WO2025023246A1 - 化粧シート - Google Patents

化粧シート Download PDF

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Publication number
WO2025023246A1
WO2025023246A1 PCT/JP2024/026332 JP2024026332W WO2025023246A1 WO 2025023246 A1 WO2025023246 A1 WO 2025023246A1 JP 2024026332 W JP2024026332 W JP 2024026332W WO 2025023246 A1 WO2025023246 A1 WO 2025023246A1
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WIPO (PCT)
Prior art keywords
decorative sheet
protective layer
surface protective
layer
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/026332
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English (en)
French (fr)
Japanese (ja)
Inventor
真志 服部
裕香 野本
恭行 柳沢
陽太 長谷
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Toppan Holdings Inc
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Toppan Holdings Inc
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Priority to JP2025535836A priority Critical patent/JPWO2025023246A1/ja
Publication of WO2025023246A1 publication Critical patent/WO2025023246A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties

Definitions

  • the present invention relates to a decorative sheet.
  • Designs can be added by forming patterns such as wood grain or stone using various printing methods. Plain, pattern-free decorative sheets are sometimes preferred. The choice of whether or not to have a pattern and the type of pattern vary according to the application and preference.
  • the glossiness of the surface is also important in the design of decorative sheets.
  • decorative sheets There are a variety of decorative sheets to choose from, ranging from mirror-like high gloss to low gloss with no reflections at all, depending on the application and preference.
  • a surface protective layer on the outermost surface of the decorative sheet. Also, to adjust the gloss mentioned above, and in particular to achieve a low gloss, it is common to add a gloss adjuster (matte additive) to the surface protective layer.
  • the objective of the present invention is to provide a decorative sheet that provides a moist feel.
  • a decorative sheet comprising an original fabric layer and a surface protective layer provided on one surface of the original fabric layer, the surface of the surface protective layer being provided with an uneven structure including a plurality of ridge-like portions each of which protrudes in a ridge-like shape, and the wrinkled area ratio on the surface of the surface protective layer being 0.45 or more and 1.0 or less.
  • a decorative sheet according to the above aspect in which the surface protective layer includes a cured resin and particles.
  • a decorative sheet according to the above aspect is provided in which the particles have an average particle size of 3 ⁇ m or more.
  • a decorative sheet according to the above aspect in which the particles have an average particle size of 3 ⁇ m or more and 11 ⁇ m or less.
  • a decorative sheet according to any of the above aspects, in which the particles are contained in the surface protective layer in an amount of 3 parts by mass or more and 11 parts by mass or less per 100 parts by mass of the resin.
  • a decorative sheet according to any of the above aspects, in which the resin is an ionizing radiation curable resin.
  • a decorative sheet according to any of the above aspects, in which the resin is an acrylate.
  • a decorative sheet according to the above aspect, in which the resin is a trifunctional acrylate containing a repeating structure, and the number of repetitions of the repeating structure is 3 or more and 20 or less.
  • a decorative sheet according to the above aspect, in which the resin is a tetrafunctional acrylate containing a repeating structure, and the number of repetitions of the repeating structure is 20 or more and 35 or less.
  • the surface protective layer further comprises a sliding property imparting agent, and the sliding property imparting agent is contained in the surface protective layer in an amount of 0.01 parts by mass or more and 0.03 parts by mass or less per 100 parts by mass of the resin.
  • a decorative sheet according to any of the above aspects, in which the thickness t of the surface protective layer is 2 ⁇ m or more and 18 ⁇ m or less.
  • a decorative sheet according to any of the above aspects, further comprising a pattern layer between the base layer and the surface protective layer.
  • the decorative sheet according to any one of the above aspects is provided, in which the gloss of the surface protective layer is less than 10.
  • a decorative material comprising a decorative sheet according to any of the above aspects and a substrate to which the decorative sheet is attached.
  • a method for producing a decorative sheet comprising stirring a coating liquid containing an ionizing radiation curable resin and particles, forming a coating film made of the coating liquid on an original layer, carrying out a first irradiation step of irradiating the coating film with light having a wavelength of 200 nm or less, and then carrying out a second irradiation step of irradiating the coating film with ionizing radiation or ultraviolet light having a longer wavelength than the light irradiated in the first irradiation step, wherein stirring the coating liquid and the first irradiation step are carried out such that the surface of the coating film after the second irradiation step has a wrinkled area ratio of 0.45 to 1.0.
  • the present invention provides a decorative sheet that provides a moist feel.
  • 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 surface protective layer included in the decorative sheet of FIG.
  • FIG. 3 is a microscope image of a surface protective layer included in a decorative sheet according to one example of the present invention.
  • Decorative material and decorative sheet 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 surface protective layer included in the decorative sheet of Fig. 1.
  • Fig. 3 is a micrograph of a surface protective layer included in a decorative sheet according to one example of the present invention.
  • the cross section shown in Figure 2 is a cross section along the thickness direction of the surface protection layer.
  • the micrograph in Figure 3 is a plan view taken with a laser microscope (OLS-4000, manufactured by Olympus Corporation).
  • the decorative material 11 shown in FIG. 1 includes a substrate B and a decorative sheet 1 attached thereto.
  • 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.
  • 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.
  • the decorative sheet 1 includes an original fabric layer 2, a pattern layer 3, a transparent resin layer 4, a surface protective layer 5, an adhesive layer 7, a primer layer 6, and a concealing layer 8.
  • the pattern layer 3, adhesive layer 7, transparent resin layer 4, and surface protective layer 5 are provided in this order from the original fabric layer 2 side on the surface of the original fabric layer 2 opposite the surface facing the substrate B.
  • the concealing layer 8 and primer layer 6 are provided in this order from the original fabric layer 2 side on the surface of the original fabric layer 2 facing the substrate B.
  • One or more of the pattern layer 3, transparent resin layer 4, primer layer 6, adhesive layer 7, and concealing layer 8 may be omitted. The elements included in the decorative sheet 1 will be explained below in order.
  • the raw fabric layer 2 or its material can be any material selected from, for example, paper, synthetic resin, synthetic resin foam, rubber, nonwoven fabric, synthetic paper, metal foil, etc.
  • paper include tissue paper, titanium paper, resin-impregnated paper, etc.
  • synthetic resin include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, etc.
  • Examples of rubber 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, polyurethane, etc.
  • Examples of nonwoven fabric include organic and inorganic nonwoven fabrics. Examples of metal foil include aluminum, iron, gold, silver, etc.
  • the thickness of the base layer 2 is preferably within the range of 20 ⁇ m to 250 ⁇ m, taking into consideration printing workability and costs.
  • Primer layer When olefin-based resin is used as the material of 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 6 between the raw fabric layer 2 and the substrate B.
  • the primer layer 6 can be omitted, and the raw fabric layer 2 can be subjected to a surface modification treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, and dichromate treatment in order to improve the adhesion between the raw fabric layer 2 and the substrate B.
  • the materials for the primer layer 6 can be, for example, the materials described below for the pattern layer 3. Since the primer layer 6 is applied to the back surface of the decorative sheet 1, and considering that the decorative sheet 1 is wound up in a web form, an inorganic filler may be added to the primer layer 6 to avoid blocking and to increase adhesion to the adhesive.
  • inorganic fillers include silica, alumina, magnesia, titanium oxide, barium sulfate, etc.
  • ⁇ 1.3> Concealing layer In order to impart the decorative sheet 1 with the ability to conceal the substrate B, for example, a colored sheet is used as the base layer 2, or an opaque concealing layer 8 is provided.
  • the concealing layer 8 can be made of the same material as that described later for the pattern layer 3. However, since the purpose of the concealing layer 8 is to provide concealment, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide, etc. as the pigment.
  • metals such as gold, silver, copper, and aluminum to the material of the concealing layer 8. In general, flake-shaped aluminum pieces are often added.
  • an olefin-based resin is suitably used as the resin material of the transparent resin layer 4.
  • the olefin-based resin include polypropylene, polyethylene, polybutene, and the like, as well as ⁇ -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-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
  • the resin for the transparent resin layer 4.
  • various additives such as heat stabilizers, light stabilizers, antiblocking agents, catalyst scatterers, colorants, light scattering agents, and gloss adjusters can also be added to the transparent resin layer 4 as necessary.
  • Phenol-based, sulfur-based, phosphorus-based, and hydrazine-based heat stabilizers, and hindered amine-based light stabilizers are generally added in any combination.
  • the surface protection layer 5 includes a core portion 5A and a plurality of ridge portions 5B each protruding in a ridge shape from one surface of the core portion 5A. These ridge portions 5B form an uneven structure.
  • ridge-like refers to a convex shape that is linear in plan view.
  • the ridge portions 5B may be curved or straight in plan view, but are preferably curved in view of the fingerprint resistance of the decorative sheet 1.
  • Each of the ridge portions 5B may or may not be branched in plan view.
  • the ridge portions 5B are, for example, the portions from the lowest part to the tip 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 excluding the ridge portions 5B.
  • the ridge portions 5B are each curved, and at least some of them are adjacent to each other in the width direction.
  • the cross section of the surface protective layer 5 parallel to the width direction and the thickness direction of the surface protective layer 5 has a wave shape, such as a sine wave shape, in the portion where the uneven structure is provided, as shown in FIG. 2.
  • the surface of the surface protection layer 5 on which the uneven structure is provided has a wrinkled area ratio of 0.45 to 1.0.
  • the wrinkled area ratio is preferably 0.8 to 1.0.
  • the wrinkled area rate is a value obtained by the following method.
  • a laser microscope is used to obtain a surface shape image of the uneven structure provided on the surface of the surface protection layer 5.
  • This surface shape image has a brightness corresponding to the height.
  • the objective lens is set to a magnification of 10 times to obtain an image of a square area with one side measuring 1 mm. This image has 1024 pixels in each direction.
  • the acquired image is converted to an 8-bit grayscale image.
  • the pixel value of the highest pixel is set to 255, and the pixel value of the lowest pixel is set to 0.
  • the resulting grayscale image is divided into a grid of 8 rows and 8 columns to obtain 64 divided images.
  • Each divided image has 128 pixels in each direction.
  • the arithmetic mean of the pixel values of the 16,384 pixels (128 x 128) it contains is calculated.
  • the resulting arithmetic mean is used as the threshold.
  • the number of pixels with pixel values below the threshold is calculated.
  • the obtained number is called the number of black pixels.
  • a divided image having a number of black pixels equal to or greater than 0.55 times 16384, i.e., equal to or greater than 9012, is determined to be a wrinkled region, and a divided image having a number of black pixels less than 9012 is determined to be a non-wrinkled region.
  • the wrinkle area rate is obtained by calculating the ratio of the number of wrinkled areas to the total number of divided images, i.e., 64.
  • the surface of the surface protection layer 5 it is desirable for the surface of the surface protection layer 5 to have wrinkles in many small areas.
  • the area of the top surface of the convex parts forming the wrinkles is large, there is a large resistance to pressing when you press your finger against it. In this case, even a slight increase in pressure when pressing your finger against it will greatly increase the contact area. As a result, you will not be able to get a moist feel. Therefore, it is desirable for the area of the top surface of the convex parts forming the wrinkles to be small.
  • the areas of the surface protective layer 5 that correspond to the divided images are sufficiently small. And, among these areas, those that correspond to the wrinkled areas have wrinkles and the proportion of convex parts is small.
  • This structure corresponds to the desirable structure described above. Therefore, when the surface of the surface protective layer 5 is pressed with a finger and the finger is slid over this surface, the decorative sheet 1 has a small pressing resistance, and the contact area gradually increases as the pressure increases, giving a moist feel.
  • the thickness t of the surface protective layer 5 is preferably 2 ⁇ m or more and 18 ⁇ m or less.
  • the thickness t of the surface protective layer 5 is more preferably 3 ⁇ m or more and 10 ⁇ m or less. If the thickness of the surface protective layer 5 is too small or too large, it becomes difficult to achieve a "moist touch". If the thickness of the surface protective layer 5 is too small, it becomes difficult to achieve a low glossiness. If the thickness of the surface protective layer 5 is too large, it becomes difficult to achieve high processability. The processability will be described later.
  • the thickness of the surface protective layer 5 is obtained by observing the cross section with a scanning electron microscope and averaging 25 points. Specifically, the thickness of the surface protective layer 5 can be obtained as described in the examples described later. If the coating liquid for the surface protective layer described later does not contain a solvent, the thickness of the coating film made of the coating liquid for the surface protective layer is equal to the thickness of the surface protective layer 5.
  • the surface protective layer 5 preferably contains a cured resin and particles.
  • the resin contained in the surface protective layer 5 is preferably an ionizing radiation curable resin.
  • ionizing radiation refers to a charged particle beam such as an electron beam.
  • the ionizing radiation curable resin is cured by irradiation with ionizing radiation.
  • the ionizing radiation curable resin may also be cured by irradiation with ultraviolet light.
  • the ionizing radiation curable resin used here is cured by irradiation with light having a wavelength of 200 nm or less, and has a large absorption coefficient for this light.
  • the amount of the cured ionizing radiation curable resin in the surface protective layer 5 is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
  • the ionizing radiation curable resin known materials such as various monomers and commercially available oligomers can be used, for example, (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins can be used.
  • the ionizing radiation curable resin may be either an aqueous resin or a non-aqueous (organic solvent-based) resin.
  • the main component of the ionizing radiation curable resin is preferably an acrylate.
  • the main component of the ionizing radiation curable resin means a component that accounts for 60% by mass or more of the ionizing radiation curable resin.
  • the ionizing radiation curable resin preferably contains 70 parts by mass or more of acrylate, and more preferably contains 80 parts by mass or more.
  • the ionizing radiation curable resin is more preferably an acrylate.
  • the acrylate is preferably an acrylate having two or more functional groups, and more preferably an acrylate having three or more functional groups.
  • the acrylate is preferably an acrylate having three or more functional groups. There is no upper limit to the number of functional groups of the acrylate, but according to one example, it is six or less functional groups.
  • the acrylate preferably contains a repeating structure.
  • This repeating structure is, for example, any one of an ethylene oxide (EO) structure, a propylene oxide (PO) structure, and an ⁇ -caprolactone (CL) structure.
  • the repeating structure is preferably ethylene oxide or propylene oxide.
  • the repeating structure may be present between the acryloyl group and the methylol group in an open ring state.
  • 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 in the first irradiation step described below, and therefore wrinkles corresponding to the ridged portions 5B are more likely to appear on the coating film surface. Furthermore, if an acrylate with a large number of repetitions is used, the gloss value tends to decrease and the design tends to improve. However, if the number of repetitions is increased, the crosslinking density decreases and the scratch resistance of the surface protective layer decreases. Furthermore, if an acrylate with a small number of repetitions is used, it may be difficult to achieve high processability.
  • the ionizing radiation curable resin is a trifunctional acrylate containing a repeating structure.
  • the trifunctional acrylate containing a repeating structure is, for example, EO-modified, PO-modified, or CL-modified trimethylolpropane triacrylate, glycerin triacrylate, isocyanurate triacrylate, or pentaerythritol triacrylate.
  • the number of repetitions of the repeating structure is preferably 3 or more, more preferably 3 to 30, and even more preferably 3 to 20.
  • the ionizing radiation curable resin is a tetrafunctional acrylate containing a repeating structure.
  • the tetrafunctional acrylate containing a repeating structure is, for example, EO-modified, PO-modified, or CL-modified pentaerythritol tetraacrylate.
  • the number of repeats of the repeating structure is preferably 12 or more, more preferably 12 to 50, even more preferably 20 to 50, and even more preferably 20 to 35.
  • the number of repetitions of the above 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 above number of repetitions should be the number of repetitions that corresponds to the molecular weight with the strongest peak in the MALDI-TOF-MS mass spectrum.
  • the particles contained in the surface protective layer 5 can 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.
  • PE polyethylene
  • PP polypropylene
  • resin beads or particles made of inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.
  • the particles preferably have an average particle size (D50) of 3 ⁇ m or more.
  • the average particle size (D50) of the particles is more preferably 3 ⁇ m or more and 11 ⁇ m or less, and even more preferably 4 ⁇ m or more and 10 ⁇ m or less.
  • the surface protective layer 5 contains particles, wrinkles can be more uniformly generated on the coating surface in the first irradiation step described below.
  • the average particle size (D50) of the particles is large, there is a tendency for the user to feel a strong unevenness of the particles. For this reason, if the average particle size (D50) is too large, it is difficult to achieve a "moist feel".
  • the particles are likely to fall off from the surface protective layer 5, making it difficult to achieve high scratch resistance.
  • large particles it may be difficult to achieve high processability.
  • the particles are small, the effect of generating wrinkles uniformly is likely to be small.
  • the particles are small, when a finger is slid over the surface of the decorative sheet 1, it is difficult to feel a slippery feeling, which may give the user a "sticky feel".
  • the particles are preferably contained in the surface protection layer 5 in an amount of 3 to 11 parts by weight per 100 parts by weight of resin. It is more preferable that the amount of particles added is 4 to 10 parts by weight per 100 parts by weight of resin. Note that "100 parts by weight of resin” refers to the parts by weight of the solid content of the resin.
  • the surface protective layer 5 preferably further contains a sliding property imparting agent.
  • the sliding property imparting agent improves the ease of sliding of a finger when a user slides a finger on the surface of the surface protective layer, i.e., improves sliding property.
  • the sliding property imparting agent may be contained in the surface protective layer 5 as the above-mentioned particles or as a part of particles, or may be contained in the surface protective layer 5 in a state dissolved in a resin.
  • a particulate sliding property imparting agent is prepared and kneaded with a resin to include the sliding property imparting agent in the surface protective layer 5.
  • an emulsion containing the sliding property imparting agent is prepared and kneaded with a resin to include the sliding property imparting agent in the surface protective layer 5.
  • the silicone when a shear force is applied, the silicone can also be exposed on the surface of the acrylic silicone resin, so that it is possible to improve the sliding property.
  • a fluorine-based resin can also be used as the sliding property imparting agent.
  • the amount of the slipperiness imparting agent contained in the surface protective layer 5 is preferably 0.01 parts by mass or more and 0.03 parts by mass or less per 100 parts by mass of the resin.
  • the decorative sheet 1 is manufactured, for example, by the following method.
  • explanations regarding the design layer 3, transparent resin layer 4, primer layer 6, adhesive layer 7, and concealing layer 8 are omitted here.
  • the coating liquid for the surface protective layer may further contain a solvent and additives for improving the functionality of the final product, such as a sliding agent, an antibacterial agent, and an antifungal agent.
  • the coating liquid for the surface protective layer may further contain other additives such as an ultraviolet absorber and a light stabilizer.
  • an ultraviolet absorber for example, a benzotriazole-based, benzoate-based, benzophenone-based, or triazine-based agent may be used.
  • As the light stabilizer for example, a hindered amine-based agent may be used. According to the method described herein, a surface protective layer 5 having a low gloss level can be formed without a gloss adjuster (matte additive).
  • the coating liquid for the surface protective layer further contains a photoinitiator.
  • the photoinitiator is not particularly limited, but examples include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based photoinitiators.
  • a coating film made of a coating liquid for the surface protection layer is formed on one side of the base layer 2.
  • This 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.
  • the first irradiation step is carried out.
  • the coating film is irradiated with light having a wavelength of 200 nm or less (hereinafter referred to as the first radiation).
  • the ionizing radiation curable resin contained in the coating liquid for the surface protective layer has a large absorption coefficient for the first radiation. Therefore, the first radiation incident on the coating film can only reach a position several tens to several hundreds of nm away from the outermost surface. Therefore, in the first irradiation step, the crosslinking reaction proceeds in the surface region of the coating film to form an extremely thin cured film, while in other regions, the crosslinking reaction does not proceed and the coating film remains uncured.
  • the coating film After the first irradiation process, the coating film has wrinkles on its surface that correspond to the ridged portion 5B.
  • the inventor believes that the reason wrinkles form on the coating film surface as a result of the first irradiation process is as follows.
  • the first radiation can only reach a position that is tens to hundreds of nanometers away from the outermost surface of the coating film.
  • the crosslinking reaction of the ionizing radiation curable resin occurs only on the surface of the coating film, and areas that are more than tens to hundreds of nanometers away from the outermost surface are uncured and contain highly fluid molecules. These highly fluid molecules swell the cured film, thereby increasing its volume. The increase in volume in the in-plane direction causes the cured film to buckle, resulting in wrinkles on the surface of the coating film.
  • the first 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 provided from the outside to a lamp that contains 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), which momentarily enters an excimer state. When returning from this excimer state to the ground state, light is emitted in a wavelength range specific to that excimer.
  • the gas used in the excimer lamp may be any conventional gas that emits light of 200 nm or less.
  • the gas may be a rare gas such as Xe, Ar, or Kr, or a mixed gas of a rare gas such as ArBr or ArF with a halogen gas.
  • the wavelength (center wavelength) of the excimer lamp varies depending on the gas, and may be, for example, about 172 nm (Xe), about 126 nm (Ar), about 146 nm (Kr), about 165 nm (ArBr), or about 193 nm (ArF).
  • 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.
  • the first irradiation step is carried out in an atmosphere with a low oxygen concentration.
  • Oxygen has a large absorption coefficient for light of 200 nm or less. Therefore, the first irradiation step is preferably carried out in, for example, a nitrogen gas atmosphere.
  • the oxygen concentration in the gas phase in the first 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.
  • oxygen in the atmosphere inhibits radical polymerization. Therefore, the residual oxygen concentration in the reaction atmosphere affects the formation of wrinkles on the coating surface. Therefore, changing the residual oxygen concentration in the reaction atmosphere can also change the surface properties of the surface protective layer 5.
  • the integrated light amount of the first radiation is preferably 0.5 mJ/ cm2 to 200 mJ/ cm2 , more preferably 1 mJ/ cm2 to 100 mJ/ cm2 , even more preferably 3 mJ/ cm2 to 50 mJ/ cm2 , and most preferably 5 mJ/ cm2 to 30 mJ/ cm2 . If the integrated light amount is reduced, the expansion of the cured film in the in-plane direction is reduced. If the integrated light amount is increased, the surface condition of the coating film is deteriorated.
  • the second irradiation step is carried out.
  • the coating film is irradiated with a second radiation to harden the entire coating film. This results in the surface protective layer 5.
  • the second radiation is ionizing radiation such as an electron beam, or ultraviolet light having a longer wavelength than the first radiation.
  • ultraviolet light When ultraviolet light is used as the second radiation, the ultraviolet light has a wavelength at which the ionizing radiation curable resin exhibits a smaller absorption coefficient.
  • the accumulated light amount of the second radiation is preferably 10 mJ/cm 2 or more and 500 mJ/cm 2 or less, more preferably 50 mJ/cm 2 or more and 400 mJ/cm 2 or less, and even more preferably 100 mJ/cm 2 or more and 300 mJ/cm 2 or less.
  • the decorative sheet 1 described with reference to Figures 1 to 3 has the surface properties of the surface protective layer 5 described above.
  • Such a decorative sheet 1 gives the user a moist tactile sensation when the user slides a finger over the surface while pressing the surface of the surface protective layer 5 with the skin, for example, when the user slides a finger over the surface while pressing the surface of the surface protective layer 5 with the finger. That is, when touched by the above action, this decorative sheet 1 can gradually increase the contact area between the finger and the convex surface while keeping the pressing resistance caused by the contact between the finger and the surface small. This gives a tactile sensation as if the surface of the decorative sheet is sticking to the finger.
  • the moist feel gives a sense of comfort and warmth to anyone who touches the decorative sheet 1.
  • the moist feel also gives the decorative sheet 1 a sense of luxury. Therefore, the decorative sheet 1 that gives the user a moist feel is suitable for use in applications where the user's skin comes into contact with the sheet frequently or where the user's skin comes into contact with the sheet for long periods of time, such as table tops, chair armrests, and handrails on stairs and in corridors.
  • the surface protective layer 5 contains the above-mentioned sliding property imparting agent, the above-mentioned pressing resistance can be further reduced. This makes it possible to give the user a strong tactile sensation as if the surface of the decorative sheet is sticking to the user's finger. Therefore, in the above case, it is possible to give the user an even more moist tactile sensation.
  • the surface protective layer 5 of the decorative sheet 1 has the above-mentioned surface properties, and therefore can achieve a low gloss even without containing a gloss regulator (matt additive).
  • Gloss regulators reduce the oil repellency of the layer formed from the resin material, so a surface protective layer 5 containing a gloss regulator is prone to fingerprints.
  • a surface protective layer 5 that does not contain a gloss regulator is less likely to absorb oil, and therefore fingerprints are less likely to adhere to it.
  • a surface protective layer 5 with excellent oil repellency is less likely to cause oil stains or adsorb contaminants.
  • the gloss regulator particles do not fall off, and therefore a decorative sheet 1 containing such a surface protective layer 5 is less likely to cause gloss changes or scratches.
  • Oxygen in the gas phase not only absorbs short-wavelength ultraviolet light, but also inhibits radical polymerization.
  • the effect of oxygen contained in the gas phase on radical polymerization is greatest in the portion of the coating film made of ionizing radiation curable resin adjacent to the gas phase, and decreases as the distance from the coating film surface increases. Therefore, by changing the oxygen concentration in the gas phase in the first irradiation step, it is possible to change the relationship between the distance from the coating film surface and the progress of the crosslinking reaction.
  • the thickness of the cured film formed on the surface of the coating by the first irradiation process and the degree of expansion of the cured film in the in-plane direction according to the progress of the crosslinking reaction change.
  • the thickness of the cured film and the degree of expansion of the cured film in the in-plane direction are also affected by the integrated light amount in the first irradiation process.
  • the thickness of the cured film and the degree of expansion of the cured film in the in-plane direction also affect the surface properties of the surface protective layer.
  • the particle size and amount of particles added in the coating film, as well as the thickness of the coating film also affect the formation of wrinkles.
  • the stirring method of the coating liquid for the surface protective layer by appropriately setting the stirring method of the coating liquid for the surface protective layer, the composition of the ionizing radiation curable resin, the particle size and amount added, the thickness of the coating film, the oxygen concentration in the gas phase in the first irradiation step, and the integrated light amount in the first irradiation step, it is possible to obtain a surface protective layer having the desired surface properties.
  • the primary transfer obtained by performing transfer using this decorative sheet 1 as a plate has a wide convex portion formed on its top surface in a small area.
  • the primary transfer with such convex portions formed is pressed with a finger, the pressing resistance is large, and even a slight increase in pressure significantly increases the contact area. For this reason, the primary transfer does not give the user a moist feel to the touch.
  • the secondary transfer obtained by performing transfer using the primary transfer as a plate has a surface shape similar to that used for the primary transfer. Therefore, this secondary transfer gives the user a moist feel to the touch.
  • Example 1 The decorative sheet 1 described with reference to Figures 1 to 3 was produced by the following method.
  • the transparent resin layer 4, the primer layer 6, the adhesive layer 7 and the concealing layer 8 were omitted.
  • an impregnated paper (GFR-506: manufactured by Kohjin Co., Ltd.) having a basis weight of 50 g/ m2 was prepared as the raw fabric layer 2.
  • a design layer 3 was formed using an oil-based nitrocellulose resin-based gravure printing ink (PCNT (PCRNT) various colors: manufactured by Toyo Ink Co., Ltd.).
  • a coating liquid for a surface protective layer was prepared.
  • the coating liquid for the surface protective layer the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 15 moles added)
  • the coating liquid for forming the surface protective layer was stirred. Stirring was carried out as follows. First, the coating liquid for the surface protective layer was placed in a stirring vessel. The stirring vessel used was ZT-20 (manufactured by Satake Multinics Co., Ltd.). For stirring, a Satake Multi A Mixer AT14-VPR-0.09BI (manufactured by Satake Multinics Co., Ltd.) was used. The stirring method was central stirring. The stirring time was 5 minutes.
  • the coating liquid for the surface protective layer was applied onto the pattern layer 3.
  • the coating film made of the coating liquid for the surface protective layer was formed to a thickness of 4.3 ⁇ m.
  • a second irradiation step was carried out. Specifically, the coating film was irradiated with ionizing radiation and cured in its entirety to form a surface protective layer 5. In this manner, a decorative sheet 1 was obtained.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 3 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.1 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 4 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.9 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.1 ⁇ m.
  • Example 6 A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 10 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.3 ⁇ m.
  • Example 7 A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 11 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 12 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.3 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 1.2 ⁇ m. The power for stirring the coating liquid for surface protective layer was 0.3 kW.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 1.1 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 2.1 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 2.8 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 9.4 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 17.2 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points.
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer, and the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 18.9 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: In this example, the following particles were added to the coating liquid for the surface protective layer.
  • Particles Product name sicastar 43-00-154 (manufactured by Corefront Co., Ltd.) Particle size: 14 ⁇ m Blend ratio: 5 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.3 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane triacrylate
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 3 moles added)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.9 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 6 moles added)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.9 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 9 moles added)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.3 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 20 moles added)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 6.1 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (EO 20 moles added)
  • EO 20 moles added Ethoxylated pentaerythritol tetraacrylate
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.1 ⁇ m.
  • a mold for shaping was prepared.
  • the mold for shaping was prepared in the same manner as the manufacturing method of the decorative sheet according to Example 26, except for the following points. That is, in the preparation of the mold for shaping, a coating film made of the coating liquid for the surface protective layer was formed to a thickness of 3.9 ⁇ m.
  • this mold was used to transfer the surface shape of the mold as a template onto the surface protection layer on the decorative sheet.
  • the transfer was performed using the following method.
  • a polydimethylsiloxane mixture was prepared by diluting a UV-curable polydimethylsiloxane liquid (Agent A: X-34-4184A, Agent B: X-34-4184B, manufactured by Shin-Etsu Chemical Co., Ltd.) with decamethylcyclopentasiloxane (KF-995, manufactured by Shin-Etsu Chemical Co., Ltd.) so that the weight ratio of Agent A to Agent B to the diluent was 1:1:7 or 1:1:8.
  • a UV-curable polydimethylsiloxane liquid Agent A: X-34-4184A, Agent B: X-34-4184B, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KF-995 decamethylcyclopentasiloxane
  • a coating film was formed on the above-mentioned mold for shaping so that the coating amount of the above-mentioned polydimethylsiloxane liquid was 10 g/m 2, and then a PET film having a thickness of 15 ⁇ m was pressed onto the coating film.
  • the mold for shaping was peeled off from the UV-cured film of the polydimethylsiloxane mixture. This UV-cured film of the polydimethylsiloxane mixture is called the primary transfer film.
  • the surface was modified with perfluorodecyltriethoxysilane by gas phase deposition, and the reaction was completed in an oven at 100 ° C. Furthermore, the above-mentioned polydimethylsiloxane mixed solution was applied on the above-mentioned primary transfer film in the same amount as above, and a PET film having a thickness of 15 ⁇ m was pressed from above the coating film. The polydimethylsiloxane mixed solution cured by UV irradiation is called a secondary transfer film. This secondary transfer film was peeled off from the primary transfer film to form a mold used in Comparative Example 3.
  • the mold used in Comparative Example 3 was pressed onto the coating film of the surface protection layer formed in the same manner as in Example 26 except that curing was performed by excimer irradiation and electron beam irradiation, and then the same electron beam irradiation as in Example 26 was repeated twice from above the PET, the surface protection layer was cured, and the secondary transfer film was peeled off, thereby forming the surface protection layer according to Comparative Example 3.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (EO 35 moles added)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.8 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 6 moles added)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 15 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.2 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Ethylene glycol diacrylate (EO 9 moles added)
  • Product name Light Acrylate 9EG-A (Kyoeisha Chemical Co., Ltd.)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.7 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 5, except for the following points: In this example, the following agent for imparting sliding properties was further added to the coating liquid for the surface protective layer.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • Example 2 Ethoxylated dipentaerythritol hexaacrylate (EO 12 moles added)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 6.2 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • ⁇ Ionizing radiation curable resin Type Pentaerythritol tetraacrylate Product name: NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • the same particles as those used in Example 2 were added to the coating liquid for surface protective layer so that the amount of the particles was 5 parts by mass.
  • a coating film made of the coating liquid for surface protective layer was formed to a thickness of 6.8 ⁇ m.
  • Thickness of the surface protective layer The thickness of the surface protective layer was measured as follows. The decorative sheet 1 was embedded in a resin such as a cold-curing epoxy resin or a UV-curable resin and fully cured, then cut so that the cross section of the decorative sheet 1 appeared, and mechanically polished to obtain a measurement surface. The thickness of the surface protective layer was then measured using a scanning electron microscope SIGMA500 manufactured by Carl Zeiss Microscopy. The length was measured at any 25 points, and the average length measurement value of the 25 points was defined as the "thickness t of the surface protective layer". The measurement conditions were an acceleration voltage of 0.5 keV (low acceleration voltage), a shooting mode of SE2 mode, and a magnification of 2000 times. No sputtering was performed on the measurement sample. The "thickness t of the surface protective layer" was equal to the thickness of the coating film made of the coating liquid for the surface protective layer.
  • Group 3 Almost no resistance was felt when pushing, but the finger felt as if it was strongly sticking to the surface of the decorative sheet. In other words, a strong, moist feel was felt. The above procedure was repeated until the evaluations by each evaluator coincided three or more times in succession and the evaluation results between the evaluators coincided three times in succession.
  • each of the evaluators was blindfolded and pressed the surface of the surface protective layer with a finger while sliding the finger over the surface, and then the tactile sensation was classified into the two groups. This procedure was repeated until the evaluations by each evaluator were consistent three or more times in a row, and the evaluation results between the evaluators were consistent three times in a row. From the results, the skin sensation was evaluated according to the following criteria.
  • A smooth: Group 1 B (moist): Group 2 BB (very moist): Group 3 (4) Fingerprint resistance
  • the ability to wipe off fingerprints was evaluated.
  • the 60-degree gloss of the surface of each decorative sheet was measured, and this 60-degree gloss was taken as the initial gloss.
  • a fingerprint-resistant evaluation liquid was applied onto the surface protective layer, and the fingerprint-resistant evaluation liquid applied to the surface of the decorative sheet was wiped off.
  • a higher fatty acid was used as the fingerprint-resistant evaluation liquid.
  • the 60-degree gloss of the part from which the fingerprint-resistant evaluation liquid was wiped off was measured, and this 60-degree gloss was taken as the gloss after wiping.
  • Fingerprint wiping rate (%) (glossiness after wiping/initial glossiness) x 100
  • the evaluation criteria were as follows. AA: 70% or more and less than 250% A: 50% or more and less than 70%, or 250% or more and less than 300% B: Less than 50%, or 300% or more (5) Stain resistance
  • a stain A test specified in the Japanese Agricultural Standards (JAS) was performed. That is, lines of 10 mm width were drawn on the surface protective layer of each decorative sheet with blue ink, black quick-drying ink, and red crayon, and left for 4 hours. After that, the blue ink, black quick-drying ink, and red crayon lines were wiped off with a cloth soaked in ethanol.
  • each decorative sheet was attached to wood substrate B. Then, a steel wool rubbing test was carried out 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 scratches and changes in gloss on the surface of the decorative sheet were visually confirmed.
  • the evaluation criteria were as follows. AA: No scratches or changes in gloss occurred on the surface. A: Minor scratches or changes in gloss occurred on the surface. B: Significant scratches or changes in gloss occurred on the surface.
  • wood base material B was bent 90 degrees along the V-shaped groove so that the surface of the decorative sheet facing the surface protection layer (i.e., the surface of the decorative sheet) formed a mountain fold.
  • the bent portion of the surface of the decorative sheet was observed using an optical microscope to see if there was any whitening or cracking, and the bending workability was evaluated.
  • the evaluation criteria were as follows. AA: No whitening or cracks were observed. A: Some whitening was observed. B: Whitening was observed over the entire surface, or cracks were observed in some areas.
  • the decorative sheets of Examples 1 to 29 provided the evaluators with a moist feel. Furthermore, the decorative sheets of Examples 1 to 6, 11, 12, 15 to 19, 23, 24, and 29 had low gloss and were excellent in fingerprint resistance, stain resistance, scratch resistance, and processability. On the other hand, as shown in Tables 2, 4, and 5, Comparative Examples 1 to 6 did not provide the evaluators with a moist feel, but rather provided a smooth feel.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014119510A1 (ja) * 2013-01-29 2014-08-07 東洋紡株式会社 表面加飾用フィルム
JP2016097510A (ja) * 2014-11-18 2016-05-30 大日本印刷株式会社 化粧シート
JP2019119138A (ja) 2018-01-05 2019-07-22 凸版印刷株式会社 化粧材
WO2022054646A1 (ja) * 2020-09-14 2022-03-17 大日本印刷株式会社 艶消物品
WO2022239270A1 (ja) * 2021-05-12 2022-11-17 凸版印刷株式会社 化粧シート、及び化粧シートの製造方法
WO2023136304A1 (ja) * 2022-01-13 2023-07-20 凸版印刷株式会社 化粧シート、及び化粧シートの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014119510A1 (ja) * 2013-01-29 2014-08-07 東洋紡株式会社 表面加飾用フィルム
JP2016097510A (ja) * 2014-11-18 2016-05-30 大日本印刷株式会社 化粧シート
JP2019119138A (ja) 2018-01-05 2019-07-22 凸版印刷株式会社 化粧材
WO2022054646A1 (ja) * 2020-09-14 2022-03-17 大日本印刷株式会社 艶消物品
WO2022239270A1 (ja) * 2021-05-12 2022-11-17 凸版印刷株式会社 化粧シート、及び化粧シートの製造方法
WO2023136304A1 (ja) * 2022-01-13 2023-07-20 凸版印刷株式会社 化粧シート、及び化粧シートの製造方法

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