of the matting agent. Due to these factors, the reflected light from the luminous pigment is blocked, so L * The values ​​are smaller compared to the decorative sheet in Example 1, and the visibility of the luminous pattern layer is also inferior.

[0197] The decorative material of Comparative Example 3 does not have a glossy pattern layer compared to the decorative sheet of Example 1. Although the internal haze and 60° gloss value are similar to those of the decorative sheet of Example 1, L * The value has decreased. [Industrial applicability]

[0198] The decorative sheet disclosed herein has excellent matte finish, visibility, and texture, and is suitable for a variety of applications, including interior components of buildings such as walls, ceilings, and floors; exterior components such as exterior walls, eaves, roofs, fences, and railings; joinery or construction components such as window frames, doors, door frames, handrails, baseboards, moldings, and trim; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; surface decorative panels for cabinets of home appliances and office equipment; and interior and exterior components of vehicles. In addition to being used as a decorative material in the aforementioned buildings, the decorative sheet disclosed herein is suitable for use as a packaging material, anti-glare film for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, and various certificates, keyboard keys, transparent panels (window glass, etc.) for windows, doors, and partitions, and artificial leather, either on its own or in a laminated, composite, or combined form with other materials (adhered materials). [Explanation of Symbols]

[0199] 2: Convex part 3: Recess 20: Top surface 21: Matte finish 22: Primer layer 23: Luminous pattern layer 24: Decorative layer 25: Base material 31: Adhesive layer 30: Adherent material 100: Decorative sheet

Claims

[Claim 1] A decorative sheet comprising a lustrous pattern layer containing a lustrous pigment and a matte layer, wherein at least a portion of the outermost surface of the matte layer has a wrinkled structure.

Images