Decorative sheet

Abstract

Provided is a decorative sheet having excellent scratch resistance and adhesion between gloss adjustment layers. This decorative sheet (1) comprises a raw fabric layer (2) and a surface protective layer, wherein the surface protective layer includes: a first gloss adjustment layer (5) which is provided on the raw fabric layer (2) and contains only a cured product of a first ionizing radiation-curable resin as a resin cured product, the first ionizing radiation-curable resin being a first mixture of acrylate and methacrylate; and a second gloss adjustment layer (6) which partially covers the upper surface of the first gloss adjustment layer (5), contains only a cured product of a second ionizing radiation-curable resin as a resin cured product, and has a lower specular glossiness GS (60º) compared to the first gloss adjustment layer (5).

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet. [Background technology]

[0002] Decorative materials used for the surface decoration of the interior and exterior of buildings, fittings, furniture, etc. are generally in the form of decorative boards, which are formed by attaching a decorative sheet to the surface of a substrate via an adhesive or the like. The decorative sheet is typically provided with a desired pattern, such as a wood grain or stone pattern. Furthermore, decorative sheets that not only simply express a wood grain or stone pattern in a two-dimensional manner, but also express a three-dimensional texture similar to the surface of natural wood or stone, are also widely used, primarily in applications where a luxurious feel is desired.

[0003] Various methods have been devised for expressing a three-dimensional textured effect in combination with a flat pattern on the surface of a decorative sheet, and are used according to the purpose. For example, rather than actually forming a three-dimensional effect on the surface of a decorative material, there is a method in which the glossiness of the surface of the decorative material is made different between the areas that should be expressed as concaves or convexities and other areas, thereby visually expressing a three-dimensional textured effect by utilizing the illusion of the human eye. With this method, even if there are no actual concaves or convexities that the viewer can perceive, the areas with a relatively high glossiness are perceived as convexities and the areas with a relatively low glossiness are perceived as concaves.

[0004] To manufacture such a decorative sheet, for example, first, a printed layer containing a pattern corresponding to the area where the depressions are to be formed is formed on one surface of the substrate. Next, a transparent or translucent first gloss-adjustment layer with low gloss is formed over the entire surface of the substrate on which the printed layer is formed. Next, a transparent or translucent second gloss-adjustment layer with high gloss is formed over the entire surface of the first gloss-adjustment layer except for the area corresponding to the pattern. Note that by reversing the relationship between high and low gloss levels between the first and second gloss-adjustment layers, a decorative sheet with a reversed relationship between the depressions and protrusions can be obtained.

[0005] This technique allows for the creation of a three-dimensional textured effect on any substrate simply by preparing two types of paint that impart different levels of gloss, without the need for special chemicals. Furthermore, the formation of gloss-adjusting layers with different levels of gloss can be achieved using conventional printing methods, such as gravure printing, following the formation of the pattern (pattern ink layer). This eliminates the need for any special equipment, increases production efficiency, and simplifies the alignment of the second synthetic paint layer with the pattern. Furthermore, the second gloss-adjusting layer can be much thinner than the height difference of the textured surface that should be perceived by the viewer, thereby reducing the amount of resin used and providing advantages in terms of flexibility, making it easy to achieve a decorative sheet with excellent foldability. Another advantage is that the surface of the decorative sheet does not have large height differences, preventing contaminants from remaining in the recesses. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2022 / 182259 [Patent Document 2] Japanese Patent Application Publication No. 2014-188842 Summary of the Invention

[0007] An object of the present invention is to provide a decorative sheet that is excellent in scratch resistance and adhesion between gloss-adjusting layers.

[0008] According to one aspect of the present invention, there is provided a decorative sheet comprising: a raw fabric layer; and a surface protective layer, wherein the surface protective layer is disposed on the raw fabric layer and contains only a cured product of a first ionizing radiation curable resin as a resin cured product, the first ionizing radiation curable resin being a first mixture of acrylate and methacrylate; and a second gloss adjustment layer that partially covers the upper surface of the first gloss adjustment layer and contains only a cured product of a second ionizing radiation curable resin as a resin cured product, and has a lower specular gloss GS(60°) than the first gloss adjustment layer.

[0009] According to another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein in the first ionizing radiation curable resin, the proportion of the number of moles of methacryloyl groups to the total number of moles of acryloyl groups and the number of moles of methacryloyl groups is in the range of 3% or more and 50% or less.

[0010] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the methacrylate is a monofunctional, difunctional, or trifunctional methacrylate.

[0011] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the second ionizing radiation curable resin is an acrylate or a second mixture of an acrylate and a methacrylate, and the second mixture has a smaller proportion of the number of moles of methacryloyl groups in the sum of the number of moles of acryloyl groups and the number of moles of methacryloyl groups compared to the first mixture.

[0012] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the second ionizing radiation curable resin contains a di- or higher functional acrylate containing a repeating structure.

[0013] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the repeating structure is repeated three or more times.

[0014] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, in which the surface of the second gloss adjustment layer is provided with an uneven structure including a plurality of ridge-like portions, each of which protrudes in a ridge-like shape.

[0015] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the uneven structure has a ratio RSm / Ra of the average length RSm of the roughness curve elements to the arithmetic mean roughness Ra in the range of 10 or more and 900 or less, preferably in the range of 10 or more and 500 or less.

[0016] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the thickness of each of the first gloss adjustment layer and the second gloss adjustment layer is within the range of 2 μm or more and 20 μm or less.

[0017] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the second gloss control layer further contains particles having an average particle size of 10 μm or less.

[0018] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, in which the mass of the particles is in the range of 0.5 parts by mass or more and 20 parts by mass or less when the mass of the second ionizing radiation curable resin is 100 parts by mass.

[0019] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the first gloss adjustment layer has a specular gloss GS(60°) of 3 or more, and the second gloss adjustment layer has a specular gloss GS(60°) of 20 or less, preferably 10 or less.

[0020] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the difference between the specular gloss GS(60°) of the first gloss adjustment layer and the specular gloss GS(60°) of the second gloss adjustment layer is 1 or more.

[0021] According to yet another aspect of the present invention, there is provided a decorative material comprising a decorative sheet according to any one of the above aspects and a substrate to which the decorative sheet is attached.

[0022] According to yet another aspect of the present invention, there is provided a method for producing a decorative sheet, comprising: forming, on an original layer, a first coating film containing only a first ionizing radiation curable resin as a resin, the first ionizing radiation curable resin being a first mixture of acrylate and methacrylate; carrying out a first irradiation step of irradiating the first coating film with ionizing radiation or ultraviolet light to semi-cure the first coating film; forming, on the semi-cured first coating film, a second coating film containing only a second ionizing radiation curable resin as a resin so as to partially cover an upper surface of the first coating film; and irradiating the first coating film and the second coating film with ionizing radiation or ultraviolet light to completely cure the first coating film and the second coating film.

[0023] According to yet another aspect of the present invention, there is provided a method for producing a decorative sheet according to the above aspect, wherein the complete curing of the first coating film and the second coating film includes a second irradiation step in which the second coating film is irradiated with light having a wavelength of 200 nm or less, and then a third irradiation step in which the first coating film and the second coating film are irradiated with ionizing radiation or ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step.

[0024] According to the present invention, a decorative sheet is provided which is excellent in scratch resistance and adhesion between gloss-adjusting layers. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view of a second gloss-adjusting layer included in the decorative sheet of FIG. [Figure 3] FIG. 3 is a microscope image of the second gloss adjustment layer contained in a decorative sheet according to one example of the present invention. [Figure 4] FIG. 4 is an enlarged cross-sectional view showing a part of the second gloss adjustment layer shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0026] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The embodiments described below are more specific embodiments of any of the above aspects. The following items can be incorporated into each of the above aspects, either singly or in combination.

[0027] Furthermore, the embodiments shown below are merely examples of configurations for embodying the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited by the materials, shapes, structures, etc. of the components described below. Various modifications can be made to the technical idea of ​​the present invention within the technical scope defined by the claims.

[0028] In the drawings, elements having the same or similar functions are denoted by the same reference numerals, and redundant explanations will be omitted. Furthermore, the drawings are schematic, and the relationship between dimensions in one direction and dimensions in another direction, and the relationship between the dimensions of one member and the dimensions of another member, etc. may differ from the actual relationship.

[0029] <1> Decorative materials and decorative sheets Fig. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. Fig. 2 is a cross-sectional view of a second gloss adjustment layer included in the decorative sheet of Fig. 1. Fig. 3 is a micrograph of a second gloss adjustment layer included in a decorative sheet according to one example of the present invention. Fig. 4 is an enlarged cross-sectional view of a portion of the second gloss adjustment layer shown in Fig. 2.

[0030] 2 and 4 are cross sections taken along the thickness direction of the second gloss adjustment layer. The micrograph in Fig. 3 is a plan view taken with a laser microscope (OLS-4000 manufactured by Olympus Corporation).

[0031] The decorative material 11 shown in FIG. 1 includes a substrate B and a decorative sheet 1 attached thereto. Here, the decorative material 11 is a decorative board. The decorative board may be a flat plate, or may be curved or folded. The decorative material 11 may have a shape other than a plate.

[0032] Here, the substrate B is a plate material. The plate material is, for example, a wood board, an inorganic board, a metal plate, or a composite board made of multiple materials. The substrate B may have a shape other than a plate.

[0033] The decorative sheet 1 includes a base fabric layer 2, a solid ink layer 3, a pattern ink layer 4, a first gloss adjustment layer 5, and a second gloss adjustment layer 6. The solid ink layer 3, the pattern ink layer 4, the first gloss adjustment layer 5, and the second gloss adjustment layer 6 are provided in this order from the base fabric layer 2 side on the surface of the base fabric layer 2 opposite the surface facing the substrate B. One or more other layers, such as a transparent resin layer, may be provided between the pattern ink layer 4 and the first gloss adjustment layer 5. A primer layer may be provided on one or more of the base fabric layer 2, the solid ink layer 3, and the pattern ink layer 4. Furthermore, one or both of the solid ink layer 3 and the pattern ink layer 4 may be omitted. The elements contained in the decorative sheet 1 will be explained below one by one.

[0034] <1.1> Raw fabric layer Examples of the raw fabric layer 2 or its materials include papers such as tissue paper, resin-mixed paper, titanium dioxide paper, resin-impregnated paper, flame-retardant paper, and inorganic paper; woven or nonwoven fabrics made from natural or synthetic fibers; synthetic resin substrates including polyolefin resins such as homo- or random-form polypropylene resin and polyethylene resin, copolymer polyester resin, amorphous crystalline polyester resin, polyethylene naphthalate resin, polybutylene resin, acrylic resin, polyamide resin, polycarbonate resin, polyvinyl chloride resin, polyvinylidene chloride resin, and fluorine-containing resin; wood substrates such as wood veneer, veneer, plywood, laminated lumber, particleboard, and medium-density fiberboard; inorganic substrates such as gypsum board, cement board, calcium silicate board, and ceramic board; metal substrates made from metals such as iron, copper, aluminum, and stainless steel; or composites or laminates thereof. The raw fabric layer 2 can have various forms, such as films, sheets, plates, and irregularly shaped molded bodies.

[0035] <1.2> Solid ink layer The solid ink layer 3 is a continuous film formed by coating one entire surface of the base fabric layer 2 with ink. The solid ink layer 3 can function as a concealing layer that conceals the substrate B or the base fabric layer 2. The solid ink layer 3 can also function as a flattening layer. The solid ink layer 3 may have a single-layer structure or a multi-layer structure.

[0036] The solid ink layer 3 can be formed, for example, using a printing ink (or coating agent) prepared by dissolving or dispersing a matrix and a colorant such as a dye or pigment in a solvent.

[0037] As the matrix, various synthetic resins such as oil-based nitrocellulose resin, two-component urethane resin, acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, epoxy resin, melamine resin, fluorine resin, silicone resin, and daimi rubber resin, or mixtures or copolymers of these can be used.

[0038] Examples of colorants that can be used include inorganic pigments such as carbon black, titanium white, zinc white, red iron oxide, yellow lead, iron blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; and mixtures thereof.

[0039] Examples of the solvent that can be used include toluene, xylene, ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, and mixtures thereof.

[0040] To the ink described above, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, drying agents, curing agents, curing accelerators, and curing retarders may be added in order to impart various functions.

[0041] <1.3> Pattern ink layer The pattern ink layer 4 is provided to add a pattern to the decorative sheet 1. The pattern pattern may be, for example, a wood grain pattern, a stone grain pattern, a sand grain pattern, a tile pattern, a brickwork pattern, a fabric pattern, a leather-grained pattern, or a geometric figure. In the example of FIG. 1, the pattern ink layer 4 is a printed pattern that partially covers the upper surface of the solid ink layer 3. This printed pattern is provided directly below the second gloss adjustment layer. In other words, the second gloss adjustment layer 6 is provided so as to overlap the pattern ink layer 4. In other words, the printed pattern contained in the pattern ink layer 4 and the pattern of the second gloss adjustment layer 6 are orthogonally projected onto a plane perpendicular to the thickness direction and have the same shape and position. Hereinafter, the state in which the orthogonal projections onto a plane perpendicular to the thickness direction are orthogonally projected onto a plane perpendicular to the thickness direction will sometimes be abbreviated as "the shapes and positions are consistent."

[0042] The pattern ink layer 4 can be formed using, for example, the ink described above for the solid ink layer 3. The pattern ink layer 4 is formed using the number of plates necessary to express the desired design. That is, the pattern ink layer 4 may be a layer consisting of one printed pattern made of a single ink, or may be a layer consisting of multiple printed patterns made of different inks. In the latter case, one printed pattern may match the shape and position of the pattern in the second gloss adjustment layer 6, or a combination of two or more printed patterns may match the shape and position of the pattern in the second gloss adjustment layer 6. For example, one printed pattern or a combination of two or more printed patterns may match the shape and position of the pattern in the second gloss adjustment layer 6, with the remaining printed patterns located in areas corresponding to the openings in the second gloss adjustment layer 6.

[0043] When the pattern ink layer 4 contains only one printing pattern, this printing pattern has a different color from the solid ink layer 3. When the pattern ink layer 4 contains multiple printing patterns, and the combination of these printing patterns matches the shape and position of the pattern in the second gloss adjustment layer 6, one or more of these printing patterns, for example, all of these printing patterns, have a different color from the solid ink layer 3. When the pattern ink layer 4 contains multiple printing patterns, and one printing pattern or a combination of two or more printing patterns matches the shape and position of the pattern in the second gloss adjustment layer 6, and the remaining printing patterns are located in areas corresponding to the openings in the second gloss adjustment layer 6, one or more of the former printing patterns have a different color from the solid ink layer 3 and one or more of the latter printing patterns. For example, all of the former printing patterns have a different color from the solid ink layer 3 and all of the latter printing patterns.

[0044] Here, as an example, the pattern ink layer 4 is a layer consisting of one print pattern made of a single ink, and is a different color from the solid ink layer 3.

[0045] <1.4>Transparent resin layer As described above, the decorative sheet 1 can further include a transparent resin layer between the pattern ink layer 4 and the first gloss adjustment layer 5. The transparent resin layer can contribute to improving the abrasion resistance of the decorative sheet 1.

[0046] The transparent resin layer is preferably made of a resin composition containing an olefin-based resin as a main material, such as polypropylene, polyethylene, or polybutene. The olefin resin may be a homopolymer or copolymer of two or more α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. The olefin-based resin may be a copolymer of ethylene or an α-olefin with another monomer, such as an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl methacrylate copolymer, an ethylene-butyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-butyl acrylate copolymer, etc. In particular, when further improvement of surface strength is desired, it is preferable to use a highly crystalline polypropylene.

[0047] The transparent resin layer may contain additives such as a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a catalyst scavenger, and a colorant. These additives can be appropriately selected from known additives. The transparent resin layer can be formed by various lamination methods such as a method using heat and pressure, an extrusion lamination method, and a dry lamination method.

[0048] <1.5> Primer layer As described above, a primer layer can be provided on one or more of the base layer 2, the solid ink layer 3 and the pattern ink layer 4.

[0049] When an olefin-based resin is used as the material for the raw fabric layer 2, the surface of the raw fabric layer 2 is often in an inactive state. Therefore, in this case, it is preferable to provide a primer layer between the raw fabric layer 2 and the substrate B. When the raw fabric layer 2 is made of an olefin-based material, this primer layer may be omitted, and the raw fabric layer 2 may be subjected to a surface modification treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, or dichromate treatment in order to improve the adhesion between the raw fabric layer 2 and the substrate B.

[0050] Materials for the primer layer include, for example, soluble nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyesters, or modified products thereof, either alone or in combination. Water-based, solvent-based, or emulsion-based primers are acceptable, as are single-component and two-component primers incorporating a curing agent. The primer layer may be formed by curing a layer formed with a curable ink by irradiation with ultraviolet light, electron beams, or the like. The most common method is to use a urethane-based ink and cure it with an isocyanate. The ink used to form the primer layer may further contain, in addition to a binder, pigments typically found in inks, colorants such as dyes, extender pigments, solvents, and various additives. Examples of versatile pigments include condensed azo compounds, insoluble azo compounds, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.

[0051] Since the primer layer 6 is applied to the back surface of the decorative sheet 1, and taking into consideration the fact that the decorative sheet 1 is in web form and will be rolled up, an inorganic filler may be added to the primer layer to avoid blocking and increase adhesion to the adhesive. Examples of inorganic fillers include silica, alumina, magnesia, titanium oxide, and barium sulfate.

[0052] <1.6> First gloss adjustment layer The first gloss adjustment layer 5 is provided on the base fabric layer 2. Here, the first gloss adjustment layer 5 covers the solid ink layer 3 and the pattern ink layer 4.

[0053] The first gloss adjustment layer 5 has a higher specular gloss GS(60°) than the second gloss adjustment layer 6. The specular gloss GS(60°) of the first gloss adjustment layer 5 is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. In one example, the specular gloss GS(60°) of the first gloss adjustment layer 5 is 30 or less. Here, the "specular gloss GS(60°)" is the specular gloss measured at an incident angle of 60 degrees using a gloss meter conforming to ISO 2813. Note that the specular gloss GS(60°) is sometimes expressed with "%" added after the numerical value, but the "%" will be omitted here.

[0054] The first gloss adjustment layer 5 is made of a cured resin. The first gloss adjustment layer 5 may further contain particles. When the mass of the first gloss adjustment layer 5 is taken as 100 parts by mass, the mass of the cured resin contained in the first gloss adjustment layer 5 is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

[0055] The first gloss adjustment layer 5 contains only a cured product of a first ionizing radiation curable resin as the cured resin. Here, "ionizing radiation" refers to a charged particle beam such as an electron beam. The first ionizing radiation curable resin is cured by irradiation with ionizing radiation. The first ionizing radiation curable resin can also be cured by irradiation with ultraviolet light.

[0056] The first ionizing radiation curable resin may be any known resin, such as various monomers or commercially available oligomers, including (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, or epoxy resins. The second ionizing radiation curable resin may be either an aqueous resin or a non-aqueous (organic solvent) resin. The second ionizing radiation curable resin may be solvent-free.

[0057] The first ionizing radiation curable resin mainly comprises a first mixture of an acrylate resin and a methacrylate resin.

[0058] The methacrylate is preferably a monofunctional, difunctional, or trifunctional methacrylate. The methacrylate may be any one of a monofunctional methacrylate, a difunctional methacrylate, and a trifunctional methacrylate, or may be two or more of them.

[0059] When a methacrylate with a large number of functional groups is used, the degree of crosslinking is increased and scratch resistance is improved compared to when a methacrylate with a small number of functional groups is used. However, when a methacrylate with an excessively large number of functional groups is used, the rate of the crosslinking reaction due to irradiation with ionizing radiation or ultraviolet light increases, narrowing the process window in which high adhesion can be achieved between the first gloss adjustment layer 5 and the second gloss adjustment layer 6.

[0060] In the first ionizing radiation curable resin, the proportion of the number of moles of methacryloyl groups to the total number of moles of acryloyl groups and methacryloyl groups is preferably in the range of 3% or more and 50% or less, and more preferably in the range of 5% or more and 40% or less.

[0061] The methacrylate allows the first coating film containing the first ionizing radiation-curable resin to be semi-cured by irradiation with ionizing radiation or ultraviolet light. Increasing the above ratio widens the process window that allows for high adhesion between the first gloss adjustment layer 5 and the second gloss adjustment layer 6. However, if the above ratio is excessively large, the scratch resistance of the decorative sheet 1 decreases.

[0062] The thickness of the first gloss adjustment layer 5 is preferably in the range of 2 μm to 20 μm, more preferably in the range of 3 μm to 20 μm, and even more preferably in the range of 5 μm to 15 μm. If the thickness of the first gloss adjustment layer 5 is reduced, scratch resistance decreases. If the thickness of the first gloss adjustment layer 5 is increased, the processability of the decorative sheet 1 decreases, and it becomes more likely to whiten when folded.

[0063] <1.7> Second gloss adjustment layer The second gloss adjustment layer 6 partially covers the upper surface of the first gloss adjustment layer 5. The second gloss adjustment layer 6, together with the first gloss adjustment layer 5, constitutes a surface protection layer.

[0064] The second gloss adjustment layer 6 faces the pattern ink layer 4 with the first gloss adjustment layer 5 sandwiched therebetween. The second gloss adjustment layer 6 matches the pattern ink layer 4 in shape and position.

[0065] Here, the second gloss adjustment layer 6 completely matches the shape and position of the pattern ink layer 4, but other configurations may also be adopted. For example, the orthogonal projection of the pattern ink layer 4 onto a plane perpendicular to the thickness direction may be at least partially separated from and located inside the outline of the orthogonal projection of the second gloss adjustment layer 6 onto the plane.

[0066] In addition, here, the pattern ink layer 4 consists of a single printing pattern, but if the pattern ink layer 4 consists of multiple printing patterns of different colors, the second gloss adjustment layer 6 may match the shape and position of a combination of these printing patterns. Alternatively, in this case, the second gloss adjustment layer 6 may match the shape and position of one or a combination of two or more of these printing patterns, and the remaining printing patterns may be provided in positions that do not directly face the second gloss adjustment layer 6.

[0067] It is preferable that the orthogonal projection of the second gloss adjustment layer 6 onto a plane perpendicular to the thickness direction overlaps with the orthogonal projection onto the same plane of one printed pattern or a combination of two or more printed patterns whose shape and position match those of the second gloss adjustment layer 6, for preferably 50% or more of its area, more preferably 70% or more, and even more preferably 90% or more.

[0068] The second gloss adjustment layer 6 has a lower specular gloss GS(60°) than the first gloss adjustment layer 5. The specular gloss GS(60°) of the second gloss adjustment layer 6 is preferably 20 or less, and more preferably 10 or less. According to one example, the specular gloss GS(60°) of the second gloss adjustment layer 6 is 0.5 or more.

[0069] The difference between the specular gloss GS(60°) of the first gloss adjustment layer 5 and the specular gloss GS(60°) of the second gloss adjustment layer 6 is preferably at least 1, more preferably at least 3, and even more preferably at least 5. According to one example, this difference is 20 or less.

[0070] An uneven structure is provided on the surface of the second gloss adjustment layer 6. The uneven structure provided on the upper surface of the second gloss adjustment layer 6 serves to make the specular gloss GS(60°) of the second gloss adjustment layer 6 lower than the specular gloss GS(60°) of the first gloss adjustment layer 5.

[0071] Here, an uneven structure including a plurality of ridge-like portions each protruding in a ridge shape is provided on the surface of the second gloss adjustment layer 6. That is, as shown in Figures 2 and 4, the second gloss adjustment layer 6 includes a core portion 6A which is a thin layer having a flat upper surface, and a plurality of ridge-like portions 6B each protruding in a ridge shape from the upper surface of the core portion 6A.

[0072] In the present disclosure, the ridge portion 6B refers to, for example, the portion from the lowest part to the tip of the protrusion provided on the surface of the second gloss adjustment layer 6, and the core portion 6A refers to the portion of the second gloss adjustment layer 6 excluding the ridge portion 6B. Furthermore, the term "ridge-like" refers to a convex shape that extends linearly in a planar view.

[0073] The ridge portions 6B may be curved or linear in plan view, but from the viewpoint of fingerprint resistance of the surface of the decorative sheet 1, a curved shape as exemplified in Fig. 3 is preferable. Note that the second gloss-adjusting layer 6 having the ridge portions 6B can be formed, for example, as described below, by irradiating the surface of a coating film containing a second ionizing radiation-curable resin with light of a specific wavelength, and causing the cured film formed on the surface of the coating film to expand in the in-plane direction.

[0074] The uneven structure on the upper surface of the second gloss adjustment layer 6 preferably has a ratio RSm / Ra of the average length RSm of the roughness curve elements to the arithmetic mean roughness Ra in the range of 10 to 900, more preferably 10 to 500, even more preferably 10 to 400, and even more preferably 50 to 350. A smaller ratio RSm / Ra reduces the pitch of the convex portions. As a result, it becomes difficult to wipe off dirt adhering to the surface of the decorative sheet 1, and the stain resistance decreases. An increased ratio RSm / Ra increases the pitch of the convex portions, reducing the effect of the uneven structure on reducing the specular gloss GS(60°) of the second gloss adjustment layer 6.

[0075] The ratio RSm / Ra is preferably 80 or greater. Increasing the ratio RSm / Ra increases the pitch of the convex portions, improving the affinity of water or detergent (water containing a surfactant or alcohol) to the upper surface of the second gloss adjustment layer 6. If the decorative sheet 1 has a second gloss adjustment layer 6 with such surface properties, even if the surface becomes dirty, the dirt can be easily wiped off with water or detergent.

[0076] It is most preferable that the ratio RSm / Ra is 100 or greater. If the ratio RSm / Ra is within this range, a commonly available cleaning sponge can be brought into contact with the boundaries of the convex portions and the areas nearby on the upper surface of the second gloss control layer 6. Therefore, even if the surface of the decorative sheet 1 becomes soiled, the dirt can be easily wiped off using a commonly available cleaning sponge.

[0077] Here, the arithmetic mean roughness Ra and the mean length of the roughness curve element RSm are values ​​measured using a line roughness meter (in accordance with JIS B0601:2013).

[0078] The arithmetic mean roughness Ra is preferably in the range of 0.2 μm to 10.0 μm, more preferably in the range of 0.5 μm to 5.0 μm, and even more preferably in the range of 0.8 μm to 4.0 μm.

[0079] The average length RSm of the roughness curve elements is preferably in the range of 50 μm or more and 800 μm or less, more preferably in the range of 80 μm or more and 600 μm or less, and even more preferably in the range of 100 μm or more and 500 μm or less.

[0080] The upper surface of the second gloss-adjusting layer 6 may have a sine wave shape in a cross section parallel to the thickness direction and the arrangement direction of the ridge portions 6B. Here, the "sine wave shape" refers to a shape in which the line from the lowest point C of the ridge portions 6B to the highest point D (vertex) can be expressed as a sine wave, as shown in FIG.

[0081] The thickness of the second gloss adjustment layer 6 is preferably in the range of 2 μm to 20 μm, more preferably in the range of 3 μm to 20 μm, even more preferably in the range of 5 μm to 15 μm, and most preferably in the range of 5 μm to 12 μm. If the thickness of the second gloss adjustment layer 6 is small, it will be difficult to achieve the above-mentioned surface texture by the method described below while referring to the ratio RSm / Ra, etc. If the thickness of the second gloss adjustment layer 6 is large, the processability of the decorative sheet 1 will decrease and it will be prone to whitening when folded.

[0082] Here, the thickness of the second gloss adjustment layer 6 is the thickness of a layer that has the same apparent area and volume as the second gloss adjustment layer 6 and a flat surface. The thickness of the second gloss adjustment layer 6 is determined, for example, by the following method. First, a cross section parallel to the thickness direction of the second gloss adjustment layer 6 and perpendicular to the length direction of the ridge portions 6B is imaged. Next, from this cross-sectional image, the dimension of the second gloss adjustment layer 6 in the width direction of the ridge portions 6B and the area of ​​the cross section of the second gloss adjustment layer 6 are determined. The thickness of the second gloss adjustment layer 6 is the value obtained by dividing this area by the above dimension. Note that when the coating liquid for the second gloss adjustment layer described below does not contain a solvent, the thickness of the coating film made of this coating liquid is equal to the thickness of the second gloss adjustment layer 6.

[0083] Furthermore, the thickness of the second gloss adjustment layer 6 is preferably set so that the ratio of the thickness (or height) of the ridge portion 6B to the thickness of the core portion 6A (thickness of the ridge portion 6B / thickness of the core portion 6A) is within the range of 0.01 or more and 2.0 or less, and more preferably within the range of 0.1 or more and 1.0 or less.

[0084] The second gloss adjustment layer 6 contains a cured resin. As described below, the second gloss adjustment layer 6 may further contain particles. When the mass of the second gloss adjustment layer 6 is taken as 100 parts by mass, the mass of the cured resin contained in the second gloss adjustment layer 6 is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

[0085] The second gloss adjustment layer 6 contains only the cured product of the second ionizing radiation curable resin as the resin cured product. As described above, the ionizing radiation is a charged particle beam such as an electron beam. The second ionizing radiation curable resin is cured by irradiation with ionizing radiation. The second ionizing radiation curable resin can also be cured by irradiation with ultraviolet light. The second ionizing radiation curable resin used here is cured by irradiation with light having a wavelength of 200 nm or less, and has a high absorption coefficient for this light.

[0086] The second ionizing radiation curable resin may be any known resin, such as various monomers or commercially available oligomers, including (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, or epoxy resins. The second ionizing radiation curable resin may be either an aqueous resin or a non-aqueous (organic solvent) resin. The second ionizing radiation curable resin may be solvent-free.

[0087] The main component of the second ionizing radiation curable resin is preferably an acrylate, where the main component means that the content is 60 parts by mass or more, more preferably 70 parts by mass or more, and most preferably 80 parts by mass or more per 100 parts by mass of the resin components constituting the second ionizing radiation curable resin.

[0088] The acrylate is preferably a difunctional or higher acrylate, and more preferably a trifunctional or higher acrylate. In order to obtain a second gloss adjusting layer 6 having excellent scratch resistance, the acrylate is preferably a trifunctional or higher acrylate. There is no upper limit to the number of functional groups of the acrylate, but according to one example, it is hexafunctional or lower.

[0089] The acrylate preferably contains a repeating unit. This repeating unit is, for example, any one of an ethylene oxide (EO) unit, a propylene oxide (PO) unit, and an ε-caprolactone (CL) unit. The repeating unit is preferably ethylene oxide or propylene oxide. In the acrylate, the repeating unit may be in a ring-opened state and interposed between the acryloyl group and the methylol group.

[0090] The number of repetitions of the repeating structure is preferably 3 or more. If an acrylate with a large number of repetitions is used, the cured film is more likely to expand in the in-plane direction during the second irradiation step described below, and therefore wrinkles corresponding to the ridge portions 6B are more likely to appear on the coating film surface. However, if the number of repetitions is increased, the crosslinking density decreases, and the scratch resistance of the surface protective layer decreases. Therefore, the number of repetitions is preferably 30 or less, and more preferably 20 or less.

[0091] The repeat number of the repeating structure can be analyzed using MALDI-TOF-MS. Ionizing radiation curable resins may have a molecular weight distribution. If there is a molecular weight distribution, the repeat number is determined to be the repeat number corresponding to the molecular weight with the strongest peak in the MALDI-TOF-MS mass spectrum.

[0092] When the second ionizing radiation curable resin contains an acrylate, it may further contain a methacrylate. For example, the second ionizing radiation curable resin may be a second mixture of an acrylate and a methacrylate, in which the proportion of the number of moles of methacryloyl groups in the total number of moles of acryloyl groups and the number of moles of methacryloyl groups is smaller than that in the first mixture. The proportion in the second mixture is preferably 90% or less, and more preferably 80% or less, of the proportion in the first mixture.

[0093] The second gloss adjustment layer 6 may further contain particles in addition to the cured resin. The particles contained in the second gloss adjustment layer 6 may be, for example, particles made of organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads, or particles made of inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.

[0094] The average particle size (D50) of the particles is preferably 10 μm or less, more preferably in the range of 1 μm to 8 μm, even more preferably in the range of 2 μm to 7 μm, and most preferably in the range of 3 μm to 6 μm. If the average particle size (D50) of the particles is large, the particles tend to fall off from the second gloss-controlling layer 6, which may make it difficult to achieve high scratch resistance. If the particles are small, the effect of generating wrinkles uniformly is reduced. Here, the "average particle size" or "average particle size (D50)" refers to the median size (D50) measured using a laser diffraction / scattering particle size distribution analyzer. If the coating liquid for the second gloss control layer contains particles, the second gloss control layer 6 obtained from this coating liquid will also contain particles. The average particle size of the particles contained in the second gloss control layer 6 can be determined by observing the cross section of the layer and averaging the particle sizes of multiple particles. The value obtained in this manner is essentially the same as the median size (D50) measured using a laser diffraction / scattering particle size distribution analyzer. Therefore, the above-mentioned average particle size range can also be interpreted as the average particle size range of the particles contained in the second gloss control layer.

[0095] The amount of particles in the second gloss adjustment layer 6 is preferably in the range of 0.5 parts by mass or more and 20 parts by mass or less, more preferably in the range of 0.5 parts by mass or more and 10 parts by mass or less, more preferably in the range of 2 parts by mass or more and 8 parts by mass or less, and most preferably in the range of 2 parts by mass or more and 6 parts by mass or less, per 100 parts by mass of the cured resin.

[0096] When the amount of particles added is within the above range, the effect of generating wrinkles uniformly is particularly large. If the amount of particles added is too large, the particles tend to fall off from the second gloss adjustment layer 6, which may make it difficult to achieve high scratch resistance.

[0097] <2> Manufacturing method of decorative sheet The decorative sheet 1 is produced, for example, by the following method. First, a solid ink layer 3 is formed on one surface of the base layer 2. The solid ink layer 3 can be formed by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing, or various coating methods such as roll coating, knife coating, microgravure coating, and die coating.

[0098] Next, a pattern ink layer 4 is formed on the solid ink layer 3. The pattern ink layer 4 can be formed by various printing methods, such as gravure printing, offset printing, screen printing, electrostatic printing, inkjet printing, etc. Among these, gravure printing is preferred because it allows for relatively high speed printing and is advantageous in terms of cost.

[0099] Next, a first coating film made of a coating liquid for the first gloss adjustment layer is formed on the above surface of the base fabric layer 2 so as to cover the solid ink layer 3 and the pattern ink layer 4. This first coating film can be formed by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing, or various coating methods such as roll coating, knife coating, microgravure coating, and die coating.

[0100] The coating liquid for the first gloss adjustment layer contains the above-mentioned first ionizing radiation curable resin. As described above, the first ionizing radiation curable resin is a first mixture of acrylate and methacrylate.

[0101] The coating liquid for the first gloss adjustment layer may further contain other components, such as the above-mentioned particles, solvents, and additives for improving the functionality of the final product, such as one or more antibacterial agents and antifungal agents. The coating liquid for the first gloss adjustment layer may further contain other additives such as ultraviolet absorbers and light stabilizers. Examples of ultraviolet absorbers that can be used include benzotriazoles, benzoates, benzophenones, and triazines. Examples of light stabilizers that can be used include hindered amines.

[0102] When the first coating film is completely cured by ultraviolet light irradiation in the third irradiation step described below, the coating liquid for the first gloss control layer preferably further contains a photoinitiator. The photoinitiator is not particularly limited, but examples thereof include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based photoinitiators.

[0103] Next, a first irradiation step is carried out. In the first irradiation step, the first coating film is irradiated with a first radiation to semi-cure the first coating film. Here, "semi-cure" refers to a state in which the coating film has become solid but still contains a sufficient amount of C=C bonds derived from the acryloyl groups and methacryloyl groups.

[0104] The first radiation is, for example, ionizing radiation. As described above, ionizing radiation is a charged particle beam such as an electron beam. The first radiation may be ultraviolet light, for which the first ionizing radiation curable resin exhibits a small absorption coefficient. The wavelength of the ultraviolet light irradiated onto the first coating film is preferably greater than 200 nm, more preferably in the range of 230 nm to 450 nm, and even more preferably in the range of 250 nm to 400 nm.

[0105] When the first coating film is irradiated with ionizing radiation or ultraviolet light, the first coating film can be cured substantially uniformly throughout its entire thickness. Therefore, unlike the second coating film described below, the semi-cured first coating film does not have an irregular surface.

[0106] The first coating film is irradiated with the first radiation so that the unreacted rate of the first coating film, i.e., the ratio of the number of C=C bonds after irradiation with the first radiation to the number of C=C bonds before irradiation with the first radiation, is preferably in the range of 5% to 80%, more preferably in the range of 10% to 60%, and even more preferably in the range of 15% to 50%.

[0107] The first coating film is irradiated with the first radiation so that the cumulative light amount is preferably in the range of 3% to 30% of the minimum cumulative light amount required to completely cure the first coating film, more preferably in the range of 5% to 25%, and even more preferably in the range of 8% to 20%.

[0108] The minimum cumulative amount of light required to completely cure the first coating is, for example, 10 mJ / cm 2 More than 1000mJ / cm 2 It is within the following range:

[0109] The first coating film is irradiated with the first radiation so that the absorbed dose is preferably in the range of 0.2% to 50% of the minimum absorbed dose required to completely cure the first coating film, more preferably in the range of 0.5% to 40%, and even more preferably in the range of 1% to 30%.

[0110] The minimum absorbed dose required to completely cure the first coating film is, for example, in the range of 5 kGy to 200 kGy.

[0111] As described above, the first ionizing radiation curable resin further contains methacrylate in addition to acrylate, which slows down the rate of the crosslinking reaction caused by exposure to the first radiation and widens the process window in which the desired cured state can be achieved.

[0112] Next, a second coating film made of the coating liquid for the second gloss control layer is formed on the semi-cured first coating film. The second coating film is formed so as to partially cover the upper surface of the first coating film. Specifically, the second coating film is formed so as to face the pattern ink layer 4 with the first coating film sandwiched therebetween. The second coating film can be formed by various printing methods, such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing. Among these, gravure printing is preferred.

[0113] The coating liquid for the second gloss-adjusting layer contains the second ionizing radiation curable resin described above. As described above, the second ionizing radiation curable resin is, according to one example, an acrylate. In another example, the second ionizing radiation curable resin is a second mixture of an acrylate and a methacrylate, in which the ratio of the number of moles of methacryloyl groups to the total number of moles of acryloyl groups and the number of moles of methacryloyl groups is smaller than that of the first mixture.

[0114] The coating liquid for the second gloss adjustment layer may further contain other components, such as the above-mentioned particles, solvents, and additives for improving the functionality of the final product, such as one or more antibacterial agents and antifungal agents. The coating liquid for the second gloss adjustment layer may further contain other additives such as ultraviolet absorbers and light stabilizers. Examples of ultraviolet absorbers that can be used include benzotriazoles, benzoates, benzophenones, and triazines. Examples of light stabilizers that can be used include hindered amines.

[0115] Next, the first coating film and the second coating film are irradiated with ionizing radiation or ultraviolet light to completely cure the first coating film and the second coating film. For example, the second irradiation step and the third irradiation step described below are carried out sequentially.

[0116] In the second step, the second coating film is irradiated with second radiation, which is light having a wavelength of 200 nm or less.

[0117] The second ionizing radiation-curable resin contained in the coating liquid for the second gloss-controlling layer has a large absorption coefficient for the second radiation. Therefore, the second radiation incident on the second coating film can only reach a position several tens to several hundreds of nanometers from the outermost surface. Therefore, in the second irradiation step, the crosslinking reaction proceeds in the surface region of the second coating film, forming an extremely thin cured film, while the crosslinking reaction does not proceed in other regions, leaving the film uncured.

[0118] The second coating film after the second irradiation step has wrinkles on its surface that correspond to the ridge portions 6 B. The present inventors believe that the reason why wrinkles are formed on the coating film surface by the second irradiation step is as follows.

[0119] As described above, the second radiation can only reach a position tens to hundreds of nanometers from the outermost surface of the second coating film. In other words, the crosslinking reaction of the second ionizing radiation-curable resin occurs only on the surface of the second coating film, and regions more than tens to hundreds of nanometers from the outermost surface are uncured and contain highly fluid molecules. These highly fluid molecules swell the cured film, increasing its volume. The increase in volume in the in-plane direction generates in-plane compressive stress, which causes the cured film to buckle, resulting in wrinkles on the surface of the second coating film.

[0120] In the second irradiation step, the second radiation may also be applied to the surface of the first coating film in the portion not covered by the second coating film. However, since the first coating film is semi-cured, molecular flow within the film is unlikely to occur. Therefore, wrinkles do not form on the exposed surface of the first coating film.

[0121] Furthermore, the second radiation does not reach the portion of the first coating film that is covered with the second coating film, and therefore, no crosslinking reaction occurs in this portion due to irradiation with the second radiation.

[0122] The second radiation can be extracted from excimer VUV (Vacuum Ultra Violet) light. Excimer VUV light can be produced from lamps that use rare gases or rare gas halide compounds. When high-energy electrons are externally applied to a lamp filled with rare gases or rare gas halide compounds, a large number of discharge plasmas (dielectric barrier discharges) are generated. This plasma discharge excites the atoms of the discharge gas (rare gas), momentarily transforming them into an excimer state. When returning from this excimer state to the ground state, light is emitted in a wavelength range specific to that excimer.

[0123] The gas used in the excimer lamp may be any conventional gas that emits light of 200 nm or less. Examples of gases that can be used include rare gases such as Xe, Ar, and Kr, and mixtures of rare gases such as ArBr and ArF with halogen gases. Excimer lamps have different wavelengths (center wavelengths) depending on the gas used, such as approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), and approximately 193 nm (ArF).

[0124] Considering the magnitude of photon energy and the difference between wavelength and bond energy of organic matter, it is preferable to use a xenon lamp that emits excimer light with a central wavelength of 172 nm as the light source. Also, considering the cost of maintaining the equipment and the availability of materials, it is preferable to use a xenon lamp as the light source.

[0125] The second irradiation step is carried out in an atmosphere with a low oxygen concentration. Oxygen has a high absorption coefficient for light of 200 nm or less. Therefore, the second irradiation step is preferably carried out in, for example, a nitrogen gas atmosphere. The oxygen concentration in the gas phase during the second irradiation step, i.e., the residual oxygen concentration in the reaction atmosphere, is preferably 2000 ppm or less, and more preferably 1000 ppm or less.

[0126] Furthermore, oxygen in the atmosphere inhibits radical polymerization. Therefore, the residual oxygen concentration in the reaction atmosphere affects the formation of wrinkles on the surface of the second coating film. Therefore, changing the residual oxygen concentration in the reaction atmosphere can also change the surface properties of the second gloss-controlling layer 6.

[0127] The cumulative light intensity of the second radiation is 0.5 mJ / cm 2 More than 200mJ / cm 2 It is preferable to set the concentration within the range of 1 mJ / cm 2 More than 100mJ / cm 2 It is more preferable to keep it within the range of 3 mJ / cm 2 More than 50mJ / cm 2 It is more preferable to set it within the range of 5 mJ / cm 2 More than 30mJ / cm2 It is most preferable to set the integrated light dose within the following range: If the integrated light dose is small, the expansion of the cured film in the in-plane direction will be small, whereas if the integrated light dose is large, the surface condition of the second coating film will deteriorate.

[0128] In the third irradiation step, the second coating film is irradiated with third radiation. The third radiation is ionizing radiation or ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step. The third radiation can be any of the radiations described above for the first radiation.

[0129] In the third irradiation step, a crosslinking reaction occurs throughout the entire thickness of each of the first and second coating films. Because the first coating film is in a semi-cured state at the start of the third irradiation step, crosslinking reactions can occur between molecules contained in the first coating film and molecules contained in the second coating film at the contact points between the first and second coating films. Therefore, high adhesion can be achieved between the first gloss adjustment layer 5 and the second gloss adjustment layer 6.

[0130] The cumulative light intensity of the third radiation is 10 mJ / cm 2 More than 500mJ / cm 2 It is preferable to set the dose within the range of 50 mJ / cm 2 More than 400mJ / cm 2 It is more preferable to set it within the range of 100 mJ / cm 2 More than 300mJ / cm 2 It is more preferable to set it within the following range.

[0131] The third radiation is preferably applied so that the absorbed dose is within the range of 5 kGy or more and 200 kGy or less, more preferably within the range of 10 kGy or more and 150 kGy or less, and even more preferably within the range of 15 kGy or more and 100 kGy or less.

[0132] In the third irradiation step, if irradiation with a single type of radiation alone does not provide a layer with sufficient strength, the type of third radiation may be changed. For example, irradiation with ionizing radiation may be performed first, followed by irradiation with ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step. Alternatively, irradiation with ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step may be performed first, followed by irradiation with ionizing radiation. Alternatively, irradiation with ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step may be performed first, followed by irradiation with ultraviolet light having an even longer wavelength.

[0133] In this manner, a decorative sheet 1 is obtained. In the decorative sheet 1 obtained by the above method, there is no interface between the core portion 6A and the rib portion 6B, and they are integrally formed.

[0134] <3> effect The decorative sheet 1 includes a first gloss adjustment layer 5 and a second gloss adjustment layer 6 that partially covers the first gloss adjustment layer 5. The first gloss adjustment layer 5 and the second gloss adjustment layer 6 have different specular glosses GS(60°). Here, the second gloss adjustment layer 6 has a lower specular gloss GS(60°) than the first gloss adjustment layer 5. In particular, when the second gloss adjustment layer 6 has the surface texture described above, the difference between the specular gloss GS(60°) of the first gloss adjustment layer 5 and the specular gloss GS(60°) of the second gloss adjustment layer 6 can be made larger. These differences in gloss can contribute to the expression of a three-dimensional effect similar to unevenness.

[0135] Furthermore, in the decorative sheet 1, the second gloss control layer 6 is identical in shape and position to the pattern ink layer 4. Therefore, the decorative sheet 1 can express a three-dimensional effect with raised portions in the areas corresponding to the pattern ink layer 4 and recessed portions in the other areas. Therefore, by appropriately selecting the color of the solid ink layer 3 and the color of the pattern ink layer 4, this decorative sheet 1 can express a luxurious design that resembles, for example, natural wood or natural stone.

[0136] Furthermore, in the decorative sheet 1, the first gloss adjustment layer 5 contains only the cured product of a first ionizing radiation curable resin as the resin cured product, and the first ionizing radiation curable resin is a first mixture of acrylate and methacrylate. The acrylate contributes to improving scratch resistance, and the methacrylate contributes to improving adhesion between the first gloss adjustment layer 5 and the second gloss adjustment layer 6. Therefore, the decorative sheet 1 has excellent scratch resistance and adhesion between the gloss adjustment layers.

[0137] Furthermore, the uneven structure including the ridge portions 6B formed on the upper surface of the second gloss adjustment layer 6 by the above-mentioned method is finer than an uneven structure formed by mechanical processing such as embossing. Because the decorative sheet 1 has such a fine uneven structure on the upper surface of the second gloss adjustment layer 6, it has a matte finish and excellent fingerprint resistance.

[0138] <4> Variations The decorative sheet 1 can be modified in various ways.

[0139] For example, the second gloss adjustment layer 6 may be the same in shape and position as the portion of the solid ink layer 3 that is not covered by the pattern ink layer 4. The decorative sheet 1 deformed in this way can express a three-dimensional effect with the portions corresponding to the pattern ink layer 4 as recesses and the other portions as protrusions, creating a relief-like three-dimensional effect.

[0140] In the decorative sheet 1, the protrusions provided on the upper surface of the second gloss adjustment layer 6 are ridge-shaped. These protrusions do not have to be ridge-shaped. For example, each of these protrusions may be part of a particle.

[0141] In the decorative sheet 1 described above, the area of ​​the upper surface of the first gloss adjustment layer 5 that is not covered by the second gloss adjustment layer 6 is flat. As long as the gloss level relationship described above is maintained, a concave-convex structure may be provided in this area. This concave-convex structure may be a structure similar to that described above for the ridge portion 6B, or may be a structure in which multiple convex portions, each consisting of a portion of a particle, are arranged. [Example]

[0142] Examples of the present invention are described below. The "particle size" described below is the above-mentioned "average particle size (D50)."

[0143] <Example 1> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced by the following method. 2 An impregnated paper (GFR-506, manufactured by Kohjin Co., Ltd.) was prepared as the raw fabric layer 2. On one side of the raw fabric layer 2, a solid ink layer 3 and a pattern ink layer 4 were formed in this order using oil-based nitrocellulose resin gravure printing inks (PCNT (PCRNT) various colors, manufactured by Toyo Ink Co., Ltd.). The pattern of the pattern ink layer 4 was a wood grain pattern.

[0144] Next, a coating liquid for a first gloss adjustment layer having the following composition was applied onto the solid ink layer 3 and the pattern ink layer 4. The coating liquid for a first gloss adjustment layer was applied so that the thickness of the first gloss adjustment layer 5 would be 5 μm.

[0145] (Coating liquid for first gloss adjustment layer) Ionizing radiation curable resin R1 Type: Trimethylolpropane EO-modified triacrylate (EO 3 moles added) Product name: Miramer M3130 (Miwon) Blend: 50 parts by mass ·Ionizing radiation curable resin R2 Type: Methoxypolyethylene glycol (400) methacrylate Product name: NK Ester M-90G (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 50 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 15 parts by mass

[0146] Thereafter, the first irradiation step was carried out. Specifically, the first coating film made of the first gloss control layer coating liquid was irradiated with an electron beam as ionizing radiation so that the absorbed dose of the first coating film was 10 kGy. This resulted in the first coating film being semi-cured.

[0147] Next, a coating liquid for a second gloss adjustment layer having the following composition was printed on the portion of the first coating film corresponding to the pattern ink layer 4. The coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 would be 5 μm.

[0148] (Coating liquid for second gloss adjustment layer) ·Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (EO 6 moles added) Product name: Miramer M3160 (Miwon) Blend: 100 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 0.5 parts by mass

[0149] Next, the second irradiation step was carried out. Specifically, under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm, ultraviolet light having a wavelength of 172 nm was irradiated onto the surfaces of the first coating film and the second coating film made of the coating liquid for the second gloss control layer using a Xe excimer lamp at an integrated light intensity of 50 mJ / cm. 2 This caused wrinkles to form on the surface of the second coating film.

[0150] Subsequently, the third irradiation step was carried out. Specifically, the first and second coating films were irradiated with 100 kGy of ionizing radiation to completely cure them as a whole, thereby forming a first gloss adjustment layer 5 and a second gloss adjustment layer 6. In this manner, a decorative sheet 1 was obtained.

[0151] <Example 2> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that in the coating liquid for the first gloss adjustment layer, the blending amount of ionizing radiation curable resin R1 was 80 parts by mass and the blending amount of ionizing radiation curable resin R2 was 20 parts by mass.

[0152] <Example 3> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that in the coating liquid for the first gloss adjustment layer, the blending amount of ionizing radiation curable resin R1 was 90 parts by mass and the blending amount of ionizing radiation curable resin R2 was 10 parts by mass.

[0153] <Example 4> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as ionizing radiation curable resin R2, and the blending amount of ionizing radiation curable resin R1 in the coating liquid for the first gloss adjustment layer was 90 parts by mass and the blending amount of ionizing radiation curable resin R2 was 10 parts by mass. ·Ionizing radiation curable resin R2 Type: Isobornyl methacrylate Product name: Light Ester IB-X (Kyoeisha Chemical Co., Ltd.)

[0154] <Example 5> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2. ·Ionizing radiation curable resin R2 Type: EO-modified bisphenol A dimethacrylate (EO 10 moles added) Product name: NK Ester BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0155] <Example 6> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as ionizing radiation curable resin R2, and the blending amount of ionizing radiation curable resin R1 in the coating liquid for the first gloss adjustment layer was 80 parts by mass and the blending amount of ionizing radiation curable resin R2 was 20 parts by mass. ·Ionizing radiation curable resin R2 Type: EO-modified bisphenol A dimethacrylate (EO 10 moles added) Product name: NK Ester BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0156] <Example 7> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as ionizing radiation curable resin R2, and the blending amount of ionizing radiation curable resin R1 in the coating liquid for the first gloss adjustment layer was 90 parts by mass and the blending amount of ionizing radiation curable resin R2 was 10 parts by mass. ·Ionizing radiation curable resin R2 Type: EO-modified bisphenol A dimethacrylate (EO 10 moles added) Product name: NK Ester BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0157] <Example 8> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as ionizing radiation curable resin R2, and the blending amount of ionizing radiation curable resin R1 in the coating liquid for the first gloss adjustment layer was 80 parts by mass and the blending amount of ionizing radiation curable resin R2 was 20 parts by mass. ·Ionizing radiation curable resin R2 Type: Polyethylene glycol (200) dimethacrylate Product name: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0158] <Example 9> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2. ·Ionizing radiation curable resin R2 Type: Trimethylolpropane EO-modified trimethacrylate (EO 3 moles added) Product name: NK Ester TMPT-3EO (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0159] <Example 10> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2. ·Ionizing radiation curable resin R2 Type: Trimethylolpropane PO modified trimethacrylate (PO 3 moles added) Product name: NK Ester TMPT-3PO (Shin-Nakamura Chemical Co., Ltd.)

[0160] <Example 11> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the amount of particles in the coating liquid for the second gloss adjustment layer was set to 20 parts by mass.

[0161] <Example 12> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except for the following points.

[0162] That is, in this example, the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjusting layer.

[0163] ·Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (EO 3 moles added) Product name: Miramer M3130 (Miwon) The second irradiation step was carried out by irradiating the surfaces of the first coating film and the second coating film made of the coating liquid for the second gloss control layer with ultraviolet light having a wavelength of 172 nm at an integrated light intensity of 100 mJ / cm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm. 2 The irradiation was carried out so that

[0164] <Example 13> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjustment layer. ·Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (EO 15 moles added) Product name: SR9035 (Sartomer)

[0165] <Example 14> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjustment layer. ·Ionizing radiation curable resin Type: Ethylene glycol diacrylate (EO 9 moles added) Product name: Light Acrylate 9EG-A (Kyoeisha Chemical Co., Ltd.)

[0166] <Example 15> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except for the following points.

[0167] That is, in this example, the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjusting layer. ·Ionizing radiation curable resin Type: Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added) Product name: NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) The second irradiation step was carried out by irradiating the surfaces of the first coating film and the second coating film made of the coating liquid for the second gloss control layer with ultraviolet light having a wavelength of 172 nm at an integrated light intensity of 50 mJ / cm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm. 2 The irradiation was carried out so that

[0168] <Example 16> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except for the following points.

[0169] That is, in this example, the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjusting layer. ·Ionizing radiation curable resin Type: Ethoxylated dipentaerythritol hexaacrylate (12 moles of EO added) Product name: NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) The second irradiation step was carried out by irradiating the surfaces of the first coating film and the second coating film made of the coating liquid for the second gloss control layer with ultraviolet light having a wavelength of 172 nm at an integrated light intensity of 150 mJ / cm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. 2 The irradiation was carried out so that

[0170] <Example 17> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 2 μm.

[0171] <Example 18> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 20 μm.

[0172] <Example 19> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except for the following points. That is, in this example, particles were omitted from the coating liquid for the second gloss adjustment layer. The coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 3 μm.

[0173] <Example 20> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the blending amount of particles in the coating liquid for the second gloss adjustment layer was 10 parts by mass.

[0174] <Example 21> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles in the coating liquid for the first gloss adjustment layer was set to 10 parts by mass. Also, in this example, the following coating liquid for the second gloss adjustment layer was used.

[0175] (Coating liquid for second gloss adjustment layer) ·Ionizing radiation curable resin 1 Type: Trimethylolpropane EO-modified triacrylate (EO 6 moles added) Product name: Miramer M3160 (Miwon) Blend: 60 parts by mass ·Ionizing radiation curable resin 2 Type: Dipentaerythritol hexaacrylate Product name: Miramer M600 (Miwon) Blend: 40 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 0.5 parts by mass

[0176] <Example 22> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles in the coating liquid for the first gloss adjustment layer was 5 parts by mass. In addition, in this example, the following coating liquid for the second gloss adjustment layer was used.

[0177] (Coating liquid for second gloss adjustment layer) ·Ionizing radiation curable resin 1 Type: Trimethylolpropane EO-modified triacrylate (EO 6 moles added) Product name: Miramer M3160 (Miwon) Blend: 40 parts by mass ·Ionizing radiation curable resin 2 Type: Dipentaerythritol hexaacrylate Product name: Miramer M600 (Miwon) Blend: 60 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 0.5 parts by mass

[0178] <Example 23> The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the particle blending ratio in the coating liquid for the first gloss adjustment layer was 10 parts by mass. In addition, in this example, the following coating liquid for the second gloss adjustment layer was used. The coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 14 μm.

[0179] (Coating liquid for second gloss adjustment layer) ·Ionizing radiation curable resin 1 Type: Trimethylolpropane EO-modified triacrylate (EO 6 moles added) Product name: Miramer M3160 (Miwon) Blend: 40 parts by mass ·Ionizing radiation curable resin 2 Type: Dipentaerythritol hexaacrylate Product name: Miramer M600 (Miwon) Blend: 60 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 0.5 parts by mass

[0180] <Comparative Example 1> A decorative sheet similar to that described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the ionizing radiation curable resin R2 was omitted from the coating liquid for the first gloss adjustment layer.

[0181] <Comparative Example 2> A decorative sheet similar to that described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the ionizing radiation curable resin R1 was omitted from the coating liquid for the first gloss adjustment layer.

[0182] <Evaluation> Each of the decorative sheets was evaluated as follows: Those rated "AAA," "AA," or "A" were deemed to pass the evaluation because they presented no problems in actual use.

[0183] (1) Thickness of the gloss adjustment layer The thickness of the second gloss-adjusting layer was measured in the same manner as described above. Specifically, the decorative sheet was embedded in a resin such as a cold-setting epoxy resin or a UV-curable resin, and the resin was allowed to harden sufficiently. Then, the sheet was cut so that the cross section of the decorative sheet was exposed, and the measurement surface was obtained by mechanical polishing.

[0184] Next, a cross section of the second gloss adjustment layer was imaged using a scanning electron microscope SIGMA 500 manufactured by Carl Zeiss Microscopy. During this imaging, the acceleration voltage was 0.5 keV (low acceleration voltage), the imaging mode was SE2 mode, and the magnification was 2000 times. Note that no sputtering was performed on the measurement sample.

[0185] Next, the dimensions of the second gloss adjustment layer in the width direction of the ridge portion and the area of ​​the cross section of the second gloss adjustment layer were determined from this cross-sectional image. The thickness of the second gloss adjustment layer was calculated by dividing this area by the above dimensions. The thickness obtained in this way was equal to the thickness of the coating film made of the coating liquid for the second gloss adjustment layer. The thickness of the first gloss control layer was measured in the same manner as above.

[0186] (2) Glossiness The gloss was measured as specular gloss GS(60°) using a micro-gloss60°xs (manufactured by BYK). The "60° gloss value" in Tables 1 to 5 below represents this specular gloss GS(60°).

[0187] (3) Adhesion The adhesion of the second gloss adjustment layer to the first gloss adjustment layer was evaluated by a cross-cut test specified in JIS K5400 (discontinued). Here, cuts were made in a grid pattern on the surface of the decorative sheet, with a depth that exceeded the interface between the first gloss adjustment layer and the second gloss adjustment layer, spaced 1 mm apart. This created 100 squares arranged in a grid pattern. Next, adhesive tape was applied to the surface of the decorative sheet, and the adhesive tape was then peeled off from the decorative sheet. The number of squares remaining on the decorative sheet was counted, and the adhesion was evaluated by referring to the following criteria:

[0188] AAA: There are 100 remaining squares. AA: The number of remaining squares was between 95 and 99. A: The number of remaining squares was between 90 and 94. B: The number of remaining squares was 89 or less.

[0189] (4) Scratch resistance Each decorative sheet was attached to wood substrate B using a urethane adhesive. A steel wool rubbing test was then conducted to evaluate scratch resistance. Specifically, the decorative sheet was rubbed back and forth 20 times with steel wool while applying a load of 100 g, and the surface of the decorative sheet was visually inspected for scratches and changes in gloss.

[0190] The evaluation criteria were as follows: AAA: No scratches or changes in gloss occurred on the surface. AA: Minor scratches or changes in gloss occurred on some parts of the surface. A: Minor scratches or changes in gloss have occurred on the surface. B: Significant scratches or changes in gloss occurred on the surface.

[0191] (5) Stain resistance To evaluate stain resistance, the Staining A Test specified in the Japanese Agricultural Standards (JAS) was conducted. Specifically, 10 mm wide lines were drawn on the surface protective layer of each decorative sheet using blue ink, black quick-drying ink, and red crayon, and the sheets were left for 4 hours. The blue ink, black quick-drying ink, and red crayon lines were then wiped off with a cloth soaked in ethanol.

[0192] The evaluation criteria were as follows: AAA: Lines of each color could be easily wiped off. AA: Part of the lines of each color could be wiped away, but some stains remained. A: Part of the lines of each color could be wiped away, but some stains remained. B: I couldn't wipe off the lines of each color.

[0193] The evaluation results are shown in Tables 1 to 5. In Tables 1 to 5, "proportion of moles of methacryloyl groups" represents the proportion of moles of methacryloyl groups to the total number of moles of acryloyl groups and methacryloyl groups.

[0194] [Table 1]

[0195] [Table 2]

[0196] [Table 3]

[0197] [Table 4]

[0198] [Table 5]

[0199] As shown in Tables 1 to 5, the decorative sheets according to Examples 1 to 23 exhibited sufficient performance in all of adhesion, scratch resistance, and stain resistance. In contrast, the sheet according to Comparative Example 1 exhibited insufficient performance in all of adhesion, scratch resistance, and stain resistance. Furthermore, the sheet according to Comparative Example 2 exhibited sufficient performance in adhesion, but insufficient performance in scratch resistance and stain resistance. [Explanation of symbols]

[0200] 1...decorative sheet, 2...raw material layer, 3...solid ink layer, 4...pattern ink layer, 5...first gloss adjustment layer, 6...second gloss adjustment layer, 6A...core portion, 6B...ridge portion, 11...decorative material, B...base material, C...position, D...position.

Claims

1. A base layer and a surface protective layer are provided, The surface protective layer is a first gloss adjustment layer provided on the base layer, the first gloss adjustment layer including only a cured product of a first ionizing radiation curable resin as a resin cured product, the first ionizing radiation curable resin being a first mixture of an acrylate and a methacrylate; a second gloss adjustment layer that partially covers an upper surface of the first gloss adjustment layer, that contains only a cured product of a second ionizing radiation curable resin as a resin cured product, that has a lower specular gloss GS (60°) than the first gloss adjustment layer, and that the second ionizing radiation curable resin contains an acrylate; Including, A decorative sheet in which the area of ​​the upper surface of the first gloss adjustment layer that is not covered by the second gloss adjustment layer is flat.

2. 2. The decorative sheet according to claim 1, wherein in said first ionizing radiation curable resin, the ratio of the number of moles of methacryloyl groups to the total number of moles of acryloyl groups and methacryloyl groups is in the range of 3% to 50%.

3. 2. The decorative sheet according to claim 1, wherein the methacrylate is a monofunctional, difunctional, or trifunctional methacrylate.

4. 2. The decorative sheet according to claim 1, wherein the second ionizing radiation curable resin is an acrylate or a second mixture of an acrylate and a methacrylate, and the second mixture has a smaller ratio of the number of moles of methacryloyl groups to the total number of moles of acryloyl groups and the number of moles of methacryloyl groups than the first mixture.

5. 2. The decorative sheet according to claim 1, wherein the second ionizing radiation curable resin contains a di- or higher functional acrylate containing a repeating unit.

6. 6. The decorative sheet according to claim 5, wherein the number of repetitions of said repeating structure is 3 or more.

7. 2. The decorative sheet according to claim 1, wherein the second gloss control layer has a surface provided with an uneven structure including a plurality of ridge-like portions, each of which protrudes in a ridge-like shape.

8. 8. The decorative sheet according to claim 7, wherein the ratio RSm / Ra of the average length RSm of the roughness curve elements to the arithmetic mean roughness Ra of the concave-convex structure is in the range of 10 or more and 900 or less.

9. 2. The decorative sheet according to claim 1, wherein the thickness of each of the first gloss adjustment layer and the second gloss adjustment layer is in the range of 2 [mu]m to 20 [mu]m.

10. The decorative sheet according to claim 1 , wherein the second gloss control layer further contains particles having an average particle size of 10 μm or less.

11. The decorative sheet according to claim 10, wherein the mass of the particles is in the range of 0.5 parts by mass to 20 parts by mass, where the mass of the second ionizing radiation curable resin is taken as 100 parts by mass.

12. 2. The decorative sheet according to claim 1, wherein the first gloss adjustment layer has a specular gloss GS(60°) of 3 or more, and the second gloss adjustment layer has a specular gloss GS(60°) of 20 or less.

13. 2. The decorative sheet according to claim 1, wherein the difference between the specular gloss GS(60°) of said first gloss adjustment layer and the specular gloss GS(60°) of said second gloss adjustment layer is 1 or more.

14. The decorative sheet according to any one of claims 1 to 13; a substrate to which the decorative sheet is attached; A cosmetic material comprising:

15. forming a first coating film on the base layer, the first coating film containing only a first ionizing radiation curable resin as a resin, the first ionizing radiation curable resin being a first mixture of acrylate and methacrylate; carrying out a first irradiation step of irradiating the first coating film with ionizing radiation or ultraviolet light to semi-cure the first coating film; forming a second coating film containing only a second ionizing radiation curable resin as a resin, the second ionizing radiation curable resin including an acrylate, on the semi-cured first coating film so as to partially cover an upper surface of the first coating film; Irradiating the first coating film and the second coating film with ionizing radiation or ultraviolet light to completely cure the first coating film and the second coating film, thereby obtaining a first gloss adjustment layer and a second gloss adjustment layer, respectively. Including, A method for manufacturing a decorative sheet, which provides the first gloss adjustment layer such that the area of ​​the upper surface thereof that is not covered by the second gloss adjustment layer is flat.

16. The complete curing of the first coating film and the second coating film is a second irradiation step of irradiating the second coating film with light having a wavelength of 200 nm or less; Thereafter, a third irradiation step is performed in which the first coating film and the second coating film are irradiated with ionizing radiation or ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step. The method for producing a decorative sheet according to claim 15, comprising:

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