Decorative sheet and method for manufacturing decorative sheet

Abstract

Provided is a decorative sheet having low gloss, i.e., excellent design properties, and having high durability, particularly, scratch resistance and stain resistance, and processability. The decorative sheet (1) according to the present embodiment includes a base material layer (2), and a surface protective layer (5) provided on one surface of the base material layer (2), the surface protective layer (5) having a ridge portion provided in a ridge shape on a surface thereof, and having a concave-convex shape, the concave-convex shape of the surface protective layer (5) having an RSm / Ra in a range of 10 or more and 300 or less, and a main material of the surface protective layer (5) being an ionizing radiation-curable resin, a main component of the ionizing radiation-curable resin being a 4-functional acrylic resin including a repeating structure, the repeating structure being any one of an oxirane structure, an oxetane structure, and an ε-caprolactone structure, and a repeating number of the repeating structure being 12 or more.

Description

Technical Field

[0001] This invention relates to decorative sheets for surface decoration of interior and exterior buildings, doors and windows, furniture, wood finishing materials, flooring materials, etc., and a method for manufacturing such decorative sheets. Background Technology

[0002] To give the surface of the aforementioned buildings design and durability, decorative panels are commonly used, which are made by attaching decorative sheets to the surface of wood, wood panels, metal panels, non-combustible boards, paper substrates, or resin substrates using adhesives or the like.

[0003] Regarding the application of design elements, the choice ranges from using various printing methods to create patterns such as wood grain or stone texture to a plain, unadorned surface, depending on the requirements and intended use. Similarly, the surface gloss is also an important design consideration, ranging from a high-gloss, mirror-like finish to a low-gloss finish with no reflection, again depending on the requirements and intended use.

[0004] In addition, as mentioned above, another function of decorative panels that is as important as design is the provision of durability. Durability is a comprehensive evaluation of resistance to damage, resistance to staining, and their ability to persist and remain intact over a long period of time. Requirements vary depending on the environment and circumstances in which the decorative panels are used, but generally, high-performance decorative panels are required.

[0005] To enhance durability, a protective coating is typically formed on the outermost surface of the decorative piece. Additionally, to adjust the gloss level, particularly to achieve a low gloss, a gloss modifier (matte additive) is usually added to the protective coating.

[0006] Furthermore, in order to form decorative panels or decorative materials, decorative sheets are usually subjected to processes such as cutting and bending, so it is preferable to have processability that can withstand these processes.

[0007] Thus, as a decorative sheet that takes into account design (low gloss), damage resistance, and stain resistance, such as the decorative sheet described in Patent Document 1.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2019-119138 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] In recent years, due to the expanding applications of decorative panels using decorative sheets and consumers' increasing awareness of quality, there is a growing demand for low-gloss finishes that also offer fingerprint resistance, damage resistance, stain resistance, and flexibility. Damage resistance is particularly important when used as tabletops and similar surfaces.

[0013] Regarding the above requirements, for low gloss, there is a method of adding gloss modifiers at high concentrations to roughen the surface. However, adding large amounts will lead to the following adverse conditions: (1) Fingerprint stains are difficult to remove, and fingerprint resistance is reduced. (2) Gloss modifiers fall off during damage resistance tests, and damage resistance is reduced. (3) Stains are difficult to remove, and stain resistance is reduced. (4) During bending processing, whitening occurs due to the gloss modifier, and bending processability is reduced. In addition, regarding the improvement of damage resistance, by increasing the crosslinking density of the resin used in the surface protective layer, (5) the sheet curls significantly due to curing shrinkage, making it difficult to laminate onto the substrate.

[0014] To address the aforementioned issues, the present invention aims to provide decorative sheets that possess low gloss (i.e., excellent designability), fingerprint resistance, high durability (particularly resistance to damage and staining), and processability (lamination onto a substrate, bending processability).

[0015] Solution for solving the problem

[0016] To achieve low gloss, the inventors optimized the uneven shape of the surface protective layer and conducted repeated experiments to identify the structural elements necessary for the material used in the surface protective layer. This led to the discovery of a decorative sheet that can provide low gloss and exhibits fingerprint resistance, high durability (especially resistance to damage and staining), and processability (lamination onto a substrate and bending processability).

[0017] To address the problem, one aspect of the present invention relates to a decorative sheet comprising a base material layer and a surface protective layer disposed on one surface of the base material layer. The surface protective layer has ridges protruding in a ridge-like manner and has an uneven shape. The RSm / Ra of the uneven shape of the surface protective layer is in the range of 10 to 300. The main material of the surface protective layer is an ionizing radiation-curable resin. The main component of the ionizing radiation-curable resin is a tetrafunctional acrylic resin containing a repeating structure. The repeating structure is any one of ethylene oxide, propylene oxide, and ε-caprolactone. The repeating number of times the repeating structure is repeated is 12 or more.

[0018] The effects of the invention

[0019] According to one aspect of the present invention, a decorative sheet with low gloss and fingerprint resistance, damage resistance, stain resistance, and bendability can be provided. Attached Figure Description

[0020] [ Figure 1 This is a schematic cross-sectional view illustrating the structure of the decorative piece according to an embodiment of the present invention.

[0021] [ Figure 2 This is a schematic cross-sectional view illustrating one configuration of the surface protective layer of the decorative sheet according to an embodiment of the present invention.

[0022] [ Figure 3 This is a plan view photograph illustrating an example of the surface configuration of the surface protective layer of a decorative sheet according to an embodiment of the present invention.

[0023] [ Figure 4 This is a schematic cross-sectional view illustrating one configuration of a decorative sheet according to an embodiment of the present invention.

[0024] [ Figure 5 This is a schematic cross-sectional view illustrating the cross-sectional shape of the ridge portion according to an embodiment of the present invention.

[0025] [ Figure 6 This is a schematic diagram illustrating the time variation of the amount of irradiation light in each irradiation light during the manufacturing process of the decorative sheet according to an embodiment of the present invention.

[0026] [ Figure 7 [A schematic cross-sectional view illustrating the method for determining the curlability test.] Detailed Implementation

[0027] Hereinafter, with reference to the accompanying drawings, the structure of the decorative sheet according to the embodiments of the present invention will be described.

[0028] The accompanying drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of thickness of each layer, etc., differ from the actual situation. Furthermore, the embodiments shown below illustrate configurations for embodying the technical concept of the present invention. The technical concept of the present invention can be modified in various ways within the scope of the claims.

[0029] (constitute)

[0030] like Figure 1 As shown, the decorative sheet 1 of this embodiment is constructed by sequentially layering a patterned layer 3, an adhesive layer 7 (heat-sensitive adhesive layer, anchoring coating, dry lamination adhesive layer), a transparent resin layer 4, and a surface protective layer 5 on one side (surface side) of the base material layer (substrate layer) 2. Additionally, a concealing layer 8 and a primer layer 6 are provided on the other side (back side) of the base material layer 2. Alternatively, the patterned layer 3, adhesive layer 7, transparent resin layer 4, concealing layer 8, and primer layer 6 may be omitted.

[0031] Then, as Figure 1 As shown, decorative material 11 is formed by attaching the decorative sheet 1 of this embodiment to substrate B. There is no particular limitation on substrate B, and it can be made of wood, inorganic board, metal plate, composite board made of multiple materials, etc.

[0032] <Material Layer 2>

[0033] For example, materials selected from paper, synthetic resin, or foamed synthetic resin, rubber, nonwoven fabric, synthetic paper, metal foil, etc., can be used as the raw material layer 2. Examples of paper include thin paper, titanium paper, and resin-impregnated paper. Examples of synthetic resins include polyethylene, polypropylene, polybutene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic resins. Examples of rubbers include ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane. For nonwoven fabric, organic or inorganic nonwoven fabrics can be used. Examples of metals used as metal foil include aluminum, iron, gold, and silver.

[0034] When using an olefin-based resin as the base material layer 2, the surface of the base material layer 2 is mostly inert. Therefore, it is preferable to provide a primer layer 6 between the base material layer 2 and the substrate B. In addition, in order to improve the adhesion between the base material layer 2, which is made of an olefin-based material, and the substrate B, the base material layer 2 can be subjected to surface modification treatments such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, and dichromate treatment.

[0035] As the primer layer 6, the same material as the pattern layer 3 described later can be used. Since the primer layer 6 is applied to the back of the decorative sheet 1, and considering that the decorative sheet 1 is rolled into a mesh, an inorganic filler can be added to the primer layer 6 to prevent adhesion and improve adhesion to the adhesive. Examples of inorganic fillers include: silica, aluminum oxide, magnesium oxide, titanium oxide, barium sulfate, etc.

[0036] Considering printability and cost, the thickness of the raw material layer 2 is preferably in the range of 20μm to 250μm.

[0037] <Pattern Layer 3>

[0038] The pattern layer 3 is a patterned printing layer applied to the base material layer 2 using ink. As a binder for the ink, it can be appropriately selected and used from individual or modified forms such as nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylics, and polyesters. The binder can be water-based, solvent-based, or emulsion-type, and can be a one-component or a two-component form using a curing agent. Alternatively, it can be cured using a curable ink by irradiation with ultraviolet light or an electron beam. The most common method is to use a urethane-based ink and cure it with isocyanate. In addition to the binder, colorants such as pigments and dyes, extender pigments, solvents, and various additives found in ordinary inks can be added to the pattern layer 3. Examples of highly versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolide, cobalt, phthalocyanine, carbon, titanium dioxide, iron oxide, and pearlescent pigments such as mica.

[0039] Alternatively, the pattern layer 3 can be designed by vapor deposition or sputtering of various metals different from those used for ink coating. In particular, it is preferable to add a light stabilizer to the ink, thereby suppressing the deterioration of the decorative sheet 1 itself caused by the light degradation of the ink, and thus extending the lifespan of the decorative sheet 1.

[0040] <Adhesive Layer 7>

[0041] Adhesive layer 7 is also known as heat-sensitive adhesive layer, anchoring coating, or dry laminated adhesive layer.

[0042] There are no particular limitations on the resin material for adhesive layer 7; for example, it can be appropriately selected and used from acrylic, polyester, polyurethane, epoxy, and other resin materials. Alternatively, ethylene-vinyl acetate copolymer adhesives can also be used as the resin material for adhesive layer 7. The coating method can be appropriately selected based on the viscosity of the adhesive, but gravure coating is typically used. The adhesive is applied to the patterned layer 3 using a gravure coating tool and then laminated with the transparent resin layer 4. It should be noted that adhesive layer 7 can be omitted if sufficient adhesive strength between the transparent resin layer 4 and the patterned layer 3 can be obtained.

[0043] <Transparent resin layer 4>

[0044] As the resin material for the transparent resin layer 4, an olefin-based resin is preferably used. Examples of olefin-based resins, besides polypropylene, polyethylene, and polybutene, include α-olefins (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecadecene, 1-hexadecene, 1-heptadecene, 1-heptadecene, 1-octadecene, 1-nonadecadecene, 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- Materials obtained by homopolymerization or copolymerization of 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.; or materials obtained by copolymerization of ethylene or α-olefins with monomers other than these, such as: ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, etc.

[0045] Furthermore, to improve the surface strength of the decorative sheet 1, highly crystalline polypropylene is preferably used as the resin for the transparent resin layer 4. It should be noted that, as needed, various additives such as heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers can be added to the transparent resin layer 4. Typically, phenolic, sulfur-based, phosphorus-based, and hydrazine-based agents are added in arbitrary combinations as heat stabilizers, and hindered amine-based agents are added as light stabilizers.

[0046] <Surface Protective Layer 5>

[0047] The surface protective layer 5 has a core portion 5A and a ridge portion 5B that protrudes in a ridge shape from one side of the core portion 5A. As a result, an uneven shape is formed on the surface of the surface protective layer 5.

[0048] Here, in the decorative piece 1 according to this embodiment, "ridge-like" refers to a shape that is elongated and raised, connected in a linear fashion in a plan view. The ridge portion 5B can be curved or straight in a plan view, but from the viewpoint of fingerprint resistance of the decorative piece 1 surface, a curved shape is preferred. In addition, in this disclosure, the ridge portion 5B is, for example, the portion from the lowest point to the top point of the uneven shape provided on the surface of the surface protective layer 5, and the core portion 5A refers to the portion of the surface protective layer 5 other than the ridge portion 5B.

[0049] Figure 2To schematically show the cross-section of the ridge 5B of the surface protective layer 5 (the cross-section of the surface protective layer 5 in the thickness direction), Figure 3 This is a planar photograph showing the surface composition of the surface protective layer 5. Here, Figure 3 This is a planar photograph obtained using a laser microscope (Olympus OLS-4000).

[0050] like Figure 3 As shown in the plan view, the ridge 5B is an elongated, raised shape that connects into a linear form in the plan view. As described later, the ridge 5B is formed by irradiating the surface of the ionizing radiation-curable resin with light of a specific wavelength, causing the surface of the ionizing radiation-curable resin to shrink.

[0051] The shape of this ridge 5B can be determined by the transverse direction (the plane direction of the surface protective layer 5, in...) Figure 2 The surface roughness index RSm (μm) in the left-right direction and the longitudinal direction (depth direction of ridge 5B, thickness direction of surface protective layer 5) are in the middle. Figure 2 The surface roughness index Ra (μm) is expressed as RSm / Ra, with RSm / Ra preferably being 10 or more and 300 or less. More preferably, it is 10 or more and 250 or less. When RSm / Ra is less than 10, the shape of the ridges 5B is too fine, making it difficult to wipe away stains and reducing stain resistance. When RSm / Ra is greater than 300, the spacing between the ridges is too wide, thus failing to create a low-gloss finish.

[0052] Furthermore, RSm / Ra is preferably 50 to 200. If RSm / Ra is within this range, the spacing between the ridges is moderately wide, thus increasing the affinity for water or cleaning agents (water containing surfactants or alcohols). Therefore, if the decorative sheet has RSm / Ra within this range, stains can be easily wiped away with water or cleaning agents even if the surface of the decorative sheet is dirty.

[0053] In addition, RSm / Ra is preferably between 80 and 150. If RSm / Ra is within this range, ordinary commercially available cleaning sponges can easily penetrate between the ridges, and even if the surface of the decorative panel is dirty, it is easy to wipe away the stains using ordinary commercially available cleaning sponges.

[0054] Here, Ra and RSm are measured values ​​when measured using a line roughness meter (based on JIS B0601).

[0055] The cross-sectional shape of the ridge 5B in the thickness direction of the surface protective layer 5 can be a sine wave shape.

[0056] Here, "sine wave shape" refers to: such as Figure 5As shown, the shape of the line from the lowest position C of the ridge 5B to the highest position (apex) D can be represented by a sine wave.

[0057] Furthermore, the shape between adjacent ridges 5B (between valleys) can be a concave, curved shape. That is, the shape of the lowest position C of the ridge 5B can be a concave, curved shape.

[0058] The mechanism of ridge 5B formation will be explained below.

[0059] When acrylate is irradiated with light of wavelength below 200 nm as the first irradiation light, the acrylate can self-excite. Therefore, by irradiating acrylate with light below 200 nm, cross-linking of the acrylate can be achieved. Light below 200 nm can reach a depth of tens to hundreds of nm in acrylate. Therefore, only the surface is cross-linked, while the underlying portion remains fluid, resulting in a fine, wavy, textured shape resembling folds and wrinkles.

[0060] Light below 200 nm is significantly attenuated by atmospheric oxygen absorption. Therefore, nitrogen gas needs to be introduced to control the reaction atmosphere when processing acrylates. Preferably, the residual oxygen concentration in the reaction atmosphere is suppressed to below 2000 ppm. More preferably, the residual oxygen concentration in the reaction atmosphere is below 1000 ppm.

[0061] In order to generate a concave-convex shape using the first irradiation light, i.e., light with a wavelength of less than 200 nm, it is preferable to set the cumulative light intensity of the first irradiation light to 0.5 mJ / cm. 2 Above 200mJ / cm 2 The following is more preferred: the cumulative light intensity is 1 mJ / cm. 2 Above 100mJ / cm 2 Further preferably, the cumulative light intensity is 3 mJ / cm². 2 Above 50mJ / cm 2 The most preferred option is a cumulative light intensity of 5 mJ / cm². 2 Above 30mJ / cm 2 Below. When the cumulative light intensity is less than 0.5 mJ / cm². 2 Under these conditions, the curing shrinkage reaction is weak, and the uneven shape cannot be fully formed, therefore the gloss will not decrease. When the cumulative light intensity is greater than 200 mJ / cm², the curing shrinkage reaction is weak. 2 In some cases, the curing shrinkage reaction is too strong, resulting in a deterioration of the surface condition.

[0062] The first illumination light, i.e., light with a wavelength below 200 nm, can be extracted from excimer VUV light. Excimer VUV light can be generated by a lamp containing a rare gas or a rare gas halide. When high-energy electrons are supplied from the outside to a lamp sealed with a rare gas or a rare gas halide, a large amount of discharge plasma (dielectric barrier discharge) is generated. Through this plasma discharge, the atoms of the discharge gas (rare gas) are excited and momentarily enter the excimer state. When returning from this excimer state to the ground state, light in the wavelength region specific to that excimer is emitted.

[0063] The gas used in excimer lamps can be any gas previously used, as long as it emits light below 200 nm. The gas can be rare gases such as Xe, Ar, and Kr, or a mixture of rare gases and halogen gases such as ArBr and ArF. The wavelength (center wavelength) of the excimer lamp varies depending on the gas used, for example, it has wavelengths of approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), and approximately 193 nm (ArF).

[0064] However, considering the difference between the energy and wavelength of the resulting photons and the bond energy of organic matter, a xenon lamp emitting excimer light with a center wavelength of 172 nm is preferred as the light source. Furthermore, considering the cost of equipment maintenance and the availability of materials, a xenon lamp is also preferred as the light source.

[0065] The first irradiation light, i.e., light with a wavelength below 200 nm, can only reach a depth of about tens to hundreds of nm from the surface of the acrylate. Therefore, the interior of the surface protective layer 5, which has ridges 5B formed by irradiation with light below 200 nm, is fluid and the curing reaction must be further advanced. In order to cure the surface protective layer 5 after irradiation with light below 200 nm, ionizing radiation or UV light with a wavelength longer than the first irradiation light (i.e., light with a wavelength below 200 nm) can be used as the second irradiation light.

[0066] It should be noted that, in this embodiment, for example, after irradiation with the second irradiation light, a third irradiation light may be used, which may be a different type of ionizing radiation or UV light with a longer wavelength than the second irradiation light. However, it is preferable to form the surface protective layer 5 with the ridge portion 5B by irradiation with only the first and second irradiation lights. Here, if the strength of the surface protective layer 5 is insufficient due to irradiation with only the second irradiation light, the third irradiation light may be used.

[0067] In order to cure the surface protective layer 5 as a whole by irradiation with the second irradiation light, it is preferable to set the cumulative light intensity of the second irradiation light to 10 mJ / cm. 2 Above 500mJ / cm 2The following is more preferred: the cumulative light intensity is 50 mJ / cm. 2 Above 400mJ / cm 2 Further preferably, the cumulative light intensity is 100 mJ / cm². 2 Above 300mJ / cm 2 The following applies when the cumulative light intensity is less than 10 mJ / cm². 2 In such cases, the curing reaction is weak and cannot impart sufficient strength to the surface protective layer 5 as a whole, thus tending to reduce damage resistance. Additionally, when the cumulative light intensity exceeds 200 mJ / cm², the curing reaction is also weak. 2 In some cases, if the curing reaction is too strong, the surface condition tends to deteriorate.

[0068] Furthermore, the cumulative light intensity of the second irradiation light is preferably greater than that of the first irradiation light. The cumulative light intensity of the second irradiation light is preferably 1.1 times to 50.0 times, more preferably 5.0 times to 30.0 times, more preferably 1.1 times to 50.0 times that of the first irradiation light. When the cumulative light intensity of the second irradiation light is less than 1.1 times that of the first irradiation light, the curing reaction is weak, and it may not impart sufficient strength to the surface protective layer 5 as a whole. Conversely, when the cumulative light intensity of the second irradiation light exceeds 50.0 times that of the first irradiation light, the curing reaction for the surface protective layer 5 as a whole is too strong, and the shape of the ridge portion 5B may deform.

[0069] The following is for reference Figure 6 The temporal changes in the amount of light irradiated by the first irradiation light and the temporal changes in the amount of light irradiated by the second irradiation light are explained.

[0070] Figure 6 A diagram illustrating the temporal variation of the illumination amount of the first illumination light and the temporal variation of the illumination amount of the second illumination light.

[0071] Figure 6 Figures (a), (c), (e), (g), and (i) are schematic diagrams illustrating the time-varying amount of the first irradiation light. Additionally, Figure 6 (b), (d), (f), (h) and (j) are diagrams schematically illustrating the time variation of the amount of irradiation light of the second irradiation light.

[0072] like Figure 6 As shown in (a), the intensity of the first irradiation light can gradually increase with the passage of irradiation time, and then gradually decrease with the passage of irradiation time. Additionally, as... Figure 6 As shown in (c), the amount of light emitted by the first irradiation beam can gradually decrease over time. Additionally, as... Figure 6 As shown in (e), the intensity of the first irradiation light can gradually increase with the passage of irradiation time. Additionally, as... Figure 6As shown in (g), the intensity of the first irradiation light can gradually decrease with the passage of irradiation time, and then gradually increase with the passage of irradiation time. Additionally, as... Figure 6 As shown in (i), the amount of illumination light of the first illumination light is constant from the start to the end of the illumination.

[0073] like Figure 6 As shown in (b), the intensity of the second irradiation light can gradually increase with the passage of irradiation time, and then gradually decrease with the passage of irradiation time. Additionally, as... Figure 6 As shown in (d), the amount of light emitted by the second irradiation can gradually decrease over time. Additionally, as... Figure 6 As shown in (f), the intensity of the second irradiation light can gradually increase with the passage of irradiation time. Additionally, as... Figure 6 As shown in (h), the intensity of the second irradiation light can gradually decrease with the passage of irradiation time, and then gradually increase with the passage of irradiation time. Additionally, as... Figure 6 As shown in (j), the amount of light irradiated by the second irradiation light is constant from the start to the end of irradiation.

[0074] In addition, in this embodiment, it is possible to Figure 6 The illumination methods of the first illumination light shown in (a), (c), (e), (g) and (i) are similar to... Figure 6 The second illumination methods shown in (b), (d), (f), (h), and (j) can be appropriately combined. For example, the illumination methods of the second illumination light can be... Figure 6 The illumination method of the first illumination light shown in (a) is the same as... Figure 6 The second illumination method shown in (f) can be used in combination. Alternatively, it can also be combined with... Figure 6 The irradiation method of the first irradiation light shown in (g) is the same as... Figure 6 The second irradiation method shown in (f) is used in combination. It should be noted that when the value of RSm / Ra is set in a more preferred range, i.e., 10 or more and 300 or less, it is possible to... Figure 6 The irradiation method of the first irradiation light shown in (c) is the same as... Figure 6 The second irradiation method shown in (f) is used in combination.

[0075] As described above, compared to the uneven shape formed by mechanical processing such as embossing the surface of the surface protective layer 5, the ridge 5B formed by irradiating light below 200 nm has a fine structure. By forming this fine uneven shape on the surface of the surface protective layer 5, fingerprint resistance can be improved while maintaining the matte finish of the decorative piece 1 surface.

[0076] Preferably, the thickness of the surface protective layer 5 is set in the range of 2 μm to 20 μm. More preferably, the thickness of the surface protective layer 5 is in the range of 3 μm to 20 μm. Further preferably, the thickness of the surface protective layer 5 is in the range of 5 μm to 15 μm. Most preferably, the thickness of the surface protective layer 5 is in the range of 5 μm to 12 μm. When the thickness of the surface protective layer 5 is less than 2 μm, the shaping effect using vacuum ultraviolet light will not penetrate deeply, thus low gloss cannot be achieved. In addition, when the thickness of the surface protective layer 5 is greater than 20 μm, the processability decreases, resulting in whitening during bending.

[0077] Furthermore, it is preferable to set the thickness of the surface protective layer 5 such that the ratio of the thickness of the ridge portion 5B to the thickness of the core portion 5A (the thickness of the ridge portion 5B / the thickness of the core portion 5A) is 0.01 or more and 2.0 or less. It is even more preferable to set the thickness of the surface layer 5 such that it is 0.1 or more and 1.0 or less.

[0078] Here, the patterned layer 3 and the surface protective layer 5 can be formed using various printing methods, such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing. Furthermore, since the surface protective layer 5 covers the entire surface of the original material layer 2, it can be formed using various coating methods, such as roller coating, doctor blade coating, microgravure coating, and die coating. These printing or coating methods can be selected separately depending on the layers being formed, or the same methods can be used for simultaneous processing.

[0079] From a design perspective, the patterned layer 3 and the surface protective layer 5 can be formed simultaneously. In this simultaneous formation, the surface protective layer 5 needs to be formed after the patterned layer 3, therefore gravure printing is preferred. Furthermore, gravure printing is advantageous in terms of cost due to its relatively high speed. Here, "simultaneous" means that at least 50%, preferably at least 70%, and most preferably at least 90%, of the portion where the surface protective layer 5 is formed overlaps with the patterned portion of the patterned layer 3 in a planar view.

[0080] To adjust the thickness of the surface protective layer 5, the coating amount can be adjusted in the above printing and coating methods. The coating amount can be calculated based on the mass difference between the surface protective layer formed on the substrate (raw material layer) and the surface protective layer not formed in various printing and coating methods.

[0081] The main material of the surface protective layer 5 is an ionizing radiation-curing resin. Here, "main material" refers to a resin containing at least 60 parts by mass, more preferably at least 70 parts by mass, and most preferably at least 80 parts by mass, relative to 100 parts by mass of the surface protective layer. As the ionizing radiation-curing resin constituting the surface protective layer 5, various monomers, commercially available oligomers, and other known resins can be used, such as (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. The ionizing radiation-curing resin can be either a water-based resin or a non-water-based (organic solvent-based) resin.

[0082] The main component of the ionizing radiation-curable resin constituting the surface protective layer 5 is a tetrafunctional acrylate resin containing a repeating structure. Examples of tetrafunctional acrylate resins include pentaerythritol tetraacrylate. Here, "main component" refers to a resin containing 60 parts by mass or more, more preferably 70 parts by mass or more, and most preferably 80 parts by mass or more, relative to 100 parts by mass of the constitutive resin. In the case of a trifunctional or less acrylate resin, the degree of crosslinking is insufficient, resulting in reduced damage resistance, and therefore it is not preferred. In the case of a pentafunctional or more acrylate resin, the crosslinking is too high, resulting in reduced processability, and therefore it is not preferred.

[0083] When using gravure printing as the coating method, the suitable viscosity range for the ionizing radiation-curable resin is 10–500 mPa·s, and the optimal viscosity range is 50–300 mPa·s. To adjust the viscosity, organic solvents or low-viscosity difunctional acrylate resins can be added. However, from an environmental perspective, it is preferable not to use organic solvents. When a large amount of difunctional acrylate resin is added, the damage resistance decreases, which is therefore undesirable. Therefore, when adding difunctional acrylate resin to tetrafunctional acrylate resin and using it, the content of the difunctional acrylate resin is preferably in the range of 10% by mass to 30% by mass, more preferably in the range of 15% by mass to 20% by mass, of the tetrafunctional acrylate resin content (by mass).

[0084] The aforementioned repeating structure is any one of ethylene oxide (EO), propylene oxide (PO), and ε-caprolactone (CL). More preferably, the repeating structure is ethylene oxide or propylene oxide. In ethylene oxide, propylene oxide, and ε-caprolactone structures, the molecules can rotate freely and are highly flexible, thus the molecules are easily folded by light below 200 nm, easily forming fine irregular shapes, and are therefore preferred. In addition, the number of repetitions of this repeating structure is set to 12 or more. More preferably, it is 12 or more and 50 or less, and most preferably 20 or more and 50 or less. When the number of repetitions is 11 or less, when irradiated with vacuum ultraviolet light (VUV light), the ionizing radiation-curable resin constituting the surface protective layer 5 does not shrink sufficiently, and the surface protective layer 5 does not become low-gloss. When the number of repetitions is greater than 50, the crosslinking density decreases, and the damage resistance of the surface protective layer 5 deteriorates.

[0085] The number of repetitions of the aforementioned repeating structure can be analyzed using MALDI-TOF-MS. The MALDI-TOF-MS spectra of ionizing radiation-cured resins sometimes exhibit a normal distribution with a molecular weight distribution. In the case of a molecular weight distribution, the number of repetitions is set to the number of repetitions corresponding to the molecular weight with the strongest peak in the MALDI-TOF-MS mass spectrum.

[0086] The surface protective layer 5 may contain particles. By adding particles of optimal size and content, a uniform surface can be formed. As particles, for example, organic materials such as PE wax, PP wax, and resin beads can be used; or inorganic materials such as silica, glass, alumina, titanium dioxide, zirconium oxide, calcium carbonate, and barium sulfate can be used.

[0087] The average particle size is preferably 10 μm or less. More preferably, it is 1 μm or more and 8 μm or less, further preferably 2 μm or more and 6 μm or less, and most preferably 3 μm or more and 5 μm or less. If the particle size is greater than 10 μm, the damage resistance decreases due to particle shedding, and therefore it is not preferred. If the particle size is less than 1 μm, the effect on surface homogenization is small, and therefore it is not preferred. Here, "particle size (average particle size)" can be a value (average value) obtained by measuring the particle size distribution of the particles used, or it can be a value obtained by actually measuring the particle size of multiple particles and averaging them based on cross-sectional observation of the obtained decorative material. The measurement methods are different, but the obtained particle size values ​​are essentially the same. For example, the average particle size of the particles added to the surface protective layer 5 can be the median particle size (D50) measured using a laser diffraction / scattering particle size distribution measuring device.

[0088] Furthermore, relative to 100 parts by mass of the ionizing radiation-curing resin, the amount of particles added is preferably 0.5 parts by mass or more and 10 parts by mass or less. More preferably, the amount of particles added is 2 parts by mass or more and 8 parts by mass, further preferably 2 parts by mass or more and 6 parts by mass or less, and most preferably 4 parts by mass or more and 5 parts by mass or less. By including the surface protective layer 5 with the above-mentioned amount of particles, a uniform surface state can be formed, which is preferred.

[0089] When the surface protective layer 5 is cured entirely by UV light, a photoinitiator needs to be added to the surface protective layer 5. There are no particular limitations on the photoinitiator, but examples include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based photoinitiators.

[0090] Antibacterial agents, antifungal agents, and other functional additives can be added to the surface protective layer 5 to impart the desired function. Additionally, ultraviolet absorbers and light stabilizers can be added to the surface protective layer 5 as needed. For example, benzotriazole series, benzoate series, benzophenone series, and triazine series are typically added in any combination as ultraviolet absorbers. Similarly, hindered amine series are typically added in any combination as light stabilizers.

[0091] Although this decorative sheet 1 does not contain gloss modifiers (matte additives), its gloss level is below 5.0, making it a decorative sheet with extremely low gloss. In conventional decorative sheets, when the gloss level of a decorative sheet with a surface protective layer is below 8, the content of gloss modifiers in the surface protective layer is high, causing the surface protective layer to become cloudy. Therefore, the color and pattern of the colored pattern layer may not be clearly displayed, or the design of the decorative sheet may be reduced. Furthermore, when attempting to obtain a decorative sheet with a gloss level close to 0, the content of gloss modifiers in the surface protective layer is even higher, making it difficult to form a smooth surface protective layer without producing streaks or spots.

[0092] Decorative sheet 1 can maintain the same level of performance as decorative sheets with a gloss level of 20 or higher, while also obtaining a low-gloss decorative sheet with a gloss level of 5.0 or lower. Here, "gloss level" is the measured value according to JIS Z8741 (ISO 2813) using a gloss meter at an incident angle of 60 degrees.

[0093] <Hidden Layer 8>

[0094] Furthermore, if it is desired to conceal the substrate B in the decorative sheet 1, this can be achieved by using colored sheets on the raw material layer 2 or by separately providing an opaque concealing layer 8. The concealing layer 8 can essentially be made of the same material as the pattern layer 3, but since concealment is the primary objective, it is preferable to use pigments such as opaque pigments, titanium dioxide, or iron oxide. Additionally, to further enhance concealment, metals such as gold, silver, copper, or aluminum can be added. Typically, sheet aluminum is added.

[0095] (Manufacturing method)

[0096] use Figure 4 A manufacturing example of decorative piece 1 (1A) will be described.

[0097] Using a resin film as the base material layer 2, a surface protective layer 5 is printed on top of the base material layer 2 for forming. The surface of the ionizing radiation-curable resin coated on the surface protective layer 5 is irradiated with light of wavelength less than 200 nm (first irradiation light) to cause the surface of the ionizing radiation-curable resin to shrink. Subsequently, ionizing radiation or UV light with a wavelength longer than the first irradiation light (i.e., light of wavelength less than 200 nm) is irradiated to cure the shrunken ionizing radiation-curable resin. As described above, a decorative sheet 1 having a surface protective layer 5 is formed, the surface protective layer 5 having a core portion 5A and a ridge portion 5B protruding in a ridge shape from one side (top) of the core portion 5A.

[0098] It should be noted that this embodiment is not limited to the above-described embodiment. For example, in order to cure the shrunken ionizing radiation-curable resin, it is also possible to irradiate it only once with ionizing radiation or with UV light whose wavelength is longer than that of the first irradiation light, i.e., light with a wavelength of 200 nm or less. Furthermore, in this case, the cumulative light intensity of the first irradiation light, i.e., light with a wavelength of 200 nm or less, can be set to 0.5 mJ / cm². 2 Above 200mJ / cm 2 the following.

[0099] (Other functions)

[0100] The decorative sheet 1 according to this embodiment has a surface protective layer 5 with an uneven surface. According to this configuration, even if the surface protective layer does not contain a gloss modifier (matte additive), the gloss (gloss level) of the surface protective layer can be adjusted. Gloss modifiers reduce the oleophobicity of layers formed from resin materials, thus making them prone to fingerprint adhesion. The surface protective layer 5 according to this embodiment does not contain a gloss modifier, therefore it does not absorb oil, and its oleophobicity is relatively improved. Therefore, in various scenarios such as on-site construction, furniture assembly, and the daily life of residents, the decorative sheet 1 with the surface protective layer 5 is less prone to fingerprint adhesion.

[0101] Furthermore, the surface protective layer 5, which has an uneven surface, improves the oleophobicity of the surface protective layer 5, thus inhibiting the adsorption of oil and pollutants on the surface of the decorative piece 1.

[0102] Furthermore, based on the composition of the surface protective layer 5 which does not contain gloss modifiers, the particles of gloss modifiers will not fall off when the surface of the decorative piece 1 is scratched, thus making it difficult to produce gloss changes or scratches on the surface of the decorative piece 1.

[0103] In this embodiment, the surface protective layer 5 is formed of a single layer, but is not limited to this configuration. For example, the surface protective layer 5 may also be multilayered. That is, the surface protective layer 5 may be formed by stacking multiple layers of the same ionizing radiation-curing resin or by stacking multiple layers of different ionizing radiation-curing resins to create an uneven surface. In the case of stacking multiple layers of different ionizing radiation-curing resins, for example, the main material of the outermost layer of the surface protective layer 5 is an ionizing radiation-curing resin, the main component of which is a tetrafunctional acrylic resin containing a repeating structure, which is any one of ethylene oxide, propylene oxide, and ε-caprolactone structures, and the repeating number of the repeating structure is 12 or more. There is no particular limitation on the layer of the surface protective layer 5 located on the side of the original material layer 2 (i.e., the layer located below the outermost layer of the surface protective layer 5).

[0104] [Example]

[0105] The following describes embodiments based on the present invention.

[0106] <Example 1>

[0107] A 55 μm thick olefin film (manufactured by RIKEN TECHNOS CORP.) was used as the base layer. One side of the base layer was corona-treated, and the surface protective coating solution described below was applied to the other side. The thickness of the surface protective coating solution was set to 5 μm. Then, the surface of the surface protective coating solution was irradiated with a 172 nm Xe excimer lamp, resulting in a cumulative light intensity of 100 mJ / cm². 2 This causes the surface to shrink. Subsequently, the surface protective layer is cured with a coating liquid by irradiation with 100 kGy of ionizing radiation to form surface protective layer 5, thereby obtaining the decorative sheet of Example 1 with a total thickness of 60 μm.

[0108] (Surface protective coating liquid)

[0109] The surface protective coating is formed by mixing the following particles into the following ionizing radiation-curing resin.

[0110] • Ionizing radiation-cured resin

[0111] Type: Ethoxylated pentaerythritol tetraacrylate (with 35 moles of EO added)

[0112] Product Name: NK Ester ATM-35E (Manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0113] Mix: 100 parts by weight

[0114] ·particle

[0115] Product Name: Silysia 250N (Manufactured by Fuji Silysia Chemical Ltd.)

[0116] Particle size: 5μm

[0117] Mixed: 0.5 parts by weight

[0118] <Example 2>

[0119] The decorative sheet of Example 2 was obtained by replacing the ionizing radiation curable resin of Example 1 with the following resin, otherwise, it was obtained in the same manner as in Example 1.

[0120] • Ionizing radiation-cured resin

[0121] Type: Ethoxylated pentaerythritol tetraacrylate (with 50 moles of EO added)

[0122] <Example 3>

[0123] The decorative sheet of Example 3 was obtained by replacing the ionizing radiation curable resin of Example 1 with the following resin, otherwise, it was obtained in the same manner as in Example 1.

[0124] • Ionizing radiation-cured resin

[0125] Type: Ethoxylated pentaerythritol tetraacrylate (with 20 moles of EO added)

[0126] <Example 4>

[0127] The decorative sheet of Example 4 was obtained by replacing the ionizing radiation curable resin of Example 1 with the following resin, otherwise, it was obtained in the same manner as in Example 1.

[0128] • Ionizing radiation-cured resin

[0129] Type: Propoxylated pentaerythritol tetraacrylate (with 35 moles of PO added)

[0130] <Example 5>

[0131] The decorative sheet of Example 5 was obtained by replacing the ionizing radiation curable resin of Example 1 with the following resin, otherwise, it was obtained in the same manner as in Example 1.

[0132] • Ionizing radiation-cured resin

[0133] Type: Caprolactone-modified pentaerythritol tetraacrylate (with 30 moles of caprolactone (CL) added)

[0134] <Example 6>

[0135] The thickness of the coating liquid used for the surface protective layer in Example 1 was set to 1 μm. Otherwise, the decorative sheet of Example 6 with a total thickness of 56 μm was obtained in the same manner as in Example 1.

[0136] <Example 7>

[0137] The thickness of the coating liquid used for the surface protective layer in Example 1 was set to 2 μm. Otherwise, the decorative sheet of Example 7 with a total thickness of 57 μm was obtained in the same manner as in Example 1.

[0138] <Example 8>

[0139] The thickness of the coating liquid used for the surface protective layer in Example 1 was set to 20 μm. Otherwise, the decorative sheet of Example 8 with a total thickness of 75 μm was obtained in the same manner as in Example 1.

[0140] <Example 9>

[0141] The thickness of the coating liquid used for the surface protective layer in Example 1 was set to 25 μm. Otherwise, the decorative sheet of Example 9 with a total thickness of 80 μm was obtained in the same manner as in Example 1.

[0142] <Example 10>

[0143] The decorative sheet of Example 10 was obtained in the same manner as that of Example 9, except that the particles of Example 9 were not mixed.

[0144] <Example 11>

[0145] The decorative sheet of Example 11 was obtained in the same manner as in Example 3, except that the particles of Example 3 were not mixed.

[0146] <Example 12>

[0147] The decorative sheet of Example 12 was obtained by replacing the particles of Example 1 with the following particles, otherwise, it was obtained in the same manner as in Example 1.

[0148] ·particle

[0149] Product Name: Silysia 450 (Manufactured by Fuji Silysia Chemical Ltd.)

[0150] Particle size: 8.0 μm

[0151] Mixed: 0.5 parts by weight

[0152] <Example 13>

[0153] The decorative sheet of Example 13 was obtained by replacing the particles of Example 1 with the following particles, otherwise, it was obtained in the same manner as in Example 1.

[0154] ·particle

[0155] Product Name: Silysia 780 (Manufactured by Fuji Silysia Chemical Ltd.)

[0156] Particle size: 11.3 μm

[0157] Mixed: 0.5 parts by weight

[0158] <Example 14>

[0159] The amount of particles from Example 1 was set to 10 parts by mass, and otherwise, the decorative sheet of Example 14 was obtained in the same manner as in Example 1.

[0160] <Example 15>

[0161] The amount of particles from Example 1 was set to 11 parts by mass, and otherwise, the decorative sheet of Example 15 was obtained in the same manner as in Example 1.

[0162] <Example 16>

[0163] The coating thickness of the surface protective layer in Example 1 was set to 1 μm and there were no particles. Otherwise, the decorative sheet of Example 16 with a total thickness of 56 μm was obtained in the same manner as in Example 1.

[0164] <Example 17>

[0165] The decorative sheet of Example 17 was obtained by replacing the ionizing radiation curable resin of Example 1 with the following resin, otherwise, it was obtained in the same manner as in Example 1.

[0166] • Ionizing radiation-cured resin

[0167] Type: Ethoxylated pentaerythritol tetraacrylate (with 12 moles of EO added)

[0168] <Example 18>

[0169] The thickness of the coating liquid used for the surface protective layer in Example 2 was set to 25 μm. Otherwise, the decorative sheet of Example 18 with a total thickness of 80 μm was obtained in the same manner as in Example 2.

[0170] <Comparative Example 1>

[0171] Without the excimer lamp irradiation of Example 1, and with the particle mixing amount set to 15 parts by mass, the decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1.

[0172] <Comparative Example 2>

[0173] The decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1, except that the ionizing radiation curable resin of Example 1 was replaced with the following resin.

[0174] • Ionizing radiation-cured resin

[0175] Type: Trimethylolpropane EO-modified triacrylate (with 6 moles of EO added)

[0176] Product Name: Miramer M3160 (Made by Miwon)

[0177] <Comparative Example 3>

[0178] The decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1, except that the ionizing radiation curable resin of Example 1 was replaced with the following resin.

[0179] • Ionizing radiation-cured resin

[0180] Type: Ethoxylated dipentaerythritol polyacrylate (with 12 moles of EO added)

[0181] Product Name: NK Ester A-DPH-12E (Manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0182] <Comparative Example 4>

[0183] The decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1, except that the ionizing radiation curable resin of Example 1 was replaced with the following resin.

[0184] • Ionizing radiation-cured resin

[0185] Type: Pentaerythritol tetraacrylate

[0186] Product Name: NK Ester A-TMMT (Made by Shin-Nakamura Chemical Co., Ltd.)

[0187] (evaluate)

[0188] The decorative sheets of Examples 1 to 18 and Comparative Examples 1 to 4 obtained by the above method were evaluated.

[0189] In this embodiment, if the evaluation is "○" and "△", there is no problem in actual use, and it is set as qualified.

[0190] <Surface Condition>

[0191] The surface uniformity was evaluated visually.

[0192] The evaluation criteria are as follows.

[0193] 〇: Uniform surface condition

[0194] △: A portion has uneven parts

[0195] ×: The surface condition of the entire surface is uneven.

[0196] <Gloss>

[0197] For gloss, the gloss level at 60 degrees was measured using the Rhopoint IQ (made by Konica Minolta).

[0198] It should be noted that if the gloss level is below 15, it is considered visually low enough. Therefore, in this embodiment, "below 15" is set as acceptable.

[0199] <Fingerprint Resistance: Wiping Performance Evaluation>

[0200] As an evaluation of fingerprint resistance, the wiping resistance of fingerprints was evaluated.

[0201] The gloss level at 60 degrees on the surface of each decorative piece was measured as the [initial gloss]. Then, a fingerprint resistance evaluation solution was applied to the surface protective layer, and the solution was wiped off the decorative piece surface. The gloss level at 60 degrees on the portion after wiping off the fingerprint resistance evaluation solution was then measured as the [post-wiping gloss]. Here, higher fatty acids were used as the fingerprint resistance evaluation solution.

[0202] The fingerprint wiping rate is calculated as follows.

[0203] Fingerprint wiping rate (%) = (gloss after wiping / initial gloss) × 100

[0204] The evaluation criteria are as follows.

[0205] 〇: 70% or more but less than 250%

[0206] △: 50% or more but less than 70%, or 250% or more but less than 300%

[0207] ×: Less than 50%, or more than 300%

[0208] <Stain Resistance>

[0209] As an evaluation of stain resistance, the stain resistance of the ink was evaluated by using the Stain A test specified in the Japanese Agricultural Standards (JAS). Blue ink, black quick-drying ink, and red crayon were used to draw lines 10 mm wide, and the lines were left for 4 hours. Then, ethanol was contained in a cloth and used to wipe the lines of blue ink, black quick-drying ink, and red crayon.

[0210] The evaluation criteria are as follows.

[0211] 〇: Can easily wipe off threads of various colors.

[0212] △: It can wipe away part of the various colored threads, but leaves some stains.

[0213] ×: The various colored threads cannot be wiped off.

[0214] <Damage Resistance Test: Steel Wire Friction Test>

[0215] The resulting decorative sheet was bonded to the wood substrate B using a urethane-based adhesive, and then a steel wool abrasion test was performed to evaluate its damage resistance. A load of 300g was applied to the steel wool and rubbed back and forth 20 times. The damage and changes in gloss on the surface of the decorative sheet were visually confirmed.

[0216] The evaluation criteria are as follows.

[0217] 〇: No damage or change in gloss was observed on the surface.

[0218] △: The surface has suffered minor damage and changes in gloss.

[0219] ×: The surface showed obvious damage and changes in gloss.

[0220] <Curlability Test>

[0221] The resulting decorative piece was cut into 10cm squares and left to stand for 48 hours at 25°C and 50% RH. Then, the average distance between the four corners and the plane was calculated. That is, in this curling test, if... Figure 7 As shown, the shortest distance d from the surface (plane) of the test stage on which the decorative sheet is placed to each corner of the decorative sheet was measured, and these values ​​were averaged to evaluate the curlability of the decorative sheet.

[0222] The evaluation criteria are as follows.

[0223] 〇: Less than 3cm

[0224] △: Greater than 3cm and less than 5cm

[0225] ×: Greater than 5cm

[0226] <Packaging processability test>

[0227] The resulting decorative sheets were packaged. The processability was evaluated by observing the curved portions of the decorative sheets using an optical microscope to determine if whitening or cracking occurred. It should be noted that this packaging processability is equivalent to so-called bending processability.

[0228] The evaluation criteria are as follows.

[0229] 〇: No whitening or cracks were observed.

[0230] △: Albinism was observed in some samples.

[0231] ×: Whitening is observed across the entire surface, or cracks are observed in one part of the surface.

[0232] The evaluation results are shown in Tables 1 and 2.

[0233]

[0234] [Table 2]

[0235]

[0236] As shown in Table 1, decorative sheets of Examples 1-18 can provide low gloss and are also resistant to fingerprints, damage, stains, and bending. In addition to the surface shape and resin composition of the surface protective layer, optimizing the layer thickness, particle size of the mixed particles, and the amount added can further improve performance.

[0237] Explanation of symbols

[0238] 1 Decorative piece

[0239] 2. Raw material layer

[0240] 3 patterned layers

[0241] 4. Transparent resin layer

[0242] 5. Surface protective layer

[0243] 6. Primer layer

[0244] 7. Adhesive layer

[0245] 8. Concealed Layer

[0246] 11 Decorative Materials

[0247] B substrate

Claims

1. A decorative sheet comprising a base material layer and a surface protective layer disposed on one surface of the base material layer, characterized in that, The surface protective layer has ridges protruding on its surface and has an uneven shape. The RSm / Ra of the uneven shape of the surface protective layer is in the range of 10 to 300. The main material of the surface protective layer is an ionizing radiation-curing resin. The main component of the ionizing radiation-curable resin is a tetrafunctional acrylic resin containing repeating structures. The repeating structure is any one of the structures of ethylene oxide, propylene oxide, and ε-caprolactone. The repeating structure is repeated 12 times or more. The surface protective layer has a core and ridges formed on the core. The ratio of the thickness of the ridge portion to the thickness of the core portion (thickness of the ridge portion / thickness of the core portion) is in the range of 0.01 to 2.

0.

2. The decorative piece according to claim 1, characterized in that, The thickness of the surface protective layer is in the range of 2 μm to 20 μm.

3. The decorative piece according to claim 2, characterized in that, The surface protective layer contains particles with an average particle size of less than 10 μm.

4. The decorative piece according to claim 3, characterized in that, The amount of the particles added is in the range of 0.5 parts by mass to 10 parts by mass relative to 100 parts by mass of the ionizing radiation-curing resin.

5. The decorative piece according to any one of claims 1 to 4, characterized in that, The gloss level of the surface protective layer is below 5.

0.

6. The decorative piece according to any one of claims 1 to 4, characterized in that, The ratio of the thickness of the ridge portion to the thickness of the core portion (thickness of the ridge portion / thickness of the core portion) is in the range of 0.1 to 1.

0.

7. The decorative piece according to any one of claims 1 to 4, characterized in that, The RSm / Ra of the uneven shape of the surface protective layer is in the range of 80 to 150.

8. The decorative piece according to any one of claims 1 to 4, characterized in that, The ridge-like portion has a sinusoidal cross-sectional shape in the thickness direction of the surface protective layer.

9. The decorative piece according to any one of claims 1 to 4, characterized in that, The 4-functional acrylic resin is a resin composed of pentaerythritol tetraacrylate.

10. A method for manufacturing a decorative sheet, characterized in that, The surface of the coated ionizing radiation-curable resin is irradiated with light of wavelength less than 200 nm, and then irradiated with ionizing radiation or UV light with a wavelength longer than 200 nm. This forms a surface protective layer with ridge-like protrusions. The surface protective layer has an uneven shape with RSm / Ra values ​​of 10 to 300. The surface protective layer has a core and ridges formed on the core. The ratio of the thickness of the ridge portion to the thickness of the core portion (thickness of the ridge portion / thickness of the core portion) is in the range of 0.01 to 2.

0.

11. The method for manufacturing a decorative sheet according to claim 10, characterized in that, The wavelength of light with a wavelength below 200nm is 172nm.

12. The method for manufacturing a decorative sheet according to claim 10 or claim 11, characterized in that, The surface of the coated ionizing radiation-curable resin is irradiated with light of wavelength less than 200 nm, and then irradiated once with ionizing radiation or UV light with a wavelength longer than 200 nm. This forms a surface protective layer with ridge-like protrusions. The cumulative light intensity of light with wavelengths below 200 nm is set to 0.5 mJ / cm. 2 Above 200mJ / cm 2 Within the following range.

13. The method for manufacturing the decorative sheet according to claim 10 or claim 11, characterized in that, The cumulative light intensity of UV light with wavelengths less than 200 nm is set to 10 mJ / cm. 2 Above 500mJ / cm 2 Within the following range.

14. The method for manufacturing a decorative sheet according to claim 10 or claim 11, characterized in that, By irradiating the surface of the coated ionizing radiation-curable resin with light of wavelengths below 200 nm, and then irradiating it with ionizing radiation, This forms a surface protective layer with ridges protruding in the shape of ridges.

15. The method for manufacturing a decorative sheet according to claim 10 or claim 11, characterized in that, The coating is applied to an ionizing radiation-curable resin with a viscosity range of 10 mPa·s to 500 mPa·s.

Images