WO2023249082A1 - 化粧シート - Google Patents

化粧シート Download PDF

Info

Publication number
WO2023249082A1
WO2023249082A1 PCT/JP2023/023147 JP2023023147W WO2023249082A1 WO 2023249082 A1 WO2023249082 A1 WO 2023249082A1 JP 2023023147 W JP2023023147 W JP 2023023147W WO 2023249082 A1 WO2023249082 A1 WO 2023249082A1
Authority
WO
WIPO (PCT)
Prior art keywords
protective layer
decorative sheet
surface protective
layer
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/JP2023/023147
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
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 JP2024529074A priority Critical patent/JPWO2023249082A1/ja
Priority to EP23827264.5A priority patent/EP4545295A4/en
Priority to KR1020247040736A priority patent/KR20250029039A/ko
Priority to CN202380044937.6A priority patent/CN119325424A/zh
Publication of WO2023249082A1 publication Critical patent/WO2023249082A1/ja
Priority to US18/984,392 priority patent/US20250115039A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/02—Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • 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
    • 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
    • C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of 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
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
    • D21H19/68—Coatings characterised by a special visual effect, e.g. patterned, textured uneven, broken, discontinuous
    • 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
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny 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
    • B32B2307/538—Roughness
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/02161—Floor elements with grooved main surface
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • E04F15/107—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials composed of several layers, e.g. sandwich panels

Definitions

  • the present invention relates to a decorative sheet.
  • Decorative sheets are used, for example, to decorate the interior and exterior materials of fittings, furniture, fixtures, and flooring materials in order to add design and durability to them.
  • a decorative sheet is generally widely used as a decorative board that is attached to the surface of a substrate such as wood, a wooden board, a metal plate, a noncombustible board, a paper substrate, a resin substrate, etc. via an adhesive or the like.
  • Designability is imparted by forming patterns such as wood grain or stone grain using various printing methods, for example. Plain sheets with no patterns are sometimes preferred for decorative sheets. The presence or absence of a pattern and the type of pattern vary depending on the purpose and preference.
  • the glossiness of the surface is also important for the design of decorative sheets.
  • a variety of decorative sheets are selected depending on the purpose and preference, from mirror-like high-gloss sheets to low-gloss sheets with no reflections at all.
  • imparting durability is an important function of decorative sheets as well as imparting design. Durability is a comprehensive evaluation of scratch resistance, stain resistance, and whether these properties can be maintained over a long period of time. Although requirements vary depending on the environment and situation in which the decorative sheet is used, there is always a demand for decorative sheets with high performance.
  • a surface protective layer on the outermost surface of the decorative sheet. Furthermore, in order to adjust the glossiness described above, particularly to achieve low gloss, it is common to add a gloss adjuster (matting additive) to the surface protective layer.
  • decorative sheets are generally subjected to processing such as cutting and bending in order to form decorative materials such as decorative boards, it is preferable that the decorative sheets have processability that can withstand these processes.
  • An object of the present invention is to provide a decorative sheet that provides a rough texture.
  • the invention includes a raw fabric layer and a surface protective layer provided on one surface of the raw fabric layer, and a plurality of ridges each protruding in the shape of a ridge on the surface of the surface protective layer.
  • the decorative sheet is provided with an uneven structure including shaped portions, and the uneven structure of the surface protective layer has a protruding peak height Rpk of 3.5 ⁇ m or more.
  • a decorative sheet according to the above aspect in which the protruding peak height Rpk is 25 ⁇ m or less.
  • a decorative sheet according to any of the above aspects, wherein the uneven structure of the surface protective layer has an average length RSm of roughness curve elements of 150 ⁇ m or more.
  • a decorative sheet according to the above aspect in which the average length RSm is 1000 ⁇ m or less.
  • a decorative sheet according to any of the above aspects, wherein the surface protective layer has a thickness of 8 ⁇ m or more.
  • a decorative sheet according to any of the above aspects, wherein the surface protective layer has a glossiness of 10.0 or less.
  • At least some of the plurality of ridged portions are adjacent to each other in the width direction, and at a position where the at least some of the plurality of ridged portions are adjacent to each other in the width direction, the above-mentioned
  • a decorative sheet according to any of the above side surfaces is provided, in which a cross section parallel to the width direction and the thickness direction of the surface protective layer has a sinusoidal wave shape in the portion where the uneven structure is provided.
  • the surface protective layer includes a cured product of an ionizing radiation-curable resin.
  • the ionizing radiation-curable resin is an acrylate containing a repeating structure as a main component, and the repeating structure is any one of ethylene oxide, propylene oxide, and ⁇ -caprolactone,
  • the repeating structure is repeated three or more times.
  • a decorative material comprising a decorative sheet according to any of the above aspects and a base material to which the decorative sheet is attached.
  • FIG. 1 is a sectional view of a decorative material including a decorative sheet according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a surface protective layer included in the decorative sheet of FIG. 1.
  • FIG. 3 is a microscopic image of a surface protective layer included in a decorative sheet according to an example of the present invention.
  • FIG. 1 is a sectional view of a decorative material including a decorative sheet according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a surface protective layer included in the decorative sheet of FIG. 1.
  • FIG. 3 is a micrograph of a surface protective layer included in a decorative sheet according to an example of the present invention.
  • the cross section shown in FIG. 2 is a cross section along the thickness direction of the surface protective layer.
  • the micrograph in FIG. 3 is a planar photograph obtained using a laser microscope (OLS-4000 manufactured by Olympus Corporation).
  • the decorative material 11 shown in FIG. 1 includes a base material B and a decorative sheet 1 attached to the base material B.
  • the decorative material 11 is a decorative board.
  • the decorative board may be flat, bent or folded.
  • the decorative material 11 may have a shape other than a plate.
  • the base material B is a plate material here.
  • the board material is, for example, a wooden board, an inorganic board, a metal board, or a composite board made of a plurality of materials.
  • the base material B may have a shape other than a plate.
  • the decorative sheet 1 includes a raw fabric layer 2, a pattern layer 3, a transparent resin layer 4, a surface protection layer 5, an adhesive layer 7, a primer layer 6, and a concealing layer 8.
  • the pattern layer 3, the adhesive layer 7, the transparent resin layer 4, and the surface protection layer 5 are provided in this order from the raw fabric layer 2 side on the surface of the raw fabric layer 2 opposite to the surface facing the substrate B.
  • the hiding layer 8 and the primer layer 5 are provided in this order on the surface of the raw material layer 2 facing the substrate B from the raw material layer 2 side.
  • One or more of the pattern layer 3, transparent resin layer 4, primer layer 6, adhesive layer 7, and hiding layer 8 may be omitted. Below, the elements included in the decorative sheet 1 will be explained in order.
  • Raw fabric layer The raw fabric layer 2 or its material can be arbitrarily selected from paper, synthetic resin, synthetic resin foam, rubber, nonwoven fabric, synthetic paper, metal foil, etc. It is.
  • paper include thin paper, titanium paper, and resin-impregnated paper.
  • synthetic resin include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic.
  • Rubbers include ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane.
  • I can give an example.
  • the nonwoven fabric organic or inorganic nonwoven fabric can be used.
  • the metal of the metal foil include aluminum, iron, gold, and silver.
  • the thickness of the raw fabric layer 2 is preferably within the range of 20 ⁇ m or more and 250 ⁇ m or less, considering printing workability, cost, etc.
  • Primer layer When using an olefin resin as the material for the raw fabric layer 2, the surface of the raw fabric layer 2 is often in an inactive state. Therefore, in this case, it is preferable to provide the primer layer 6 between the raw fabric layer 2 and the base material B.
  • the primer layer 6 is omitted, and in order to improve the adhesion between the raw fabric layer 2 and the base material B, the raw fabric layer 2 is subjected to, for example, corona treatment.
  • Surface modification treatments such as , plasma treatment, ozone treatment, electron beam treatment, ultraviolet ray treatment, and dichromic acid treatment may be performed.
  • the material for the primer layer 6 for example, the material described later for the pattern layer 3 can be used. Since the primer layer 6 is applied to the back side of the decorative sheet 1, considering that the decorative sheet 1 will be wound up into a web, the primer layer 6 is applied to avoid blocking and increase adhesion with the adhesive.
  • Inorganic fillers may also be added to layer 6. Examples of the inorganic filler include silica, alumina, magnesia, titanium oxide, and barium sulfate.
  • a colored sheet may be used as the raw fabric layer 2, or an opaque hiding layer 8 may be provided.
  • the concealing layer 8 can be made of, for example, the same material as that described later for the pattern layer 3.
  • the purpose of the hiding layer 8 is to provide hiding properties, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide, etc. as the pigment.
  • metals such as gold, silver, copper, aluminum, etc. to the material of the hiding layer 8, for example. Generally, flaky aluminum pieces are often added.
  • the pattern layer 3 is a layer formed by printing a pattern on the raw fabric layer 2 using ink.
  • the binder for the ink for example, nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyesters, or modified products thereof may be used alone or in combination. can.
  • the binder may be water-based, solvent-based, or emulsion type, and may be a one-part type or a two-part type using a hardening agent.
  • the pattern layer 3 may be formed by a method in which a layer made of curable ink is cured by irradiation with ultraviolet rays, electron beams, or the like.
  • the ink used to form the pattern layer 3 may further contain, for example, colorants such as pigments and dyes, extender pigments, solvents, and various additives that are contained in ordinary inks. can.
  • colorants such as pigments and dyes, extender pigments, solvents, and various additives that are contained in ordinary inks. can.
  • highly versatile pigments include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.
  • Adhesive layer 7 is a layer also called a heat-sensitive adhesive layer, an anchor coat layer, or a dry laminate adhesive layer.
  • the resin material for the adhesive layer 7 is not particularly limited, but can be appropriately selected from, for example, acrylic, polyester, polyurethane, and epoxy resin materials. Further, as the resin material for the adhesive layer 7, for example, an ethylene-vinyl acetate copolymer resin adhesive can also be used.
  • the coating method can be appropriately selected depending on the viscosity of the adhesive and the like. Generally, gravure coating is used, and after forming an adhesive layer 7 on the upper surface of the pattern layer 3 by gravure coating, the transparent resin layer 4 is laminated thereon. Note that the adhesive layer 7 can be omitted if sufficient adhesive strength can be obtained between the transparent resin layer 4 and the pattern layer 3.
  • olefin resin As the resin material for the transparent resin layer 4, an olefin resin is suitably used.
  • olefin resins include polypropylene, polyethylene, polybutene, and ⁇ -olefins (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1 -decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3 -Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-penten
  • ethylene-vinyl acetate copolymer ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer
  • examples include copolymers of ethylene or ⁇ -olefin and other monomers, such as ethylene-ethyl acrylate copolymer and ethylene-butyl acrylate copolymer.
  • the resin for the transparent resin layer 4.
  • various additives such as a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a coloring agent, a light scattering agent, and a gloss adjusting agent may be added to the transparent resin layer 4 as necessary. You can also.
  • heat stabilizers phenol-based, sulfur-based, phosphorus-based, hydrazine-based, etc. are generally added, and as light stabilizers, hindered amine-based, etc. are added in arbitrary combinations.
  • the surface protective layer 5 includes a core portion 5A and a plurality of ridged portions 5B, each of which protrudes in a ridge shape from one surface of the core portion 5A. These ridged portions 5B form an uneven structure.
  • ridged refers to a convex shape that is linear in plan view.
  • the ridged portion 5B may have a curved or linear shape in plan view, but is preferably curved from the viewpoint of fingerprint resistance of the decorative sheet 1.
  • Each of the ridged portions 5B may or may not be branched in plan view.
  • the ridged portion 5B is, for example, a portion 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 is the ridged portion of the surface protective layer 5. This refers to the part excluding section 5B.
  • the ridged portions 5B are each curved, and at least some of them are adjacent to each other in the width direction.
  • a cross section of the surface protection layer 5 parallel to the width direction and the thickness direction of the surface protection layer 5 has an uneven structure as shown in FIG.
  • the portion where is provided has a wave shape such as a sine wave shape.
  • the uneven structure of the surface protective layer 5 has a protruding peak height Rpk of 3.5 ⁇ m or more.
  • the "protruding peak height Rpk” is a surface texture parameter defined in JIS B0671-2:2002. This protruding peak height Rpk is more preferably 4.5 ⁇ m or more, and even more preferably 7.0 ⁇ m or more.
  • This decorative sheet with a reduced protruding peak height Rpk is designed to provide a comfortable surface to the user when the user slides his/her skin on the surface of the surface protective layer, for example, when the user slides his/her finger on the surface of the surface protective layer. Does not give a rough texture.
  • This protruding peak height Rpk is preferably 25 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 15 ⁇ m or less. It is difficult to manufacture a decorative sheet with a large protruding peak height Rpk with high reproducibility.
  • the uneven structure of the surface protective layer 5 preferably has an average length RSm of roughness curve elements of 150 ⁇ m or more, more preferably 200 ⁇ m or more, and even more preferably 250 ⁇ m or more.
  • the "average length RSm of roughness curve elements" is a surface texture parameter defined in JIS B0601:2013.
  • the average of the roughness curve elements is important.
  • the length RSm is within the above range.
  • This average length RSm is preferably 1000 ⁇ m or less, more preferably 900 ⁇ m or less, and even more preferably 800 ⁇ m or less. If the average length RSm is increased, the user may perceive the presence of the ridged portions 5B less frequently when the user slides his/her skin on the surface of the surface protective layer. According to other examples, the average length RSm may be less than or equal to 600 ⁇ m, may be less than or equal to 550 ⁇ m, and may be less than or equal to 500 ⁇ m.
  • the thickness of the surface protective layer 5 is preferably 8 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 15 ⁇ m or more.
  • the thickness of the surface protective layer 5 is reduced, it becomes difficult to increase the protruding peak height Rpk and the average length RSm.
  • the thickness of the surface protective layer 5 is increased, the protruding peak height Rpk and the average length RSm tend to increase.
  • the thickness of the surface protective layer 5 is preferably 30 ⁇ m or less, and more preferably 25 ⁇ m or less.
  • the thickness of the surface protective layer 5 is the thickness of a layer that has the same apparent area and volume as the surface protective layer 5 and has a flat surface.
  • the thickness of the surface protective layer 5 is determined, for example, by the following method. First, a cross section parallel to the thickness direction of the surface protective layer 5 and perpendicular to the length direction of the ridged portion 5B is imaged. Next, from this cross-sectional image, the dimensions of the surface protective layer 5 in the width direction of the ridged portion 5B and the cross-sectional area of the surface protective layer 5 are determined. The thickness of the surface protective layer 5 is a value obtained by dividing this area by the above dimension.
  • the thickness of the coating film made of the surface protective layer coating liquid is equal to the thickness of the surface protective layer 5.
  • the glossiness of the surface protective layer 5 is preferably 10.0 or less, more preferably 8.0 or less.
  • gloss is a value measured at an incident angle of 60 degrees using a gloss meter based on JIS Z8741:1997.
  • the decorative sheet 1 is manufactured, for example, by the following method.
  • the pattern layer 3, transparent resin layer 4, primer layer 6, adhesive layer 7, and concealing layer 8 will be omitted.
  • a coating film made of a surface protective layer coating liquid is formed on one side of the raw fabric layer 2.
  • This coating film can be applied, for example, by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing, as well as roll coating, knife coating, microgravure coating, die coating, etc. It can be formed by various coating methods.
  • the coating liquid for the surface protective layer contains an ionizing radiation-curable resin.
  • ionizing radiation is a charged particle beam such as an electron beam.
  • Ionizing radiation-curable resins are cured by irradiation with ionizing radiation.
  • Ionizing radiation-curable resins can also be cured by ultraviolet irradiation.
  • the ionizing radiation-curable resin used here is cured by irradiation with light having a wavelength of 200 nm or less, and has a large absorption coefficient for this light.
  • the amount of the ionizing radiation-curable resin is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, More preferably, the amount is 80 parts by mass or more.
  • the ionizing radiation-curable resin known ones such as various monomers and commercially available oligomers can be used, such as (meth)acrylic resins, silicone resins, polyester resins, urethane resins, and amide resins. Resin and epoxy resin can be used.
  • the ionizing radiation-curable resin may be either an aqueous resin or a non-aqueous (organic solvent-based) resin.
  • the main component of the ionizing radiation curable resin is preferably acrylate.
  • the main component of the ionizing radiation-curable resin means that it is 60 parts by mass or more when the total solid content contained in the ionizing radiation-curable resin is 100 parts by mass.
  • the ionizing radiation-curable resin preferably contains acrylate in an amount of 70 parts by mass or more, more preferably 80 parts by mass or more.
  • the acrylate is preferably a difunctional or higher functional acrylate, more preferably a trifunctional or higher functional acrylate.
  • the acrylate is preferably trifunctional or more functional.
  • there is no upper limit to the number of functional groups in the acrylate one example is 6 functional groups or less.
  • the acrylate 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 ethylene oxide or propylene oxide.
  • the above-mentioned repeating structure may be interposed between an acryloyl group and a methylol group in an open ring state.
  • the number of repetitions of the repeating structure is preferably 3 or more. If an acrylate is used which is repeated a large number of times, the cured film is likely to expand in the in-plane direction in the first irradiation step described later, and therefore wrinkles corresponding to the ridged portions 5B are likely to be formed on the surface of the coating film. Become. However, if the number of repetitions is increased, the crosslinking density will decrease and the scratch resistance of the surface protective layer will decrease.
  • 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.
  • the tetrafunctional acrylate containing a repeating structure is, for example, EO-modified, PO-modified, or CL-modified pentaerythritol tetraacrylate.
  • the number of repeats of the repeating structure is preferably 12 or more, more preferably 12 or more and 50 or less, and even more preferably 20 or more and 50 or less.
  • the number of repetitions of the above-mentioned repeating structure can be analyzed by using MALDI-TOF-MS.
  • Ionizing radiation-curable resins may have a molecular weight distribution.
  • the number of repetitions described above is the number of repetitions corresponding to the molecular weight having the strongest peak in the mass spectrum of MALDI-TOF-MS.
  • the surface protective layer coating liquid further contains particles.
  • particles When particles are included in the surface protective layer coating liquid, wrinkles can be more uniformly formed on the surface of the coating film in the first irradiation step.
  • the particles include 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. Particles can be used.
  • organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads
  • inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate. Particles can be used.
  • the average particle diameter (D50) of the particles is preferably 10 ⁇ m or less.
  • the average particle diameter (D50) of the particles is more preferably 1 ⁇ m or more and 8 ⁇ m or less, and still more preferably 2 ⁇ m or more and 6 ⁇ m or less.
  • the particles tend to fall off from the surface protective layer 5, and it may be difficult to achieve high scratch resistance.
  • the particles are small, the effect of uniformly forming wrinkles is small.
  • the "average particle size (D50)" is the median diameter (D50) measured with a laser diffraction/scattering particle size distribution measuring device.
  • the coating liquid for surface protective layer contains particles
  • the surface protective layer 5 obtained from this coating liquid also contains particles.
  • the average particle diameter of the particles included in the surface protective layer 5 can be determined by observing the cross section, actually measuring the particle diameters of a plurality of particles, and averaging them. The value obtained in this manner is substantially the same as the median diameter (D50) measured by a laser diffraction/scattering particle size distribution measuring device. Therefore, the range of the average particle size mentioned above can also be read as the range of the average particle size of the particles included in the surface protective layer 5.
  • the amount of particles added is preferably 0.5 parts by mass or more and 10 parts by mass or less, more preferably 2 parts by mass or more and 8 parts by mass or less, and 2 parts by mass or less, based on 100 parts by mass of the ionizing radiation curable resin. It is more preferably at least 6 parts by mass. When the amount of particles is within the above range, the effect of uniformly forming wrinkles is particularly large.
  • the coating liquid for the surface protective layer can further contain a solvent and additives for improving the functionality of the final product, such as antibacterial agents and antifungal agents.
  • the surface protective layer coating liquid can further contain other additives such as ultraviolet absorbers and light stabilizers.
  • ultraviolet absorber for example, benzotriazole type, benzoate type, benzophenone type, triazine type, etc. can be used.
  • light stabilizer for example, hindered amine type and the like can be used. Note that, according to the method described herein, the surface protective layer 5 having low glossiness can be formed without using a gloss adjuster (matting additive).
  • the surface protective layer coating liquid further contains a photoinitiator.
  • the photoinitiator include, but are not limited to, benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based photoinitiators.
  • a first irradiation step is performed.
  • the coating film is irradiated with light having a wavelength of 200 nm or less (hereinafter referred to as first irradiation light).
  • the ionizing radiation-curable resin contained in the surface protective layer coating liquid has a large extinction coefficient with respect to the first irradiation light. Therefore, the first irradiation light incident on the coating film can only reach a distance of several tens to hundreds of nanometers from the outermost surface. Therefore, in the first irradiation step, the crosslinking reaction proceeds in the surface area of the coating film to form an extremely thin cured film, while the other areas do not undergo the crosslinking reaction and remain uncured.
  • the coating film after the first irradiation step has wrinkles on the surface corresponding to the ridged portions 5B.
  • the present inventor considers the reason why wrinkles occur on the surface of the coating film due to the first irradiation step as follows.
  • the first irradiation light can only reach a distance of several tens to several hundred nm from the outermost surface of the coating film. That is, the crosslinking reaction of the ionizing radiation-curable resin occurs only on the surface of the coating film.
  • the monomers, etc. present on the surface of the coating film form a cured film by crosslinking through their functional groups when irradiated with the first irradiation light, but all of those functional groups are It is not used for crosslinking between monomers present on the surface of the coating film. That is, uncrosslinked functional groups may remain in the cured film.
  • the first irradiation light does not reach the monomers located at a distance from the surface of the coating film, so their crosslinking reaction does not occur. However, some of the monomers located away from the surface of the coating migrate to the cured film, where they undergo a crosslinking reaction. In this way, the number of molecules involved in the crosslinking reaction is increased.
  • the volume of the cured film increases. Since the crosslinking reaction occurs only on the surface of the coating film, the cured film cannot increase its volume in the thickness direction, but expands in the in-plane direction. As a result, wrinkles occur on the surface of the coating film.
  • the first irradiation light can be extracted from excimer VUV (Vacuum Ultra Violet) light.
  • Excimer VUV light can be produced from lamps using noble gases or noble gas halide compounds.
  • a gas such as a rare gas or a rare gas halide compound
  • This plasma discharge excites the atoms of the discharge gas (rare gas) and instantaneously becomes an excimer state.
  • this excimer state When returning from this excimer state to the ground state, it emits light in a wavelength range unique to that excimer.
  • the gas used in the excimer lamp may be any conventionally used gas as long as it emits light of 200 nm or less.
  • a rare gas such as Xe, Ar, or Kr
  • a mixed gas of a rare gas such as ArBr or ArF and a halogen gas
  • Excimer lamps have different wavelengths (center wavelengths) depending on the gas, such as approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), and approximately 193 nm (ArF).
  • a xenon lamp that emits excimer light with a center wavelength of 172 nm as the light source. Further, even considering the cost of equipment maintenance and the availability of materials, it is preferable to use a xenon lamp as the light source.
  • the first irradiation step is performed in an atmosphere with a low oxygen concentration.
  • Oxygen has a large absorption coefficient for light of 200 nm or less. Therefore, the first irradiation step is preferably performed under a nitrogen gas atmosphere, for example.
  • the oxygen concentration in the gas phase in the first irradiation step, that is, the residual oxygen concentration in the reaction atmosphere is preferably 2000 ppm or less, more preferably 1000 ppm or less.
  • oxygen in the atmosphere inhibits radical polymerization. Therefore, the residual oxygen concentration in the reaction atmosphere influences the formation of wrinkles on the coating surface. Therefore, when the residual oxygen concentration in the reaction atmosphere is changed, the surface properties of the surface protective layer 5 can also be changed.
  • the cumulative light amount of the first irradiation light is preferably 0.5 mJ/cm 2 or more and 200 mJ/cm 2 or less, more preferably 1 mJ/cm 2 or more and 100 mJ/cm 2 or less, and 3 mJ/cm 2 or more and 50 mJ It is more preferable to set it to below / cm2 .
  • the integrated light amount is reduced, the expansion of the cured film in the in-plane direction becomes smaller.
  • the cumulative amount of light is increased, the surface condition of the coating film deteriorates.
  • a second irradiation step is performed.
  • the coating film is irradiated with second radiation or irradiation light to cure the entire coating film. Thereby, a surface protective layer 5 is obtained.
  • the second radiation or irradiation light is ionizing radiation such as an electron beam, or ultraviolet light whose wavelength is longer than that of the first irradiation light.
  • the cumulative light amount of the second irradiation light is preferably 10 mJ/cm 2 or more and 500 mJ/cm 2 or less, and preferably 50 mJ/cm 2 or more and 400 mJ/cm 2 or less. More preferably, it is 100 mJ/cm 2 or more and 300 mJ/cm 2 or less.
  • the decorative sheet 1 can be manufactured, for example, by the method described above.
  • the decorative sheet 1 may 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 an uneven structure on the surface may be formed by transfer using this plate.
  • the surface protective layer 5 has the surface properties described above.
  • Such a decorative sheet 1 provides a rough tactile sensation to the user when the user slides his/her skin on the surface of the surface protective layer 5, for example, when the user slides his/her finger on the surface of the surface protective layer 5. give. That is, this decorative sheet 1 allows the user to feel the presence of large irregularities.
  • the decorative sheet 1 that provides a rough tactile sensation to the user is suitable for use when the item that comes into contact with the user's skin often has a rough tactile feel and whose appearance is to be reproduced with the decorative sheet 1.
  • the decorative sheet 1 is suitable for use on furniture and the like.
  • the surface protective layer 5 of the decorative sheet 1 has the above-mentioned surface properties, it can achieve a low degree of gloss even if it does not contain a gloss adjuster (matting additive). Since the gloss modifier reduces the oil repellency of the layer formed from the resin material, the surface protective layer containing the gloss modifier is likely to be susceptible to fingerprints.
  • the surface protective layer 5 that does not contain a gloss modifier does not easily absorb oil, so fingerprints are not easily attached to it. Furthermore, the surface protective layer 5 having excellent oil repellency is unlikely to cause oil stains or adsorption of contaminants.
  • the surface protective layer 5 that does not contain a gloss modifier does not have gloss modifier particles falling off when its surface is scratched, and therefore, the decorative sheet 1 that includes such a surface protective layer 5 has no gloss Not easy to change or scratch.
  • the reason why the surface protective layer 5 having the above-mentioned surface properties can be obtained by the above-mentioned method is as follows.
  • Oxygen in the gas phase not only absorbs short wavelength ultraviolet rays, but also inhibits radical polymerization.
  • the effect of oxygen contained in the gas phase on radical polymerization is greatest in the parts of the coating film made of ionizing radiation-curable resin that are adjacent to the gas phase, and decreases as the distance from the coating film surface increases. . Therefore, in the first irradiation step, by changing the oxygen concentration in the gas phase, the relationship between the distance from the coating surface and the degree of progress of the crosslinking reaction can be changed.
  • the thickness of the cured film produced on the surface of the coating film by the first irradiation step and the degree of expansion of the cured film in the in-plane direction according to the progress of the crosslinking reaction will change.
  • the cumulative amount of light in the first irradiation step also influences the thickness of the cured film and the degree of expansion of the cured film in the in-plane direction.
  • the thickness of the cured film and the degree of expansion of the cured film in the in-plane direction affect the surface properties of the surface protective layer. Furthermore, the thickness of the coating film also influences the formation of wrinkles.
  • a desired surface can be obtained.
  • a surface protective layer having specific properties can be obtained.
  • Example 1 The decorative sheet 1 described with reference to FIGS. 1 to 3 was manufactured by the following method. In addition, in this example, the transparent resin layer 4, primer layer 6, adhesive layer 7, and hiding layer 8 were omitted.
  • impregnated paper GFR-506, manufactured by Kojin Co., Ltd.
  • a basis weight of 50 g/m 2 was prepared as the raw fabric layer 2.
  • a pattern layer 3 was formed on one side of the original fabric layer 2 using an oil-based nitrified cotton resin-based gravure printing ink (PCNT (PCRNT) in various colors: manufactured by Toyo Ink Co., Ltd.).
  • PCNT gravure printing ink
  • the coating liquid for the surface protective layer used was one in which the following particles were blended with the following ionizing radiation curable resin.
  • ⁇ Ionizing radiation curable resin Type Ethylene glycol diacrylate (9 moles of EO added)
  • Product name Light acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) Blend: 100 parts by mass/particles
  • Particle size 5 ⁇ m
  • Blend 0.5 parts by mass
  • a coating film made of the surface protective layer coating liquid was formed to have a thickness of 10 ⁇ m.
  • a first irradiation step was performed. Specifically, under atmospheric pressure and in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm, a Xe excimer lamp was used to emit an integrated amount of ultraviolet light with a wavelength of 172 nm onto the surface of a coating film made of a coating liquid for a surface protective layer. The irradiation was performed so that the amount of irradiation was 150 mJ/cm 2 . This caused wrinkles on the surface of the coating film.
  • the surface protective layer 5 was formed by irradiating the coating film with ionizing radiation and curing the entire coating film.
  • the decorative sheet 1 was obtained as described above.
  • Decorative sheet 1 was manufactured in the same manner as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (6 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured in the same manner as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (15 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured in the same manner as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (3 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured in the same manner as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane PO modified triacrylate (addition of 6 moles of PO)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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. A coating film made of the surface protective layer coating liquid was formed to have a thickness of 8 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (6 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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. A coating film made of the surface protective layer coating liquid was formed to have a thickness of 15 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (6 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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 (35 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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 (50 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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 (addition of 20 moles of EO)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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 (35 moles of PO added)
  • the first irradiation step consists of a coating liquid for the surface protective layer under atmospheric pressure and in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm.
  • the surface of the coating film was irradiated with ultraviolet rays with a wavelength of 172 nm using a Xe excimer lamp so that the cumulative amount of light was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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 pentaerythritol tetraacrylate (addition of 20 moles of CL)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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. A coating film made of the surface protective layer coating liquid was formed to have a thickness of 8 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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. A coating film made of the surface protective layer coating liquid was formed to have a thickness of 15 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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 dipentaerythritol hexaacrylate (12 moles of EO added)
  • the first irradiation step starts from the surface protective layer coating liquid under atmospheric pressure and in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm.
  • the surface of the coating film was irradiated with ultraviolet rays with a wavelength of 172 nm using a Xe excimer lamp so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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 (addition of 20 moles of EO)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 200 mJ/cm 2 .
  • Decorative sheet 1 was manufactured 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. A coating film made of the surface protective layer coating liquid was formed to have a thickness of 8 ⁇ m.
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative light amount was 150 mJ/cm 2 .
  • 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 (6 moles of EO added)
  • Particle size 5 ⁇ m Blend: 15 parts by mass
  • the first irradiation step was not performed, and the coating film made of the surface protective layer coating liquid was cured only by the second irradiation step.
  • 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 Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added)
  • Blend 100 parts by mass/particles
  • Particle size 5 ⁇ m
  • Blend 15 parts by mass
  • the first irradiation step was not performed, and the coating film made of the surface protective layer coating liquid was cured only by the second irradiation step.
  • Example 3 A decorative sheet 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. A coating film made of the surface protective layer coating liquid was formed to have a thickness of 5 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (6 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 50 mJ/cm 2 .
  • Example 4 A decorative sheet 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. A coating film made of the surface protective layer coating liquid was formed to have a thickness of 5 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added)
  • a Xe excimer lamp is used to apply ultraviolet light with a wavelength of 172 nm to the surface of the coating film made of the coating liquid for the surface protective layer. was irradiated so that the cumulative amount of light was 50 mJ/cm 2 .
  • the skin feel was evaluated by the following method. First, preliminary preparations were made to match the evaluation criteria among the evaluators. Specifically, ten standard test pieces with different surface properties were prepared. Next, each of the 20 evaluators was asked to slide their fingers on the surface of the standard test piece while blindfolded, and then categorized the tactile sensation into the following five groups.
  • Group 1 The presence of unevenness was clearly felt, and there was a strong rough texture.
  • 2nd group There was a rough texture (roughness between the 1st and 3rd groups).
  • Group 3 There was a slight rough texture.
  • Group 4 There was no rough texture.
  • each of the evaluators was asked to slide their fingers on the surface of the surface protective layer while blindfolded, and then to classify the tactile sensation into the five groups described above. This procedure was repeated until the evaluations by each evaluator matched three or more consecutive times and the evaluation results matched three times in a row between the evaluators. Based on the results, the skin feel was evaluated according to the following criteria.
  • AAA 1st group AA: 2nd group A: 3rd group B: 4th group.
  • Fingerprint resistance As a fingerprint resistance evaluation, a fingerprint wiping property evaluation was performed. Specifically, first, the 60 degree glossiness of the surface of each decorative sheet was measured, and this 60 degree glossiness was taken as the initial glossiness. Subsequently, a fingerprint resistance evaluation liquid was applied onto the surface protective layer, and the fingerprint resistance evaluation liquid adhering to the surface of the decorative sheet was wiped off. Here, higher fatty acids were used as the fingerprint resistance evaluation liquid. Thereafter, the 60 degree glossiness of the portion where the fingerprint resistance evaluation liquid was wiped off was measured, and this 60 degree glossiness was defined as the glossiness after wiping.
  • Fingerprint wiping rate (%) (Glossiness after wiping/Initial glossiness) x 100
  • the evaluation criteria were as follows.
  • AA 70% or more and less than 250%
  • A 50% or more and less than 70%, or 250% or more and less than 300%
  • B Less than 50%, or 300% or more.
  • the evaluation criteria were as follows. AA: No scratches or changes in gloss occurred on the surface. A: Minor scratches and changes in gloss occurred on the surface. B: Significant scratches and changes in gloss occurred on the surface.
  • the decorative sheets according to Examples 1 to 16 gave the evaluators a rough texture. Furthermore, the decorative sheets according to Examples 1 to 16 had low gloss and were excellent in fingerprint resistance and stain resistance. Furthermore, the decorative sheets according to Examples 2 to 16 also had excellent scratch resistance. On the other hand, as shown in Table 3, the decorative sheets according to Comparative Examples 1 and 2 did not give a rough feel to the evaluators and were inferior in fingerprint resistance, stain resistance, and scratch resistance. Furthermore, although the decorative sheets according to Comparative Examples 3 and 4 had low gloss and were excellent in fingerprint resistance, stain resistance, and scratch resistance, they did not give a rough feel to the evaluators.
  • SYMBOLS 1 Decorative sheet, 2... Original fabric layer, 3... Pattern layer, 4... Transparent resin layer, 5... Surface protective layer, 6... Primer layer, 7... Adhesive layer, 8... Hiding layer, 11... Decorative material, B... substrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Architecture (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/023147 2022-06-24 2023-06-22 化粧シート Ceased WO2023249082A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2024529074A JPWO2023249082A1 (https=) 2022-06-24 2023-06-22
EP23827264.5A EP4545295A4 (en) 2022-06-24 2023-06-22 DECORATIVE LEAF
KR1020247040736A KR20250029039A (ko) 2022-06-24 2023-06-22 화장 시트
CN202380044937.6A CN119325424A (zh) 2022-06-24 2023-06-22 装饰片
US18/984,392 US20250115039A1 (en) 2022-06-24 2024-12-17 Decorative sheet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022102037 2022-06-24
JP2022-102037 2022-06-24

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/984,392 Continuation US20250115039A1 (en) 2022-06-24 2024-12-17 Decorative sheet

Publications (1)

Publication Number Publication Date
WO2023249082A1 true WO2023249082A1 (ja) 2023-12-28

Family

ID=89380050

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/023147 Ceased WO2023249082A1 (ja) 2022-06-24 2023-06-22 化粧シート

Country Status (6)

Country Link
US (1) US20250115039A1 (https=)
EP (1) EP4545295A4 (https=)
JP (1) JPWO2023249082A1 (https=)
KR (1) KR20250029039A (https=)
CN (1) CN119325424A (https=)
WO (1) WO2023249082A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024157859A1 (ja) * 2023-01-25 2024-08-02 Ｔｏｐｐａｎホールディングス株式会社 化粧シート

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6663952B1 (en) * 1998-10-09 2003-12-16 Wkp Wurttembergische Kunststoffplatten-Werke Gmbh & Co. Kg Stratified material and a method for producing the same
US20160152833A1 (en) * 2013-06-14 2016-06-02 Covestro Deutschland Ag Direction-independently impact-resistant 3-d molded parts
JP2016150473A (ja) * 2015-02-16 2016-08-22 リンテック株式会社 粗面化フィルム及びその製造方法
JP2017171794A (ja) * 2016-03-24 2017-09-28 東洋インキＳｃホールディングス株式会社 紫外線硬化型コート剤組成物および積層体
US20200024439A1 (en) * 2017-05-22 2020-01-23 Lg Hausys, Ltd. Low-gloss cured product having excellent stain resistance, and manufacturing method therefor
KR20200025050A (ko) * 2018-08-29 2020-03-10 (주)엘지하우시스 내오염성 및 논슬립성이 우수한 바닥재
KR20200059905A (ko) * 2018-11-22 2020-05-29 (주)엘지하우시스 내오염성 및 심미적 효과가 우수한 장식재 및 이의 제조방법
JP2020111715A (ja) * 2019-01-17 2020-07-27 三菱ケミカル株式会社 硬化物
JP2020163829A (ja) * 2019-03-28 2020-10-08 大日本印刷株式会社 化粧材
JP2021101090A (ja) * 2016-07-06 2021-07-08 東リ株式会社 床材
WO2021235493A1 (ja) * 2020-05-20 2021-11-25 日本ペイント・オートモーティブコーティングス株式会社 積層フィルムおよび成形体、ならびにこれらの製造方法
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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6398261B2 (ja) * 2013-09-30 2018-10-03 大日本印刷株式会社 加飾シート及び加飾樹脂成形品
WO2015046549A1 (ja) * 2013-09-30 2015-04-02 大日本印刷株式会社 加飾シート及び加飾樹脂成形品
JP7003667B2 (ja) 2018-01-05 2022-02-10 凸版印刷株式会社 化粧材
JP7215558B2 (ja) * 2020-03-03 2023-01-31 凸版印刷株式会社 化粧シート及び化粧板

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6663952B1 (en) * 1998-10-09 2003-12-16 Wkp Wurttembergische Kunststoffplatten-Werke Gmbh & Co. Kg Stratified material and a method for producing the same
US20160152833A1 (en) * 2013-06-14 2016-06-02 Covestro Deutschland Ag Direction-independently impact-resistant 3-d molded parts
JP2016150473A (ja) * 2015-02-16 2016-08-22 リンテック株式会社 粗面化フィルム及びその製造方法
JP2017171794A (ja) * 2016-03-24 2017-09-28 東洋インキＳｃホールディングス株式会社 紫外線硬化型コート剤組成物および積層体
JP2021101090A (ja) * 2016-07-06 2021-07-08 東リ株式会社 床材
US20200024439A1 (en) * 2017-05-22 2020-01-23 Lg Hausys, Ltd. Low-gloss cured product having excellent stain resistance, and manufacturing method therefor
KR20200025050A (ko) * 2018-08-29 2020-03-10 (주)엘지하우시스 내오염성 및 논슬립성이 우수한 바닥재
KR20200059905A (ko) * 2018-11-22 2020-05-29 (주)엘지하우시스 내오염성 및 심미적 효과가 우수한 장식재 및 이의 제조방법
JP2020111715A (ja) * 2019-01-17 2020-07-27 三菱ケミカル株式会社 硬化物
JP2020163829A (ja) * 2019-03-28 2020-10-08 大日本印刷株式会社 化粧材
WO2021235493A1 (ja) * 2020-05-20 2021-11-25 日本ペイント・オートモーティブコーティングス株式会社 積層フィルムおよび成形体、ならびにこれらの製造方法
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4545295A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024157859A1 (ja) * 2023-01-25 2024-08-02 Ｔｏｐｐａｎホールディングス株式会社 化粧シート

Also Published As

Publication number Publication date
EP4545295A1 (en) 2025-04-30
EP4545295A4 (en) 2025-10-22
US20250115039A1 (en) 2025-04-10
CN119325424A (zh) 2025-01-17
JPWO2023249082A1 (https=) 2023-12-28
KR20250029039A (ko) 2025-03-04

Similar Documents

Publication Publication Date Title
EP4116095A1 (en) Decorative sheet and production method for decorative sheet
EP4101640A1 (en) Decorative sheet and method for manufacturing decorative sheet
US12303937B2 (en) Decorative sheet and method for producing decorative sheet
US12594741B2 (en) Decorative sheet, and method for producing decorative sheet
US20240359210A1 (en) Decorative sheet and method for producing decorative sheet
WO2023249080A1 (ja) 化粧シート
US20250332810A1 (en) Decorative sheet
WO2023191052A1 (ja) 化粧シート、及び化粧シートの製造方法
US20240425717A1 (en) Decorative sheet and method for manufacturing decorative sheet
JP7632761B2 (ja) 化粧シート
JP2026063152A (ja) 化粧シート
US20250115039A1 (en) Decorative sheet
JP7601294B1 (ja) 化粧シート
JP7582561B1 (ja) 化粧シート
WO2023249081A1 (ja) 化粧シート
WO2025159123A1 (ja) 化粧シート
WO2025023246A1 (ja) 化粧シート
WO2025159124A1 (ja) 化粧シート
WO2025220703A1 (ja) 化粧シート
JP2026043502A (ja) 化粧シート
WO2023238893A1 (ja) 化粧シート、及び化粧シートの製造方法
WO2026038502A1 (ja) 化粧シート

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23827264

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024529074

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202380044937.6

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 202380044937.6

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2023827264

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023827264

Country of ref document: EP

Effective date: 20250124

WWP Wipo information: published in national office

Ref document number: 1020247040736

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2023827264

Country of ref document: EP