WO2024147319A1 - 化粧シート - Google Patents

化粧シート Download PDF

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Publication number
WO2024147319A1
WO2024147319A1 PCT/JP2023/046696 JP2023046696W WO2024147319A1 WO 2024147319 A1 WO2024147319 A1 WO 2024147319A1 JP 2023046696 W JP2023046696 W JP 2023046696W WO 2024147319 A1 WO2024147319 A1 WO 2024147319A1
Authority
WO
WIPO (PCT)
Prior art keywords
decorative sheet
protective layer
surface protective
layer
mass
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.)
Ceased
Application number
PCT/JP2023/046696
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
大輔 村田
まち子 森田
絵理佳 阿久津
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Holdings Inc
Original Assignee
Toppan Holdings Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to EP23914805.9A priority Critical patent/EP4647251A4/en
Priority to KR1020257021100A priority patent/KR20250133655A/ko
Priority to CN202380089577.1A priority patent/CN120435381A/zh
Priority to JP2024522411A priority patent/JP7582559B1/ja
Publication of WO2024147319A1 publication Critical patent/WO2024147319A1/ja
Priority to JP2024192149A priority patent/JP2025010357A/ja
Priority to US19/258,539 priority patent/US20250332810A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/02—Patterned paper
    • 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
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31F—MECHANICAL WORKING OR DEFORMATION OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31F1/00—Mechanical deformation without removing material, e.g. in combination with laminating
    • B31F1/07—Embossing, i.e. producing impressions formed by locally deep-drawing, e.g. using rolls provided with complementary profiles
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/06—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/002—Tissue paper; Absorbent paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/408—Matt, dull surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • 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
    • B32B2451/00—Decorative or ornamental articles

Definitions

  • Decorative sheets are used to decorate the surfaces of interior and exterior materials such as building fixtures, furniture, construction materials, and flooring, for the purpose of imparting design and durability to these materials.
  • Decorative sheets are generally widely used as decorative panels that are attached to the surfaces of substrates such as wood, wood boards, metal plates, non-flammable boards, paper substrates, and resin substrates via adhesives or the like.
  • 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.
  • Durability is a comprehensive assessment of scratch resistance, stain resistance, and whether these can be maintained over the long term. Requirements vary depending on the environment and situation in which the decorative sheet is used, but there is always a demand for decorative sheets with high performance.
  • 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 smooth feel and has excellent uniformity of feel.
  • an original fabric layer and a surface protective layer provided on one surface of the original fabric layer, and an uneven structure including a plurality of ridge-like portions each protruding in a ridge shape is provided on the surface of the surface protective layer, and the uneven structure of the surface protective layer has a protruding peak height Rpk of less than 3.5 ⁇ m, and the surface protective layer has a mass concentration C (mass %) of carbon atoms, a mass concentration O (mass %) of oxygen atoms, and a mass concentration Si (mass %) of silicon atoms that satisfy the following relationship formula: 0.5 ⁇ Si/(C+O+Si) ⁇ 100 A decorative sheet that satisfies the above requirements is provided.
  • a decorative sheet relating to the above aspect is provided in which the protruding peak height Rpk is 0.5 ⁇ m or more.
  • the surface protective layer has a mass concentration C (mass %) of carbon atoms, a mass concentration O (mass %) of oxygen atoms, and a mass concentration Si (mass %) of silicon atoms that satisfy the following relationship: 0.5 ⁇ Si/(C+O+Si) ⁇ 100 ⁇ 5.0
  • a decorative sheet according to any of the above aspects which satisfies the above.
  • the surface protective layer includes a cured product of an ionizing radiation curable resin.
  • the ink used to form the design layer 3 may further contain, in addition to the binder, for example, pigments contained in ordinary inks, colorants such as dyes, extender pigments, solvents, and various additives.
  • pigments having high versatility include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.
  • the resin material of the adhesive layer 7 is not particularly limited, but may be appropriately selected from acrylic, polyester, polyurethane, epoxy, and other resin materials.
  • An ethylene-vinyl acetate copolymer resin adhesive may also be used as the resin material of the adhesive layer 7.
  • the coating method may be appropriately selected depending on the viscosity of the adhesive. Generally, gravure coating is used, and the adhesive layer 7 is formed on the upper surface of the pattern layer 3 by gravure coating, and then the transparent resin layer 4 is laminated. Note that the adhesive layer 7 may be omitted if sufficient adhesive strength is obtained between the transparent resin layer 4 and the pattern layer 3.
  • 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 uneven structure of the surface protective layer 5 preferably has an average length RSm of the roughness curve element of 800 ⁇ m or less, more preferably 550 ⁇ m or less, even more preferably 350 ⁇ m or less, even more preferably 320 ⁇ m or less, and even more preferably 300 ⁇ m or less.
  • the "average length RSm of the roughness curve element” is a surface property parameter defined in JIS B0601:2013.
  • This average length RSm is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more, and even more preferably 80 ⁇ m or more. It is difficult to manufacture a structure in which this average length RSm is small and the protruding peak height Rpk is relatively large.
  • the mass concentration C (mass %) of carbon atoms, the mass concentration O (mass %) of oxygen atoms, and the mass concentration Si (mass %) of silicon atoms satisfy the following relational expression (1).
  • the surface protective layer 5 contains an ionizing radiation curable resin and silica particles, which will be described later.
  • the value of ⁇ Si/(C+O+Si) ⁇ 100 is preferably 0.75 or more, and more preferably 1.0 or more.
  • the contents of C (mass %), O (mass %), and Si (mass %) preferably satisfy the following relational expression (2).
  • 0.5 ⁇ Si/(C+O+Si) ⁇ 100 ⁇ 5.0 It is preferable that the value of ⁇ Si/(C+O+Si) ⁇ 100 is 5.0 or less from the viewpoints of scratch resistance, contamination resistance, weather resistance, etc. From the same viewpoint, the value of ⁇ Si/(C+O+Si) ⁇ 100 is more preferably 3.5 or less, and further preferably 2.0 or less.
  • the main component of the ionizing radiation curable resin is preferably an acrylate.
  • the main component of the ionizing radiation curable resin means 60 parts by mass or more when the total solid content of the ionizing radiation curable resin is taken as 100 parts by mass.
  • 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 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 second irradiation step described below, and therefore wrinkles corresponding to the ridged portions 5B are more likely to appear on the coating film surface. It also makes it possible to uniformly generate wrinkles over a wide area, which contributes to improving the uniformity of the tactile feel. However, if the number of repetitions is increased, the crosslinking density decreases, and the scratch resistance of the surface protective layer decreases.
  • 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 and 30 or less, more preferably 3 or more and 20 or less.
  • a tetrafunctional acrylate containing a repeating structure is 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 or more and 50 or less, and even more preferably 20 or more and 50 or less.
  • 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 main component of the ionizing radiation curable resin is preferably an acrylate.
  • the acrylate may be composed of the acrylate described above.
  • the acrylate may be composed of the acrylate described above (hereinafter referred to as the first acrylate) and a second acrylate different from the first acrylate.
  • the compounding ratio of the first acrylate to the second acrylate is not particularly limited, but can be, for example, a mass ratio within the range of 90:10 to 20:80.
  • the second acrylate is, for example, a monofunctional to hexafunctional acrylate.
  • the acrylate may be composed of a first acrylate containing a repeating structure and a mono- to hexa-functional second acrylate.
  • the repeating structure of the first acrylate is any one of ethylene oxide, propylene oxide, and ⁇ -caprolactone, and the number of repetitions of the repeating structure is 3 or more.
  • Examples of the second acrylate include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
  • the peak height Rpk tends to be smaller and the average length RSm of the roughness curve element tends to be larger.
  • the glossiness of the surface protective layer 5 can be increased to increase the glossiness variation, or the thickness of the surface protective layer 5 can be increased to increase the thickness variation.
  • the coating liquid for the surface protective layer contains silica particles.
  • silica particles are contained in the coating liquid for the surface protective layer, wrinkles can be more uniformly generated on the coating surface in the second irradiation step described below, which contributes to improving the uniformity of the tactile feel.
  • the coating liquid for the surface protective layer may further contain particles other than silica particles.
  • the particles other than silica particles that can be used include particles made of organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads, and particles made of inorganic materials such as glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.
  • the particles other than silica particles may be contained in the coating liquid for the surface protective layer in an amount of, for example, 20% by mass or less of the total particles.
  • the average particle size (D50) of the above particles, including silica particles, is preferably 10 ⁇ m or less.
  • the average particle size (D50) of the particles is more preferably 1 ⁇ m or more and 8 ⁇ m or less, and even more preferably 2 ⁇ m or more and 6 ⁇ m or less.
  • the particles are likely to fall off from the surface protective layer 5, which may make it difficult to achieve high scratch resistance.
  • the particles are small, the effect of generating wrinkles uniformly is small.
  • the "average particle size (D50)" is the median size (D50) measured by a laser diffraction/scattering type particle size distribution measuring device. If the coating liquid for the surface protective layer contains particles, the surface protective layer 5 obtained from this coating liquid will also contain particles. The average particle size of the particles contained in the surface protective layer 5 can be determined by observing the cross section of the layer and averaging the particle sizes of multiple particles. The value obtained in this manner is substantially the same as the median size (D50) measured by a laser diffraction/scattering type particle size distribution measuring device. Therefore, the above-mentioned range of average particle sizes can also be interpreted as the range of average particle sizes of the particles contained in the surface protective layer 5.
  • the amount of particles containing silica particles added is preferably 1.3 parts by mass or more and 22 parts by mass or less, more preferably 1.3 parts by mass or more and 15 parts by mass or less, and even more preferably 3 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of ionizing radiation curable resin.
  • the above amount added refers to the amount of silica particles added.
  • the amount of particles is within the above range, the effect of generating wrinkles uniformly is particularly large.
  • 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 antibacterial agents and antifungal agents.
  • 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.
  • 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.
  • the amount of photoinitiator added is preferably 0.1 to 10 parts by mass, more preferably 0.25 to 8 parts by mass, and even more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of ionizing radiation curable resin. If the amount of photoinitiator is less than 0.1 parts by mass, the effect of the first irradiation step described below is less likely to be achieved. If the amount of photoinitiator is more than 10 parts by mass, the coating film will be completely cured, and wrinkles will be less likely to form in the subsequent second irradiation step.
  • the coating film is preferably semi-cured by carrying out the first irradiation step.
  • the coating film is irradiated with light having a wavelength of about 200 nm or more and 400 nm or less (hereinafter referred to as the first irradiation light).
  • the first irradiation light By semi-curing the coating film by carrying out the first irradiation step, it is possible to form wrinkles more uniformly in the second irradiation step described below.
  • a high-pressure mercury lamp, a metal halide lamp, or a single-wavelength LED lamp with a wavelength of 200 nm or more and 400 nm or less can be selected and used.
  • the integrated light amount of the first irradiation light is preferably 2 mJ/cm2 or more and 100 mJ/cm2 or less, more preferably 10 mJ/cm2 or more and 80 mJ/ cm2 or less, and even more preferably 20 mJ/ cm2 or more and 60 mJ/ cm2 or less. If the integrated light amount is small, the effect of the first irradiation step is difficult to appear. If the integrated light amount is large, the coating film is completely cured, and wrinkles are difficult to form in the subsequent second irradiation step.
  • the second 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 second irradiation light).
  • the ionizing radiation curable resin contained in the coating liquid for the surface protective layer has a large absorption coefficient for the second irradiation light. Therefore, the second irradiation light incident on the coating film can only reach a position that is several tens to several hundreds of nm away from the outermost surface. Therefore, in the second 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 second irradiation light can only reach a position several tens to several hundreds of nm 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.
  • the monomers present on the surface of the coating film crosslink via the functional groups they possess to form a cured film, but not all of these functional groups are used to crosslink the monomers present on the surface of the coating film. In other words, uncrosslinked functional groups may remain in the cured film.
  • the second irradiation light does not reach monomers that are located away from the surface of the coating film, so no crosslinking reaction occurs there. However, some of the monomers that are located away from the surface of the coating film migrate to the cured film, where they undergo a crosslinking reaction. In this way, the number of molecules involved in the crosslinking reaction increases.
  • the volume of the cured film increases. Since the crosslinking reaction only occurs on the surface of the coating, the cured film cannot increase in volume in the thickness direction, but expands in the in-plane direction. As a result, wrinkles appear on the surface of the coating.
  • the second irradiation light 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.
  • 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 third radiation or irradiation light is ionizing radiation such as an electron beam, or ultraviolet light having a longer wavelength than the second irradiation light.
  • the integrated light amount of the third irradiation light is preferably 10 mJ/ cm2 or more and 500 mJ/ cm2 or less, more preferably 50 mJ/ cm2 or more and 400 mJ/ cm2 or less, and even more preferably 100 mJ/ cm2 or more and 300 mJ/ cm2 or less.
  • the decorative sheet 1 can be manufactured, for example, by the above method.
  • the decorative sheet 1 may also be manufactured by other methods.
  • a plate may be formed using the method described above for the surface protective layer 5, and the surface protective layer 5 having a concave-convex structure on its surface may be formed by transfer using this plate.
  • the decorative sheet 1 described with reference to Figures 1 to 3 has the above-mentioned surface properties in the surface protective layer 5.
  • Such a decorative sheet 1 provides the user with a smooth and uniform feel when the user slides the skin over the surface of the surface protective layer 5, for example, when the user slides a finger over the surface of the surface protective layer 5.
  • this decorative sheet 1 allows the user to slide a finger or the like with little frictional force over the entire surface of the surface protective layer 5 without the user feeling the presence of significant irregularities.
  • the decorative sheet 1 which gives the user a smooth 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 is in contact with the sheet for long periods of time, such as furniture.
  • An article using the decorative sheet 1 described above does not cause discomfort to the user when it comes into contact with the user's skin.
  • 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 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 second 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 second 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 second 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. Furthermore, the thickness of the coating also affects the formation of wrinkles.
  • 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.) with a basis weight of 50 g/ m2 was prepared as the original 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.).
  • the coating liquid for the surface protective layer was a mixture of the following ionizing radiation curable resin and the following particles.
  • - Ionizing radiation curable resin Type Ethylene glycol diacrylate (EO 9 moles added)
  • Product name Light Acrylate 9EG-A (Kyoeisha Chemical Co., Ltd.)
  • Formulation 100 parts by weight, particles
  • Particle size 5 ⁇ m
  • Formulation 2 parts by weight
  • Formulation 1 part by mass
  • a coating film made of the coating liquid for surface protection layer was formed to a thickness of 5 ⁇ m.
  • the first irradiation step was carried out. Specifically, in the atmosphere, the surface of the coating film made of the coating liquid for surface protection layer was irradiated with ultraviolet light having a main wavelength of 365 nm using a high-pressure mercury lamp so that the cumulative light amount was 50 mJ/ cm2 . This resulted in semi-curing of the coating film.
  • the second irradiation step was carried out. Specifically, under atmospheric pressure and in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm, the surface of the coating film made of the coating liquid for surface protection layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp so that the cumulative light amount was 50 mJ/ cm2 . This caused wrinkles to form on the surface of the coating film.
  • Decorative sheet 1 was produced in the same manner as in Example 2, except for the following points: In this example, the blending amounts of the following particles were changed.
  • Decorative sheet 1 was produced in the same manner as in Example 2, except for the following points: In this example, the blending amounts of the following particles were changed.
  • 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 Caprolactone modified tris-(2-acryloxyethyl) isocyanurate (3 moles of caprolactone (CL) added)
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, so that the accumulated light amount was 100 mJ/ cm2 .
  • 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. The coating film made of the coating liquid for the surface protective layer was formed to a thickness of 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 35 moles added)
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, so that the accumulated light amount was 50 mJ/ cm2 .
  • 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 Propoxylated pentaerythritol tetraacrylate (PO35 moles added)
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, so that the accumulated light amount was 50 mJ/ cm2 .
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, so that the accumulated light amount was 10 mJ/ cm2 .
  • 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 1 Trimethylolpropane EO modified triacrylate (EO 6 moles added)
  • the surface of the coating film made of the coating liquid for surface protection layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm under atmospheric pressure, so that the accumulated light amount was 10 mJ/ cm2 .
  • 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. The coating film made of the coating liquid for the surface protective layer was formed to a thickness of 14 ⁇ m.
  • the coating liquid for the surface protective layer was a mixture of the following ionizing radiation curable resin and the following particles.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 6 moles added)
  • Particle size 5 ⁇ m Blending ratio: 15 parts by mass
  • the first and second irradiation steps were not carried out, and the coating film made of the coating liquid for forming a surface protective layer was cured only by the third irradiation step.
  • 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
  • Stain resistance To evaluate stain resistance, the stain A test specified in the Japanese Agricultural Standards (JAS) was carried out. That is, on the surface protective layer of each decorative sheet, lines of 10 mm width were drawn 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.
  • JS Japanese Agricultural Standards
  • 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 decorative sheets according to Examples 1 to 24 provided the evaluators with a smooth feel and uniformity of the feel.
  • the decorative sheets according to Examples 1 to 24 also had low gloss and were excellent in fingerprint resistance, stain resistance, and scratch resistance.
  • the decorative sheets according to Comparative Examples 1 and 2 did not provide the evaluators with a smooth feel and were poor in fingerprint resistance, stain resistance, and scratch resistance, as shown in Table 4.
  • the decorative sheets according to Comparative Examples 3 and 4 also had low gloss and were excellent in fingerprint resistance, stain resistance, and scratch resistance, but did not provide the evaluators with a smooth feel.
  • the decorative sheet according to Comparative Example 5 also had low gloss and was excellent in fingerprint resistance, stain resistance, and scratch resistance, and provided the evaluators with a smooth feel, but was poor in uniformity of the feel.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Floor Finish (AREA)
PCT/JP2023/046696 2023-01-04 2023-12-26 化粧シート Ceased WO2024147319A1 (ja)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP23914805.9A EP4647251A4 (en) 2023-01-04 2023-12-26 Decorative sheet
KR1020257021100A KR20250133655A (ko) 2023-01-04 2023-12-26 화장 시트
CN202380089577.1A CN120435381A (zh) 2023-01-04 2023-12-26 装饰片
JP2024522411A JP7582559B1 (ja) 2023-01-04 2023-12-26 化粧シート
JP2024192149A JP2025010357A (ja) 2023-01-04 2024-10-31 化粧シート
US19/258,539 US20250332810A1 (en) 2023-01-04 2025-07-02 Decorative sheet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023000276 2023-01-04
JP2023-000276 2023-01-04

Related Child Applications (1)

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JPWO2025159123A1 (https=) * 2024-01-22 2025-07-31
WO2025159124A1 (ja) * 2024-01-22 2025-07-31 Ｔｏｐｐａｎホールディングス株式会社 化粧シート

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WO2017033972A1 (ja) * 2015-08-24 2017-03-02 凸版印刷株式会社 化粧シート
JP2018144437A (ja) * 2017-03-08 2018-09-20 凸版印刷株式会社 化粧シートおよび化粧シートの製造方法
JP2020075420A (ja) * 2018-11-08 2020-05-21 凸版印刷株式会社 化粧シート及びその製造方法
JP2021137990A (ja) * 2020-03-03 2021-09-16 凸版印刷株式会社 化粧シート、化粧板及び化粧シートの製造方法
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

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WO2017033972A1 (ja) * 2015-08-24 2017-03-02 凸版印刷株式会社 化粧シート
JP2018144437A (ja) * 2017-03-08 2018-09-20 凸版印刷株式会社 化粧シートおよび化粧シートの製造方法
JP2020075420A (ja) * 2018-11-08 2020-05-21 凸版印刷株式会社 化粧シート及びその製造方法
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JPWO2025159123A1 (https=) * 2024-01-22 2025-07-31
WO2025159123A1 (ja) * 2024-01-22 2025-07-31 Ｔｏｐｐａｎホールディングス株式会社 化粧シート
WO2025159124A1 (ja) * 2024-01-22 2025-07-31 Ｔｏｐｐａｎホールディングス株式会社 化粧シート
JPWO2025159124A1 (https=) * 2024-01-22 2025-07-31

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JP2025010357A (ja) 2025-01-20
KR20250133655A (ko) 2025-09-08
CN120435381A (zh) 2025-08-05
JP7582559B1 (ja) 2024-11-13
US20250332810A1 (en) 2025-10-30
JPWO2024147319A1 (https=) 2024-07-11
EP4647251A4 (en) 2026-04-29

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