WO2024262457A1 - 化粧シート - Google Patents

化粧シート Download PDF

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Publication number
WO2024262457A1
WO2024262457A1 PCT/JP2024/021878 JP2024021878W WO2024262457A1 WO 2024262457 A1 WO2024262457 A1 WO 2024262457A1 JP 2024021878 W JP2024021878 W JP 2024021878W WO 2024262457 A1 WO2024262457 A1 WO 2024262457A1
Authority
WO
WIPO (PCT)
Prior art keywords
adjustment layer
decorative sheet
gloss adjustment
coating film
ionizing radiation
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/JP2024/021878
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
絵理佳 阿久津
典子 笹木
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 JP2024559943A priority Critical patent/JP7758223B2/ja
Priority to KR1020267001382A priority patent/KR20260025845A/ko
Priority to EP24825858.4A priority patent/EP4733063A1/en
Priority to CN202480039085.6A priority patent/CN121335804A/zh
Publication of WO2024262457A1 publication Critical patent/WO2024262457A1/ja
Priority to US19/427,720 priority patent/US20260108912A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/02—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a matt or rough surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
    • 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
    • B32B3/10—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 discontinuous layer, i.e. formed of separate pieces of material
    • 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
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements

Definitions

  • the present invention relates to a decorative sheet.
  • Decorative materials used for the surface decoration of the interior and exterior of buildings, fittings, furniture, etc. are generally in the form of decorative boards, which are made by attaching a decorative sheet to the surface of a substrate via an adhesive or the like.
  • the decorative sheet is usually given a desired pattern, such as a wood grain or stone pattern.
  • decorative sheets that do not simply express a wood grain or stone pattern in a two-dimensional manner, but also express a three-dimensional unevenness similar to the surface of natural wood or stone are widely used, mainly in applications where a luxurious feel is desired.
  • a printed layer containing a pattern corresponding to the area where the depressions are to be expressed is formed on one side of the substrate.
  • a transparent or semi-transparent first gloss adjustment layer with low gloss is formed on the entire surface of the substrate on which the printed layer is formed.
  • a transparent or semi-transparent second gloss adjustment layer with high gloss is formed on the entire surface of the first gloss adjustment layer except for the area corresponding to the pattern. Note that if the relationship between high and low gloss levels is reversed between the first and second gloss adjustment layers, a decorative sheet with a reversed relationship between the depressions and protrusions can be obtained.
  • This method allows the creation of a three-dimensional textured effect on any substrate without the need for special chemicals, simply by preparing two types of paint that impart different levels of gloss. Furthermore, the formation of the gloss-adjusting layer with a different gloss level can be performed by a conventional printing method such as gravure printing, following the formation of the pattern (pattern ink layer). Therefore, no special equipment is required, production efficiency is high, and alignment of the second synthetic paint layer with the above pattern is easy. Furthermore, the second gloss-adjusting layer can be much thinner than the height difference of the unevenness that should be perceived by the observer, so the amount of resin used can be reduced, and it is also advantageous in terms of flexibility, making it easy to realize a decorative sheet with excellent suitability for folding processing. Another advantage is that there are no large height differences in the surface of the decorative sheet, so contaminants do not remain in the recesses.
  • the objective of the present invention is to provide a decorative sheet that has excellent scratch resistance and adhesion between gloss-adjusting layers.
  • a decorative sheet comprising: an original fabric layer; a surface protective layer; the surface protective layer being disposed on the original fabric layer; a first gloss adjustment layer, the first ionizing radiation curable resin containing only a cured product of a first ionizing radiation curable resin as a resin cured product, the first ionizing radiation curable resin being a first mixture of acrylate and methacrylate; and a second gloss adjustment layer, partially covering an upper surface of the first gloss adjustment layer, containing only a cured product of a second ionizing radiation curable resin as a resin cured product, and having a lower specular gloss GS (60°) than the first gloss adjustment layer.
  • a decorative sheet according to the above aspect, in which in the first ionizing radiation curable resin, the ratio of the number of moles of methacryloyl groups to the total number of moles of acryloyl groups and the number of moles of methacryloyl groups is within the range of 3% to 50%.
  • a decorative sheet according to any of the above aspects, in which the methacrylate is a monofunctional, difunctional, or trifunctional methacrylate.
  • a decorative sheet according to any of the above aspects, in which the second ionizing radiation curable resin is an acrylate or a second mixture of an acrylate and a methacrylate, and the second mixture has a smaller proportion of the number of moles of methacryloyl groups in the sum of the number of moles of acryloyl groups and the number of moles of methacryloyl groups compared to the first mixture.
  • the second ionizing radiation curable resin is an acrylate or a second mixture of an acrylate and a methacrylate
  • the second mixture has a smaller proportion of the number of moles of methacryloyl groups in the sum of the number of moles of acryloyl groups and the number of moles of methacryloyl groups compared to the first mixture.
  • a decorative sheet according to any of the above aspects, in which the second ionizing radiation curable resin contains a bifunctional or higher functional acrylate having a repeating structure.
  • a decorative sheet according to the above aspect in which the repeating structure is repeated three or more times.
  • a decorative sheet according to any of the above aspects, in which the surface of the second gloss adjustment layer is provided with an uneven structure including a plurality of ridge-like portions, each of which protrudes in a ridge-like shape.
  • a decorative sheet according to the above aspect in which the uneven structure has a ratio RSm/Ra of the average length RSm of the roughness curve elements to the arithmetic mean roughness Ra in the range of 10 to 900, preferably in the range of 10 to 500.
  • a decorative sheet according to any of the above aspects, in which the thickness of each of the first gloss adjustment layer and the second gloss adjustment layer is within the range of 2 ⁇ m or more and 20 ⁇ m or less.
  • the second gloss adjustment layer further contains particles having an average particle size of 10 ⁇ m or less.
  • a decorative sheet according to the above aspect in which the mass of the particles is in the range of 0.5 parts by mass or more and 20 parts by mass or less when the mass of the second ionizing radiation curable resin is 100 parts by mass.
  • the first gloss adjustment layer has a specular gloss GS(60°) of 3 or more
  • the second gloss adjustment layer has a specular gloss GS(60°) of 20 or less, preferably 10 or less.
  • a decorative sheet according to any of the above aspects, in which the difference between the specular gloss GS(60°) of the first gloss adjustment layer and the specular gloss GS(60°) of the second gloss adjustment layer is 1 or more.
  • 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: forming a first coating film on an original layer, the first coating film containing only a first ionizing radiation curable resin as a resin, the first ionizing radiation curable resin being a first mixture of acrylate and methacrylate; carrying out a first irradiation step of irradiating the first coating film with ionizing radiation or ultraviolet light to semi-cure the first coating film; forming a second coating film containing only a second ionizing radiation curable resin as a resin on the semi-cured first coating film so as to partially cover an upper surface of the first coating film; and irradiating the first coating film and the second coating film with ionizing radiation or ultraviolet light to completely cure the first coating film and the second coating film.
  • the complete curing of the first coating film and the second coating film includes a second irradiation step of irradiating the second coating film with light having a wavelength of 200 nm or less, and then a third irradiation step of irradiating the first coating film and the second coating film with ionizing radiation or ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step.
  • the present invention provides a decorative sheet that has excellent scratch resistance and adhesion between gloss-adjusting layers.
  • FIG. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a second gloss-adjusting layer included in the decorative sheet of FIG.
  • FIG. 3 is a microscope image of a second gloss adjustment layer included in a decorative sheet according to one example of the present invention.
  • FIG. 4 is an enlarged cross-sectional view showing a part of the second gloss adjustment layer shown in FIG.
  • 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 second gloss adjustment layer included in the decorative sheet of Fig. 1.
  • Fig. 3 is a micrograph of a second gloss adjustment layer included in a decorative sheet according to one example of the present invention.
  • Fig. 4 is a cross-sectional view showing an enlarged portion of the second gloss adjustment layer shown in Fig. 2.
  • the cross sections shown in Figures 2 and 4 are cross sections along the thickness direction of the second gloss adjustment 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 solid ink layer 3, a pattern ink layer 4, a first gloss adjustment layer 5, and a second gloss adjustment layer 6.
  • the solid ink layer 3, the pattern ink layer 4, the first gloss adjustment layer 5, and the second gloss adjustment layer 6 are provided in this order from the original fabric layer 2 side on the surface opposite to the surface of the original fabric layer 2 facing the substrate B.
  • One or more other layers such as a transparent resin layer may be provided between the pattern ink layer 4 and the first gloss adjustment layer 5.
  • a primer layer may be provided on one or more of the original fabric layer 2, the solid ink layer 3, and the pattern ink layer 4.
  • one or both of the solid ink layer 3 and the pattern ink layer 4 may be omitted.
  • Raw cloth layer 2 or its material can be any of the following: tissue paper, resin-mixed paper, titanium paper, resin-impregnated paper, flame-retardant paper, and inorganic paper; woven or nonwoven fabrics made of natural or synthetic fibers; synthetic resin-based substrates containing synthetic resins such as homo or random polyolefin resins such as polypropylene resins and polyethylene resins, copolymerized polyester resins, amorphous crystalline polyester resins, polyethylene naphthalate resins, polybutylene resins, acrylic resins, polyamide resins, polycarbonate resins, polyvinyl chloride resins, polyvinylidene chloride resins, and fluorine-based resins; wood-based substrates such as wood veneer, veneer, plywood, laminated lumber, particle board, and medium density fiberboard; inorganic substrates such as gypsum boards, cement boards, calcium silicate boards, and ceramic boards; metal substrates made of metals such as iron, copper, aluminum
  • Solid ink layer The solid ink layer 3 is a continuous film formed by covering one entire surface of the original fabric layer 2 with ink.
  • the solid ink layer 3 can function as a concealing layer that conceals the substrate B or the original fabric layer 2.
  • the solid ink layer 3 can also function as a flattening layer.
  • the solid ink layer 3 may have a single-layer structure or a multi-layer structure.
  • the solid ink layer 3 can be formed, for example, using a printing ink (or coating agent) made by dissolving or dispersing a matrix and a colorant such as a dye or pigment in a solvent.
  • a printing ink or coating agent
  • a colorant such as a dye or pigment in a solvent
  • various synthetic resins such as oil-based nitrocellulose resin, two-component urethane resin, acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, epoxy resin, melamine resin, fluorine resin, silicone resin, and daimi rubber resin, or mixtures or copolymers of these can be used.
  • Colorants that can be used include, for example, inorganic pigments such as carbon black, titanium white, zinc oxide, red iron oxide, yellow lead, iron blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; or mixtures of these.
  • inorganic pigments such as carbon black, titanium white, zinc oxide, red iron oxide, yellow lead, iron blue, and cadmium red
  • organic pigments such as azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; or mixtures of these.
  • solvent examples include toluene, xylene, ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, or mixtures thereof.
  • Functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, hardeners, hardening accelerators, and hardening retarders may be added to the inks described above to impart various functions.
  • Pattern ink layer The pattern ink layer 4 is provided to add a pattern to the decorative sheet 1.
  • the pattern pattern is, for example, a wood grain pattern, a stone grain pattern, a sand grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, or a geometric figure.
  • the pattern ink layer 4 is a printing pattern that partially covers the upper surface of the solid ink layer 3. This printing pattern is provided directly under the second gloss adjustment layer. In other words, the second gloss adjustment layer 6 is provided so as to overlap with the pattern ink layer 4.
  • the printing pattern contained in the pattern ink layer 4 and the pattern of the second gloss adjustment layer 6 are orthogonally projected onto a plane perpendicular to the thickness direction and have the same shape and position.
  • shape and position are the same.
  • the pattern ink layer 4 can be formed, for example, using the ink described above for the solid ink layer 3.
  • the pattern ink layer 4 is formed using the number of plates required to express the desired design. That is, the pattern ink layer 4 may be a layer consisting of one printing pattern made of a single ink, or a layer consisting of multiple printing patterns made of different inks. In the latter case, one printing pattern may match the shape and position of the pattern of the second gloss adjustment layer 6, or a combination of two or more printing patterns may match the shape and position of the pattern of the second gloss adjustment layer 6. For example, one printing pattern or a combination of two or more printing patterns may match the shape and position of the pattern of the second gloss adjustment layer 6, and the remaining printing patterns may be located in the area corresponding to the openings of the second gloss adjustment layer 6.
  • the pattern ink layer 4 contains only one printing pattern, this printing pattern is different in color from the solid ink layer 3. If the pattern ink layer 4 contains multiple printing patterns, and the combination of these printing patterns matches the pattern of the second gloss adjustment layer 6 in shape and position, one or more of these printing patterns, for example, all of these printing patterns, are different in color from the solid ink layer 3. If the pattern ink layer 4 contains multiple printing patterns, and one printing pattern or a combination of two or more printing patterns matches the pattern of the second gloss adjustment layer 6 in shape and position, and the remaining printing patterns are located in the area corresponding to the opening of the second gloss adjustment layer 6, one or more of the former printing patterns are different in color from the solid ink layer 3 and one or more of the latter printing patterns. For example, all of the former printing patterns are different in color from the solid ink layer 3 and all of the latter printing patterns.
  • the pattern ink layer 4 is a layer consisting of one printing pattern made of a single ink, and is a different color from the solid ink layer 3.
  • the decorative sheet 1 can further include a transparent resin layer between the pattern ink layer 4 and the first gloss adjustment layer 5.
  • the transparent resin layer can contribute to improving the abrasion resistance of the decorative sheet 1.
  • the transparent resin layer it is preferable to use, for example, a resin composition whose main material is an olefin-based resin.
  • a resin composition whose main material is an olefin-based resin for example, polypropylene, polyethylene, or polybutene can be used as the olefin-based resin.
  • the olefin resin may be a homopolymer or copolymer of two or more ⁇ -olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1
  • the olefin resin may be a copolymer of ethylene or an ⁇ -olefin with other monomers, such as an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl methacrylate copolymer, an ethylene-butyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-butyl acrylate copolymer.
  • ethylene-vinyl acetate copolymer an ethylene-vinyl alcohol copolymer
  • an ethylene-methyl methacrylate copolymer an ethylene-ethyl methacrylate copolymer
  • an ethylene-butyl methacrylate copolymer an ethylene-methyl acrylate copolymer
  • Additives such as heat stabilizers, UV absorbers, light stabilizers, antiblocking agents, catalyst scavengers, and colorants may be added to the transparent resin layer. These additives can be appropriately selected from known additives and used.
  • the transparent resin layer can be formed by various lamination methods such as a method using heat and pressure, an extrusion lamination method, and a dry lamination method.
  • a primer layer can be provided on one or more of the base layer 2, the solid ink layer 3 and the pattern ink layer 4.
  • the surface of the original fabric layer 2 is often in an inactive state. Therefore, in this case, it is preferable to provide a primer layer between the original fabric layer 2 and the substrate B.
  • this primer layer may be omitted, and the original fabric layer 2 may be subjected to a surface modification treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, or dichromate treatment in order to improve the adhesion between the original fabric layer 2 and the substrate B.
  • the primer layer may be made of, for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyesters, or modified products thereof, either alone or in combination. It may be water-based, solvent-based, or emulsion type, and may be either a one-liquid type or a two-liquid type using a hardener.
  • the primer layer may be formed by a method in which a layer formed of a curable ink is cured by exposure to ultraviolet light or electron beams. The most common method is to use a urethane-based ink and harden it with isocyanate.
  • the ink used to form the primer layer may further contain, in addition to a binder, for example, pigments contained in ordinary inks, colorants such as dyes, extender pigments, solvents, various additives, etc.
  • a binder for example, pigments contained in ordinary inks, colorants such as dyes, extender pigments, solvents, various additives, etc.
  • versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, pearl pigments such as mica, etc.
  • an inorganic filler may be added to the primer layer to avoid blocking and to increase adhesion to the adhesive.
  • inorganic fillers include silica, alumina, magnesia, titanium oxide, barium sulfate, etc.
  • the first gloss adjustment layer 5 is provided on the base layer 2.
  • the first gloss adjustment layer 5 covers the solid ink layer 3 and the pattern ink layer 4.
  • the first gloss adjustment layer 5 has a higher specular gloss GS(60°) than the second gloss adjustment layer 6.
  • the specular gloss GS(60°) of the first gloss adjustment layer 5 is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. In one example, the specular gloss GS(60°) of the first gloss adjustment layer 5 is 30 or less.
  • specular gloss GS(60°) is the specular gloss measured at an incident angle of 60 degrees using a glossmeter conforming to ISO2813. Note that the specular gloss GS(60°) is sometimes expressed by adding "%" after the numerical value, but here the "%" is omitted.
  • the first gloss adjustment layer 5 is made of a cured resin.
  • the first gloss adjustment layer 5 may further contain particles.
  • the mass of the cured resin contained in the first gloss adjustment layer 5 is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.
  • the first gloss adjustment layer 5 contains only the cured product of the first ionizing radiation curable resin as the resin cured product.
  • ionizing radiation refers to a charged particle beam such as an electron beam.
  • the first ionizing radiation curable resin is cured by exposure to ionizing radiation.
  • the first ionizing radiation curable resin can also be cured by exposure to ultraviolet light.
  • the first ionizing radiation curable resin may be any known resin, such as various monomers or commercially available oligomers, for example, (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, or epoxy resins.
  • the second ionizing radiation curable resin may be either an aqueous resin or a non-aqueous (organic solvent-based) resin.
  • the second ionizing radiation curable resin may be solvent-free.
  • the main component of the first ionizing radiation curable resin is a first mixture of an acrylate resin and a methacrylate resin.
  • the methacrylate is preferably a monofunctional, difunctional or trifunctional methacrylate.
  • the methacrylate may be any one of a monofunctional methacrylate, a difunctional methacrylate and a trifunctional methacrylate, or may be two or more of them.
  • the ratio of the number of moles of methacryloyl groups to the total number of moles of acryloyl groups and methacryloyl groups is preferably in the range of 3% to 50%, and more preferably in the range of 5% to 40%.
  • Methacrylate allows the first coating film containing the first ionizing radiation curable resin to be semi-cured by exposure to ionizing radiation or ultraviolet light. Increasing the above ratio widens the process window that allows high adhesion to be achieved between the first gloss adjustment layer 5 and the second gloss adjustment layer 6. However, if the above ratio is made excessively large, the scratch resistance of the decorative sheet 1 decreases.
  • the thickness of the first gloss adjustment layer 5 is preferably in the range of 2 ⁇ m to 20 ⁇ m, more preferably in the range of 3 ⁇ m to 20 ⁇ m, and even more preferably in the range of 5 ⁇ m to 15 ⁇ m. If the thickness of the first gloss adjustment layer 5 is reduced, the scratch resistance decreases. If the thickness of the first gloss adjustment layer 5 is increased, the processability of the decorative sheet 1 decreases, and it becomes more likely to whiten when folded.
  • the second gloss adjustment layer 6 partially covers the upper surface of the first gloss adjustment layer 5.
  • the second gloss adjustment layer 6 and the first gloss adjustment layer 5 form a surface protection layer.
  • the second gloss adjustment layer 6 faces the pattern ink layer 4, sandwiching the first gloss adjustment layer 5 between them.
  • the second gloss adjustment layer 6 is consistent in shape and position with the pattern ink layer 4.
  • the second gloss adjustment layer 6 completely matches the shape and position of the pattern ink layer 4, but other configurations can also be adopted.
  • the orthogonal projection of the pattern ink layer 4 onto a plane perpendicular to the thickness direction may be at least partially separated from and located inside the contour of the orthogonal projection of the second gloss adjustment layer 6 onto the plane.
  • the pattern ink layer 4 is composed of a single printed pattern, but if the pattern ink layer 4 is composed of multiple printed patterns of different colors, the second gloss adjustment layer 6 may match the shape and position of the combination of these printed patterns. Alternatively, in this case, the second gloss adjustment layer 6 may match the shape and position of one or a combination of two or more of these printed patterns, and the remaining printed patterns may be provided in a position that is not directly opposite the second gloss adjustment layer 6.
  • the orthogonal projection of the second gloss adjustment layer 6 onto a plane perpendicular to the thickness direction preferably overlaps with the orthogonal projection onto the plane of one printed pattern or a combination of two or more printed patterns whose shape and position are identical to those of the second gloss adjustment layer 6, for preferably 50% or more of its area, more preferably 70% or more, and even more preferably 90% or more.
  • the second gloss adjustment layer 6 has a lower specular gloss GS(60°) than the first gloss adjustment layer 5.
  • the specular gloss GS(60°) of the second gloss adjustment layer 6 is preferably 20 or less, and more preferably 10 or less. In one example, the specular gloss GS(60°) of the second gloss adjustment layer 6 is 0.5 or more.
  • the difference between the specular gloss GS(60°) of the first gloss adjustment layer 5 and the specular gloss GS(60°) of the second gloss adjustment layer 6 is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more. In one example, this difference is 20 or less.
  • the surface of the second gloss adjustment layer 6 has an uneven structure.
  • the uneven structure on the upper surface of the second gloss adjustment layer 6 serves to make the specular gloss GS(60°) of the second gloss adjustment layer 6 lower than the specular gloss GS(60°) of the first gloss adjustment layer 5.
  • the surface of the second gloss adjustment layer 6 has an uneven structure including a plurality of ridge-like portions, each of which protrudes in a ridge-like shape. That is, as shown in Figures 2 and 4, the second gloss adjustment layer 6 includes a core portion 6A, which is a thin layer having a flat upper surface, and a plurality of ridge-like portions 6B, each of which protrudes in a ridge-like shape from the upper surface of the core portion 6A.
  • the ridged portion 6B is, for example, the portion from the lowest part to the tip of the protrusion provided on the surface of the second gloss adjustment layer 6, and the core portion 6A refers to the portion of the second gloss adjustment layer 6 excluding the ridged portion 6B.
  • ridged refers to a convex shape that extends linearly in a planar view.
  • the ridged portions 6B may be curved or straight in plan view, but from the viewpoint of fingerprint resistance of the surface of the decorative sheet 1, it is preferable that they are curved as illustrated in FIG. 3.
  • the second gloss adjustment layer 6 having the ridged portions 6B can be formed, for example, as described below, by irradiating the surface of a coating film containing a second ionizing radiation curable resin with light of a specific wavelength and causing the cured film formed on the surface of the coating film to expand in the in-plane direction.
  • the uneven structure on the upper surface of the second gloss adjustment layer 6 has a ratio RSm/Ra of the average length RSm of the roughness curve elements to the arithmetic mean roughness Ra, which is preferably in the range of 10 to 900, more preferably in the range of 10 to 500, even more preferably in the range of 10 to 400, and even more preferably in the range of 50 to 350. If the ratio RSm/Ra is made smaller, the pitch of the convex portions becomes smaller. As a result, it becomes difficult to wipe off dirt adhering to the surface of the decorative sheet 1, and the contamination resistance decreases. If the ratio RSm/Ra is made larger, the pitch of the convex portions becomes larger, and the effect of the uneven structure in reducing the specular gloss GS (60°) of the second gloss adjustment layer 6 becomes smaller.
  • the ratio RSm/Ra is preferably 80 or more. Increasing the ratio RSm/Ra increases the pitch of the convex portions, improving the affinity of water or a cleaning agent (water containing a surfactant or alcohol) to the upper surface of the second gloss adjustment layer 6. If the decorative sheet 1 has the second gloss adjustment layer 6 with such surface properties, even if the surface becomes dirty, the dirt can be easily wiped off with water or a cleaning agent.
  • the ratio RSm/Ra is most preferably 100 or more. If the ratio RSm/Ra is within this range, a commonly available cleaning sponge can be brought into contact with the boundary of the convex portion and the area nearby on the upper surface of the second gloss adjustment layer 6. Therefore, even if the surface of the decorative sheet 1 becomes dirty, the dirt can be easily wiped off using a commonly available cleaning sponge.
  • the arithmetic mean roughness Ra and the average length of the roughness curve element RSm are the measured values when measured using a line roughness meter (in accordance with JIS B0601:2013).
  • the arithmetic mean roughness Ra is preferably in the range of 0.2 ⁇ m to 10.0 ⁇ m, more preferably in the range of 0.5 ⁇ m to 5.0 ⁇ m, and even more preferably in the range of 0.8 ⁇ m to 4.0 ⁇ m.
  • the average length RSm of the roughness curve elements is preferably in the range of 50 ⁇ m to 800 ⁇ m, more preferably in the range of 80 ⁇ m to 600 ⁇ m, and even more preferably in the range of 100 ⁇ m to 500 ⁇ m.
  • the upper surface of the second gloss adjustment layer 6 may have a sine wave shape in a cross section parallel to the thickness direction and the arrangement direction of the ridge portions 6B.
  • sine wave shape refers to a shape in which the line from the lowest point C of the ridge portions 6B to the highest point D (apex) can be expressed as a sine wave, as shown in Figure 4.
  • the thickness of the second gloss adjustment layer 6 is preferably in the range of 2 ⁇ m to 20 ⁇ m, more preferably in the range of 3 ⁇ m to 20 ⁇ m, even more preferably in the range of 5 ⁇ m to 15 ⁇ m, and most preferably in the range of 5 ⁇ m to 12 ⁇ m. If the thickness of the second gloss adjustment layer 6 is small, it is difficult to achieve the above-mentioned surface properties by the method described below while referring to the ratio RSm/Ra, etc. If the thickness of the second gloss adjustment layer 6 is large, the processability of the decorative sheet 1 decreases and it becomes more likely to whiten when folded.
  • the thickness of the second gloss adjustment layer 6 is the thickness of a layer that has the same apparent area and volume as the second gloss adjustment layer 6 and has a flat surface.
  • the thickness of the second gloss adjustment layer 6 is determined, for example, by the following method. First, a cross section parallel to the thickness direction of the second gloss adjustment layer 6 and perpendicular to the length direction of the ridge portion 6B is imaged. Next, from this cross-sectional image, the dimension of the second gloss adjustment layer 6 in the width direction of the ridge portion 6B and the area of the cross section of the second gloss adjustment layer 6 are determined. The thickness of the second gloss adjustment layer 6 is a value obtained by dividing this area by the above dimension. Note that when the coating liquid for the second gloss adjustment layer described later does not contain a solvent, the thickness of the coating film made of this coating liquid is equal to the thickness of the second gloss adjustment layer 6.
  • the thickness of the second gloss adjustment layer 6 is preferably set so that the ratio of the thickness (or height) of the ridge portion 6B to the thickness of the core portion 6A (thickness of the ridge portion 6B/thickness of the core portion 6A) is within the range of 0.01 to 2.0, and more preferably within the range of 0.1 to 1.0.
  • the second gloss adjustment layer 6 contains a cured resin. As described below, the second gloss adjustment layer 6 may further contain particles. When the mass of the second gloss adjustment layer 6 is 100 parts by mass, the mass of the cured resin contained in the second gloss adjustment layer 6 is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.
  • the second gloss adjustment layer 6 contains only the cured product of the second ionizing radiation curable resin as the resin cured product.
  • the ionizing radiation is a charged particle beam such as an electron beam.
  • the second ionizing radiation curable resin is cured by irradiation with ionizing radiation.
  • the second ionizing radiation curable resin can also be cured by irradiation with ultraviolet light.
  • the second ionizing radiation curable resin used here is cured by irradiation with light having a wavelength of 200 nm or less, and has a large absorption coefficient for this light.
  • the second ionizing radiation curable resin may be any known resin, such as various monomers or commercially available oligomers, for example, (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, or epoxy resins.
  • the second ionizing radiation curable resin may be either an aqueous resin or a non-aqueous (organic solvent-based) resin.
  • the second ionizing radiation curable resin may be solvent-free.
  • the main component of the second ionizing radiation curable resin is preferably an acrylate.
  • the main component means that the resin contains 60 parts by mass or more, more preferably 70 parts by mass or more, and most preferably 80 parts by mass or more, per 100 parts by mass of the resin component.
  • the acrylate is preferably a bifunctional or higher acrylate, and more preferably a trifunctional or higher acrylate. To obtain a second gloss adjustment layer 6 with excellent scratch resistance, the acrylate is preferably a trifunctional or higher acrylate. There is no upper limit to the number of functional groups of the acrylate, but in one example, it is 6-functional or lower.
  • 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 6B are more likely to appear on the coating film surface. However, if the number of repetitions is increased, the crosslinking density decreases, and the scratch resistance of the surface protective layer decreases. Therefore, the number of repetitions is preferably 30 or less, and more preferably 20 or less.
  • 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 second ionizing radiation curable resin may further contain a methacrylate.
  • the second ionizing radiation curable resin may be a second mixture of an acrylate and a methacrylate, in which the proportion of the number of moles of methacryloyl groups in the total number of moles of acryloyl groups and the number of moles of methacryloyl groups is smaller than that of the first mixture.
  • the above proportion in the second mixture is preferably 90% or less, and more preferably 80% or less, of the above proportion in the first mixture.
  • the second gloss adjustment layer 6 may further contain particles in addition to the cured resin.
  • the particles contained in the second gloss adjustment layer 6 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.
  • the average particle size (D50) of the particles is preferably 10 ⁇ m or less, more preferably 1 ⁇ m or more and 8 ⁇ m or less, even more preferably 2 ⁇ m or more and 7 ⁇ m or less, and most preferably 3 ⁇ m or more and 6 ⁇ m or less. If the average particle size (D50) of the particles is increased, the particles may easily fall off from the second gloss adjustment layer 6, making it difficult to achieve high scratch resistance. If the particles are small, the effect of uniformly generating wrinkles becomes small.
  • the "average particle size” or “average particle size (D50)” is the median diameter (D50) measured by a laser diffraction/scattering type particle size distribution measuring device.
  • the second gloss adjustment layer 6 obtained from this coating liquid also contains particles.
  • the average particle size of the particles contained in the second gloss adjustment layer 6 can be a value obtained by observing the cross section and measuring the particle sizes of multiple particles and averaging them. The value thus obtained is substantially the same as the median diameter (D50) measured by a laser diffraction/scattering particle size distribution measuring device. Therefore, the above-mentioned range of average particle size can also be interpreted as the range of average particle size of the particles contained in the second gloss control layer.
  • the amount of particles in the second gloss adjustment layer 6 is preferably in the range of 0.5 parts by mass to 20 parts by mass to 100 parts by mass of the cured resin, more preferably in the range of 0.5 parts by mass to 10 parts by mass, even more preferably in the range of 2 parts by mass to 8 parts by mass, and most preferably in the range of 2 parts by mass to 6 parts by mass.
  • the decorative sheet 1 is manufactured, for example, by the following method.
  • a solid ink layer 3 is formed on one surface of the base layer 2.
  • the solid ink layer 3 can be formed by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing, and various coating methods such as roll coating, knife coating, microgravure coating, and die coating.
  • the pattern ink layer 4 is formed on the solid ink layer 3.
  • the pattern ink layer 4 can be formed by various printing methods, such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing.
  • the gravure printing method is preferable because it allows for relatively high speed processing and is advantageous in terms of cost.
  • a first coating film made of a coating liquid for the first gloss adjustment layer is formed on the above surface of the base layer 2 so as to cover the solid ink layer 3 and the pattern ink layer 4.
  • This first coating film can be formed by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing, or various coating methods such as roll coating, knife coating, microgravure coating, and die coating.
  • the coating liquid for the first gloss adjustment layer contains the first ionizing radiation curable resin described above.
  • the first ionizing radiation curable resin is a first mixture of acrylate and methacrylate.
  • the coating liquid for the first gloss adjustment layer may further contain other components, such as the above-mentioned particles, a solvent, and additives for improving the functionality of the final product, such as one or more antibacterial agents and antifungal agents.
  • the coating liquid for the first gloss adjustment layer may further contain other additives such as an ultraviolet absorber and a light stabilizer.
  • an ultraviolet absorber for example, a benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, etc. may be used.
  • As the light stabilizer for example, a hindered amine-based, etc. may be used.
  • the coating liquid for the first gloss adjustment 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 first irradiation step is carried out.
  • the first coating film is irradiated with the first radiation to semi-cure the first coating film.
  • the first radiation is, for example, ionizing radiation.
  • ionizing radiation is a charged particle beam such as an electron beam.
  • the first radiation may be ultraviolet light for which the first ionizing radiation curable resin exhibits a small absorption coefficient.
  • the wavelength of the ultraviolet light irradiated to the first coating film is preferably greater than 200 nm, more preferably in the range of 230 nm to 450 nm, and even more preferably in the range of 250 nm to 400 nm.
  • the curing can proceed approximately uniformly throughout the entire thickness of the first coating film. Therefore, unlike the second coating film described below, the first coating film after semi-curing does not have any irregularities on its surface.
  • the first coating film is preferably irradiated with the first radiation so that the accumulated light amount is within the range of 3% to 30% of the minimum accumulated light amount required to completely cure the first coating film, more preferably within the range of 5% to 25%, and even more preferably within the range of 8% to 20%.
  • the minimum integrated amount of light required to completely cure the first coating film is, for example, in the range of 10 mJ/cm 2 to 1000 mJ/cm 2 .
  • the first coating film is preferably irradiated with the first radiation so that the absorbed dose is within the range of 0.2% to 50% of the minimum absorbed dose required to completely cure the first coating film, more preferably within the range of 0.5% to 40%, and even more preferably within the range of 1% to 30%.
  • the minimum absorbed dose required to completely cure the first coating is in the range of 5 kGy to 200 kGy.
  • the first ionizing radiation curable resin further contains methacrylate in addition to acrylate.
  • the methacrylate slows down the rate of the crosslinking reaction caused by the first radiation exposure, widening the process window in which the desired cured state can be achieved.
  • a second coating film made of the coating liquid for the second gloss adjustment layer is formed on the semi-cured first coating film.
  • the second coating film is formed so as to partially cover the upper surface of the first coating film.
  • the second coating film is formed so as to face the pattern ink layer 4 with the first coating film sandwiched therebetween.
  • the second coating film can be formed by various printing methods, such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing. Of these, gravure printing is preferred.
  • the coating liquid for the second gloss adjustment layer contains the second ionizing radiation curable resin described above.
  • the second ionizing radiation curable resin is, in one example, an acrylate.
  • the second ionizing radiation curable resin is a second mixture of an acrylate and a methacrylate, in which the proportion of the number of moles of methacryloyl groups in the total number of moles of acryloyl groups and the number of moles of methacryloyl groups is smaller than that of the first mixture.
  • the coating liquid for the second gloss adjustment layer may further contain other components, such as the above-mentioned particles, a solvent, and additives for improving the functionality of the final product, such as one or more antibacterial agents and antifungal agents.
  • the coating liquid for the second gloss adjustment layer may further contain other additives such as an ultraviolet absorber and a light stabilizer.
  • an ultraviolet absorber for example, a benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, etc. may be used.
  • As the light stabilizer for example, a hindered amine-based, etc. may be used.
  • the first coating film and the second coating film are irradiated with ionizing radiation or ultraviolet light to completely cure the first coating film and the second coating film.
  • the second irradiation step and the third irradiation step described below are carried out in sequence.
  • the second coating film is irradiated with a second radiation.
  • the second radiation is light with a wavelength of 200 nm or less.
  • the second ionizing radiation curable resin contained in the coating liquid for the second gloss adjustment layer has a large absorption coefficient for the second radiation. Therefore, the second radiation incident on the second coating film can only reach a position several tens to several hundreds of nm away from the outermost surface. Therefore, in the second irradiation step, the crosslinking reaction proceeds in the surface region of the second coating film, forming an extremely thin cured film, while in other regions the crosslinking reaction does not proceed and the film remains uncured.
  • the second coating film After the second irradiation process, the second coating film has wrinkles on its surface that correspond to the ridged portion 6B.
  • the inventors believe that the reason wrinkles form on the coating film surface as a result of the second irradiation process is as follows.
  • the second radiation can only reach a position that is tens to hundreds of nanometers away from the outermost surface of the second coating film.
  • the crosslinking reaction of the second ionizing radiation curable resin occurs only on the surface of the second 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 second coating film.
  • the second radiation may also be irradiated to the surface of the portion of the first coating film that is not covered by the second coating film.
  • the first coating film is semi-cured, molecular flow within the film is unlikely to occur. Therefore, wrinkles do not form on the exposed surface of the first coating film.
  • the second radiation does not reach the portion of the first coating that is covered by the second coating. Therefore, in this portion, no crosslinking reaction occurs due to irradiation with the second radiation.
  • the second radiation can be extracted from excimer VUV (Vacuum Ultra Violet) light.
  • Excimer VUV light can be produced from lamps that use rare gases or rare gas halide compounds.
  • a large number of discharge plasmas dielectric barrier discharges
  • This plasma discharge excites the atoms of the discharge gas (rare gas), which momentarily enters an excimer 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 second 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 second irradiation step is preferably carried out in, for example, a nitrogen gas atmosphere.
  • the oxygen concentration in the gas phase in the second irradiation step i.e., the residual oxygen concentration in the reaction atmosphere, is preferably 2000 ppm or less, and more preferably 1000 ppm or less.
  • the cumulative light amount of the second radiation is preferably in the range of 0.5 mJ/ cm2 to 200 mJ/ cm2 , more preferably in the range of 1 mJ/ cm2 to 100 mJ/ cm2 , even more preferably in the range of 3 mJ/cm2 to 50 mJ/ cm2 , and most preferably in the range of 5 mJ/ cm2 to 30 mJ/ cm2 . If the cumulative light amount is reduced, the expansion of the cured film in the in-plane direction is reduced. If the cumulative light amount is increased, the surface condition of the second coating film is deteriorated.
  • the second coating film is irradiated with a third radiation.
  • the third radiation is ionizing radiation or ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step.
  • the third radiation can be any of the types described above for the first radiation.
  • a crosslinking reaction progresses throughout the entire thickness of each of the first and second coating films.
  • the first coating film is in a semi-cured state, so in the area where the first and second coating films are in contact, a crosslinking reaction may also occur between the molecules contained in the first and second coating films. Therefore, high adhesion can be achieved between the first gloss adjustment layer 5 and the second gloss adjustment layer 6.
  • the integrated light amount of the third radiation is preferably in the range of 10 mJ/ cm2 to 500 mJ/ cm2 , more preferably in the range of 50 mJ/ cm2 to 400 mJ/ cm2 , and even more preferably in the range of 100 mJ/ cm2 to 300 mJ/ cm2 .
  • the third radiation is preferably applied so that the absorbed dose is within the range of 5 kGy to 200 kGy, more preferably within the range of 10 kGy to 150 kGy, and even more preferably within the range of 15 kGy to 100 kGy.
  • the type of third radiation may be changed.
  • irradiation with ionizing radiation may be performed first, and then irradiation with ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step.
  • irradiation with ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step may be performed first, and then irradiation with ionizing radiation.
  • irradiation with ultraviolet light having a longer wavelength than the light irradiated in the second irradiation step may be performed first, and then irradiation with ultraviolet light having an even longer wavelength.
  • the decorative sheet 1 is obtained. Note that in the decorative sheet 1 obtained by the above method, there is no interface between the core portion 6A and the rib portion 6B, and they are formed integrally.
  • the decorative sheet 1 includes a first gloss adjustment layer 5 and a second gloss adjustment layer 6 partially covering the first gloss adjustment layer 5.
  • the first gloss adjustment layer 5 and the second gloss adjustment layer 6 have different specular gloss GS (60°).
  • the second gloss adjustment layer 6 has a lower specular gloss GS (60°) than the first gloss adjustment layer 5.
  • the difference between the specular gloss GS (60°) of the first gloss adjustment layer 5 and the specular gloss GS (60°) of the second gloss adjustment layer 6 can be increased.
  • the second gloss adjustment layer 6 is consistent in shape and position with the pattern ink layer 4. Therefore, the decorative sheet 1 can express a three-dimensional effect with bumps in the areas that correspond to the pattern ink layer 4 and recesses in the other areas. Therefore, by appropriately selecting the color of the solid ink layer 3 and the color of the pattern ink layer 4, this decorative sheet 1 can express a luxurious design that is close to that of natural wood or natural stone, for example.
  • the first gloss adjustment layer 5 contains only the cured product of the first ionizing radiation curable resin as the resin cured product, and the first ionizing radiation curable resin is a first mixture of acrylate and methacrylate.
  • the acrylate contributes to improving scratch resistance
  • the methacrylate contributes to improving adhesion between the first gloss adjustment layer 5 and the second gloss adjustment layer 6. Therefore, the decorative sheet 1 has excellent scratch resistance and adhesion between the gloss adjustment layers.
  • the uneven structure including the ridged portion 6B created on the upper surface of the second gloss adjustment layer 6 by the above-mentioned method is finer than an uneven structure formed by mechanical processing such as embossing. Since the decorative sheet 1 has such a fine uneven structure on the upper surface of the second gloss adjustment layer 6, it has a matte feel and is highly resistant to fingerprints.
  • the decorative sheet 1 can be modified in various ways.
  • the second gloss adjustment layer 6 may be the same in shape and position as the portion of the solid ink layer 3 that is not covered by the pattern ink layer 4.
  • the decorative sheet 1 deformed in this way can express a three-dimensional effect with a concave-convex shape, with the portion corresponding to the pattern ink layer 4 as a concave portion and the other portion as a convex portion.
  • the convex portions provided on the upper surface of the second gloss adjustment layer 6 are ridge-shaped. These convex portions do not have to be ridge-shaped. For example, each of these convex portions may be a part of a particle.
  • the area of the upper surface of the first gloss adjustment layer 5 that is not covered by the second gloss adjustment layer 6 is flat. As long as the above-mentioned relationship regarding gloss is maintained, an uneven structure may be provided in this area.
  • This uneven structure may be a structure similar to that described above for the ridge portion 6B, or may be a structure in which multiple protrusions, each of which is made up of a portion of a particle, are arranged.
  • the decorative sheet 1 described with reference to Figures 1 to 4 was manufactured by the following method.
  • impregnated paper GFR-506: manufactured by Kohjin Co., Ltd.
  • a basis weight of 50 g/ m2 was prepared as the original fabric layer 2.
  • a solid ink layer 3 and a pattern ink layer 4 were formed in this order using oil-based nitrocellulose resin-based gravure printing ink (PCNT (PCRNT) various colors: manufactured by Toyo Ink Co., Ltd.).
  • PCNT nitrocellulose resin-based gravure printing ink
  • the pattern of the pattern ink layer 4 was a wood grain pattern.
  • a coating liquid for the first gloss adjustment layer having the following composition was applied onto the solid ink layer 3 and the pattern ink layer 4.
  • the coating liquid for the first gloss adjustment layer was applied so that the thickness of the first gloss adjustment layer 5 would be 5 ⁇ m.
  • the first irradiation step was carried out. Specifically, the first coating film made of the coating liquid for the first gloss adjustment layer was irradiated with an electron beam as ionizing radiation so that the absorbed dose of the first coating film was 10 kGy. This caused the first coating film to be semi-cured.
  • a coating liquid for a second gloss adjustment layer having the following composition was printed on the portion of the first coating film that corresponds to the pattern ink layer 4.
  • the coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 5 ⁇ m.
  • the second irradiation step was carried out. Specifically, under atmospheric pressure, in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm, the surface of the first coating film and the second coating film composed of the coating liquid for the second gloss adjustment layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp so that the integrated light amount was 50 mJ/ cm2 . This caused wrinkles to form on the surface of the second coating film.
  • the third irradiation step was carried out. Specifically, the first and second coating films were irradiated with 100 kGy of ionizing radiation to completely cure them as a whole, thereby forming a first gloss adjustment layer 5 and a second gloss adjustment layer 6. In this manner, a decorative sheet 1 was obtained.
  • Example 2 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that in the coating liquid for the first gloss adjustment layer, the blending amount of ionizing radiation curable resin R1 was 80 parts by mass and the blending amount of ionizing radiation curable resin R2 was 20 parts by mass.
  • Example 3 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that in the coating liquid for the first gloss adjustment layer, the blending amount of ionizing radiation curable resin R1 was 90 parts by mass and the blending amount of ionizing radiation curable resin R2 was 10 parts by mass.
  • Example 4 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2 and the blending amount of the ionizing radiation curable resin R1 in the coating liquid for the first gloss adjustment layer was 90 parts by mass and 10 parts by mass of the ionizing radiation curable resin R2.
  • ⁇ Ionizing radiation curable resin R2 Type Isobornyl methacrylate Product name: Light Ester IB-X (Kyoeisha Chemical Co., Ltd.)
  • Example 5 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2.
  • ⁇ Ionizing radiation curable resin R2 Type EO-modified bisphenol A dimethacrylate (EO 10 moles added)
  • ⁇ Ionizing radiation curable resin R2 Type EO-modified bisphenol A dimethacrylate (EO 10 moles added)
  • Example 7 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2 and the blending amount of the ionizing radiation curable resin R1 in the coating liquid for the first gloss adjustment layer was 90 parts by mass and 10 parts by mass of the ionizing radiation curable resin R2.
  • ⁇ Ionizing radiation curable resin R2 Type EO-modified bisphenol A dimethacrylate (EO 10 moles added)
  • Example 9 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2.
  • ⁇ Ionizing radiation curable resin R2 Type Trimethylolpropane EO modified trimethacrylate (EO 3 moles added)
  • Example 10 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin R2.
  • ⁇ Ionizing radiation curable resin R2 Type Trimethylolpropane PO modified trimethacrylate (3 moles of PO added)
  • Example 11 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the amount of particles in the coating liquid for the second gloss adjusting layer was 20 parts by mass.
  • Example 12 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except for the following points.
  • the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjustment layer.
  • the surface of the second coating film consisting of the first coating film and the coating liquid for the second gloss adjustment layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm, so that the accumulated light amount was 100 mJ/ cm2 .
  • Example 13> The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjusting layer.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 15 moles added)
  • Example 14 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjusting layer.
  • - Ionizing radiation curable resin Type Ethylene glycol diacrylate (EO 9 moles added)
  • Product name Light Acrylate 9EG-A (Kyoeisha Chemical Co., Ltd.)
  • Example 15 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except for the following points.
  • the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjusting layer.
  • - Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (EO 35 moles added)
  • the surface of the second coating film consisting of the first coating film and the coating liquid for the second gloss adjustment layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm, so that the accumulated light amount was 50 mJ/ cm2 .
  • Example 16 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except for the following points.
  • the following resin was used as the ionizing radiation curable resin in the coating liquid for the second gloss adjusting layer.
  • - Ionizing radiation curable resin Type Ethoxylated dipentaerythritol hexaacrylate (EO 12 moles added)
  • the surface of the second coating film consisting of the first coating film and the coating liquid for the second gloss adjustment layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm, so that the accumulated light amount was 150 mJ/ cm2 .
  • Example 17 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 2 ⁇ m.
  • Example 18 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except that the coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 20 ⁇ m.
  • Example 19 The decorative sheet 1 described with reference to Figures 1 to 4 was manufactured in the same manner as in Example 1, except for the following points. That is, in this example, particles were omitted from the coating liquid for the second gloss adjustment layer. The coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 3 ⁇ m.
  • Example 20 The decorative sheet 1 described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the blending amount of the particles in the coating liquid for the second gloss adjusting layer was 10 parts by mass.
  • Example 21 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except for the following points.
  • the amount of particles in the coating liquid for the first gloss control layer was 10 parts by mass.
  • the following coating liquid for the second gloss control layer was used in this example.
  • Example 22 The decorative sheet 1 described with reference to Figures 1 to 4 was produced in the same manner as in Example 1, except for the following points.
  • the amount of particles in the coating liquid for the first gloss control layer was 5 parts by mass.
  • the following coating liquid for the second gloss control layer was used in this example.
  • Example 23 The decorative sheet 1 described with reference to Figures 1 to 4 was manufactured in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles in the coating liquid for the first gloss adjustment layer was 10 parts by mass. In addition, in this example, the following coating liquid for the second gloss adjustment layer was used. The coating liquid for the second gloss adjustment layer was printed so that the thickness of the second gloss adjustment layer 6 was 14 ⁇ m.
  • Example 1 A decorative sheet similar to that described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the ionizing radiation curable resin R2 was omitted from the coating liquid for the first gloss adjusting layer.
  • Example 2 A decorative sheet similar to that described with reference to FIGS. 1 to 4 was produced in the same manner as in Example 1, except that the ionizing radiation curable resin R1 was omitted from the coating liquid for the first gloss adjusting layer.
  • the thickness of the second gloss adjusting layer was measured by the same method as described above. Specifically, the decorative sheet was embedded in a resin such as a cold-setting epoxy resin or a UV-curable resin, and the resin was allowed to fully harden. Then, the decorative sheet was cut so that the cross section of the decorative sheet was exposed, and the measurement surface was obtained by mechanically polishing the sheet.
  • a resin such as a cold-setting epoxy resin or a UV-curable resin
  • a scanning electron microscope SIGMA 500 manufactured by Carl Zeiss Microscopy was used to image the cross section of the second gloss adjustment layer.
  • the acceleration voltage was set to 0.5 keV (low acceleration voltage)
  • the imaging mode was set to SE2 mode
  • the magnification was set to 2000x. No sputtering was performed on the measurement sample.
  • the dimension of the second gloss adjustment layer in the width direction of the ridge portion and the area of the cross section of the second gloss adjustment layer were obtained from the cross-sectional image.
  • the thickness of the second gloss adjustment layer was calculated by dividing the area by the above dimension. The thickness thus obtained was equal to the thickness of the coating film made of the coating liquid for the second gloss adjustment layer.
  • the thickness of the first gloss adjusting layer was measured by the same method as above.
  • AAA The number of remaining squares is 100. AA: The number of remaining squares was between 95 and 99. A: The number of remaining squares was between 90 and 94. B: The number of remaining squares was 89 or less.
  • 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. AAA: No scratches or changes in gloss occurred on the surface. AA: Slight scratches or changes in gloss occurred on some parts of the surface. A: Minor scratches or changes in gloss occurred on the surface. B: Significant scratches or changes in gloss occurred on the surface.
  • Stain resistance To evaluate stain resistance, a stain A test specified in the Japanese Agricultural Standards (JAS) was carried out. That is, on the surface protective layer of each decorative sheet, a line of 10 mm width was 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
  • AAA Lines of each color could be easily wiped off.
  • AA Part of the lines of each color could be wiped off, but some slight stains remained.
  • A Part of the lines of each color could be wiped off, but some stains remained.
  • B Lines of each color could not be wiped off.
  • the decorative sheets according to Examples 1 to 23 exhibited sufficient performance in all of adhesion, scratch resistance, and stain resistance.
  • the sheet according to Comparative Example 1 exhibited insufficient performance in all of adhesion, scratch resistance, and stain resistance.
  • the sheet according to Comparative Example 2 exhibited sufficient performance in adhesion, but insufficient performance in scratch resistance and stain resistance.
  • 1...decorative sheet 2...base layer, 3...solid ink layer, 4...pattern ink layer, 5...first gloss adjustment layer, 6...second gloss adjustment layer, 6A...core portion, 6B...ridge portion, 11...decorative material, B...base material, C...position, D...position.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Architecture (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Laminated Bodies (AREA)
PCT/JP2024/021878 2023-06-20 2024-06-17 化粧シート Ceased WO2024262457A1 (ja)

Priority Applications (5)

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JP2024559943A JP7758223B2 (ja) 2023-06-20 2024-06-17 化粧シート
KR1020267001382A KR20260025845A (ko) 2023-06-20 2024-06-17 화장 시트
EP24825858.4A EP4733063A1 (en) 2023-06-20 2024-06-17 Decorative sheet
CN202480039085.6A CN121335804A (zh) 2023-06-20 2024-06-17 装饰片
US19/427,720 US20260108912A1 (en) 2023-06-20 2025-12-19 Decorative sheet

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JP2023-100842 2023-06-20

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008087269A (ja) * 2006-09-29 2008-04-17 Dainippon Printing Co Ltd 化粧シート
JP2014188842A (ja) 2013-03-27 2014-10-06 Dainippon Printing Co Ltd 化粧シート及びこれを用いた化粧板
JP2016173492A (ja) * 2015-03-17 2016-09-29 大日本印刷株式会社 光学フィルムの製造方法
JP2019001120A (ja) * 2017-06-19 2019-01-10 凸版印刷株式会社 化粧シート
WO2022182259A1 (en) 2021-02-24 2022-09-01 SCHATTDECOR Sp. z o.o. Process for the production of a multilayer coated surface and a product containing a multilayer coated surface
WO2023106340A1 (ja) * 2021-12-07 2023-06-15 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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Publication number Priority date Publication date Assignee Title
JP2012001578A (ja) * 2010-06-15 2012-01-05 Aica Kogyo Co Ltd 硬化性樹脂組成物および積層体
WO2018084267A1 (ja) * 2016-11-02 2018-05-11 凸版印刷株式会社 化粧材
CN110087879A (zh) * 2016-12-22 2019-08-02 凸版印刷株式会社 装饰材料
JP7003667B2 (ja) * 2018-01-05 2022-02-10 凸版印刷株式会社 化粧材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008087269A (ja) * 2006-09-29 2008-04-17 Dainippon Printing Co Ltd 化粧シート
JP2014188842A (ja) 2013-03-27 2014-10-06 Dainippon Printing Co Ltd 化粧シート及びこれを用いた化粧板
JP2016173492A (ja) * 2015-03-17 2016-09-29 大日本印刷株式会社 光学フィルムの製造方法
JP2019001120A (ja) * 2017-06-19 2019-01-10 凸版印刷株式会社 化粧シート
WO2022182259A1 (en) 2021-02-24 2022-09-01 SCHATTDECOR Sp. z o.o. Process for the production of a multilayer coated surface and a product containing a multilayer coated surface
WO2023106340A1 (ja) * 2021-12-07 2023-06-15 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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CN121335804A (zh) 2026-01-13
EP4733063A1 (en) 2026-04-29
KR20260025845A (ko) 2026-02-24
JPWO2024262457A1 (https=) 2024-12-26
JP7758223B2 (ja) 2025-10-22

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