WO2023191052A1 - 化粧シート、及び化粧シートの製造方法 - Google Patents

化粧シート、及び化粧シートの製造方法 Download PDF

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Publication number
WO2023191052A1
WO2023191052A1 PCT/JP2023/013562 JP2023013562W WO2023191052A1 WO 2023191052 A1 WO2023191052 A1 WO 2023191052A1 JP 2023013562 W JP2023013562 W JP 2023013562W WO 2023191052 A1 WO2023191052 A1 WO 2023191052A1
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Prior art keywords
protective layer
surface protective
less
decorative sheet
layer
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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/JP2023/013562
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English (en)
French (fr)
Japanese (ja)
Inventor
絵理佳 阿久津
洋平 西川
宏祐 清水
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Toppan Inc
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Toppan 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 Inc filed Critical Toppan Inc
Priority to CN202380030434.3A priority Critical patent/CN118946459A/zh
Priority to JP2024512904A priority patent/JPWO2023191052A1/ja
Priority to EP23781060.1A priority patent/EP4501632A4/en
Publication of WO2023191052A1 publication Critical patent/WO2023191052A1/ja
Priority to US18/899,425 priority patent/US20250019546A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • B32B27/16—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/30—Particles characterised by physical dimension
    • B32B2264/303—Average diameter greater than 1µm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/408—Matt, dull surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • 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
    • E04F15/10—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 used for surface decoration of the interior and exterior of buildings, fittings, furniture, fixtures, flooring, etc., and a method for manufacturing the decorative sheet.
  • decorative sheets are applied to the surfaces of wood, wood boards, metal plates, noncombustible boards, paper substrates, resin substrates, etc. using adhesives to add design and durability to the surfaces.
  • the design can be selected depending on the requirements and purpose, from patterns such as wood grain or stone grain formed using various printing methods to a plain surface without a pattern.
  • the glossiness of the surface is also an important item in terms of design, and can be selected from high gloss like a mirror to low gloss with no reflections, depending on requirements and uses.
  • imparting durability is an important function of decorative sheets as well as design. Durability is a comprehensive evaluation of scratch resistance, stain resistance, and whether these can be guaranteed over a long period of time.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. To impart durability, it is common to form 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 boards and decorative materials, it is preferable that the decorative sheets have processability that can withstand these processes.
  • An example of a decorative sheet in which design (low gloss), scratch resistance, and stain resistance are taken into consideration is the decorative sheet described in Patent Document 1, for example.
  • the sheet tends to curl significantly due to curing shrinkage, making it difficult to laminate to the base material. There is. Furthermore, (6) the decorative sheet tends to tear because the surface protective layer is too hard.
  • the present invention has low gloss and excellent design, and also has fingerprint resistance, high durability (particularly scratch resistance and stain resistance), and processability (on the base material).
  • An object of the present invention is to provide a decorative sheet that is easy to laminate and is hard to tear, and a method for manufacturing the same.
  • the present inventors optimized the uneven shape of the surface protective layer and conducted repeated experiments to find the necessary structural elements for the material used for the surface protective layer, thereby achieving a gloss level of 15 or less and fingerprint resistance. It has been found that it is possible to provide a decorative sheet that exhibits high durability (particularly scratch resistance and stain resistance) and processability (can be easily laminated to a base material and is resistant to tearing).
  • a decorative sheet includes a raw fabric layer and a surface protective layer provided on one surface of the raw fabric layer, and the glossiness of the surface protective layer is is 15 or less, the surface protective layer has a ridge-like protruding portion on its surface, and an uneven shape is formed, and the surface protective layer has a main material that is free from ionizing radiation.
  • the ionizing radiation curable resin is a tetrafunctional acrylic resin whose main component includes a repeating structure, the number of repeats of the repeating structure is 12 or more, and the Martens hardness of the surface protective layer is is within the range of 20 N/mm 2 or more and 200 N/mm 2 or less, and the RSm/Ra of the uneven shape of the surface protective layer is within the range of 10 or more and 300 or less.
  • a decorative sheet that has a gloss level of 15 or less and is compatible with fingerprint resistance, scratch resistance, stain resistance, and processability.
  • FIG. 1 is a schematic cross-sectional view illustrating one configuration of a surface protective layer of a decorative sheet according to an embodiment of the present invention.
  • 1 is a plan view photograph showing an example of the surface structure of a surface protective layer of a decorative sheet according to an embodiment of the present invention.
  • It is a schematic sectional view explaining the cross-sectional shape of the ridged part concerning an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view illustrating a measurement method of a curl test.
  • the decorative sheet 1 of this embodiment has a pattern layer 3, an adhesive layer 7 (thermal adhesive layer, anchor coat layer) on one surface side of the raw fabric layer (base material layer) 2. , dry laminate adhesive layer), transparent resin layer 4 and surface protection layer 5 are laminated in this order.
  • a concealing layer 8 and a primer layer 6 are provided on the other surface of the raw fabric layer 2, that is, the back surface side.
  • the pattern layer 3, adhesive layer 7, transparent resin layer 4, hiding layer 8, and primer layer 6 may be omitted.
  • the decorative sheet 1 of this embodiment constitutes a decorative material 11 by being bonded to a substrate B, as shown in FIG.
  • the substrate B is not particularly limited, but may be made of, for example, a wooden board, an inorganic board, a metal plate, a composite board made of a plurality of materials, or the like.
  • any material selected from among, for example, paper, synthetic resin, foamed material of synthetic resin, rubber, nonwoven fabric, synthetic paper, metal foil, etc. can be used.
  • 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 surface of the raw fabric layer 2 is often in an inactive state, so a primer layer 6 is provided between the raw fabric layer 2 and the base material B. It is preferable to provide one.
  • the raw fabric layer 2 may be subjected to, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, etc. Surface modification treatments such as ultraviolet ray treatment, dichromic acid treatment, etc. may be performed.
  • the primer layer 6 the same material as the pattern layer 3, which will be described later, can be used.
  • the primer layer 6 is applied to the back side of the decorative sheet 1, considering that the decorative sheet 1 is wound up into a web shape, the primer layer 6 is applied to avoid blocking and improve adhesion with the adhesive.
  • An inorganic filler may be added to 6. Examples of the inorganic filler include silica, alumina, magnesia, titanium oxide, and barium sulfate.
  • the thickness of the original fabric layer 2 is preferably within the range of 20 ⁇ m or more and 250 ⁇ m or less, considering printing workability, cost, and the like.
  • the pattern layer 3 is a pattern printed layer that is printed on the original fabric layer 2 using ink.
  • the binder for the ink for example, nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, and the like can be used alone or appropriately selected from modified products thereof.
  • the binder may be aqueous, solvent-based, or emulsion type, and may be a one-part type or a two-part type using a hardening agent.
  • a method may be used in which a curable ink is used and the ink is cured by irradiation with ultraviolet rays, electron beams, or the like.
  • the most common method is to use urethane-based ink, which is hardened with isocyanate.
  • the pattern layer 3 includes, for example, pigments contained in ordinary inks, coloring agents such as dyes, extender pigments, solvents, various additives, and the like.
  • 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.
  • ink In addition to applying ink, it is also possible to create a design on the pattern layer 3 by vapor deposition or sputtering of various metals. In particular, it is preferable that a light stabilizer is added to the ink, thereby suppressing the deterioration of the decorative sheet 1 itself caused by photodeterioration of the ink and extending the life of the decorative sheet 1.
  • the adhesive layer 7 is 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 selected appropriately depending on the viscosity of the adhesive, etc., but generally gravure coating is used, and after coating the upper surface of the pattern layer 3 by gravure coating, the transparent resin layer is coated. It is designed to be laminated with 4. Note that the adhesive layer 7 can be omitted if sufficient adhesive strength between the transparent resin layer 4 and the pattern layer 3 can be obtained.
  • olefin resin As the resin material for the transparent resin layer 4, 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-pentene
  • Copolymer ethylene/vinyl alcohol copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer
  • examples include copolymerization of ethylene or ⁇ -olefin with other monomers, such as 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 has a core portion 5A and a ridge-like portion 5B provided in a ridge-like manner protruding from one surface of the core portion 5A. Thereby, an uneven shape is formed on the surface of the surface protection layer 5.
  • the term "ridged” refers to a shape that is elongated and raised in a linear manner in a plan view.
  • the ridged portions 5B may be curved or linear in plan view, but are preferably curved from the viewpoint of anti-fingerprint properties of the surface of the decorative sheet 1.
  • 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 5B.
  • FIG. 2 is a cross-sectional view schematically showing a cross section of the ridged portion 5B of the surface protective layer 5 (a cross section in the thickness direction of the surface protective layer 5), and FIG. This is a planar photograph showing.
  • FIG. 3 is a plane photograph obtained using a laser microscope (OLS-4000 manufactured by Olympus).
  • OLS-4000 manufactured by Olympus
  • the ridged portion 5B has a shape that is elongated and swollen and linearly connected in a plan view.
  • the ridged portion 5B is formed by irradiating the surface of the ionizing radiation curable resin with light of a specific wavelength to cause the surface of the ionizing radiation curable resin to contract, as will be described later.
  • the shape of the ridged portion 5B is determined by the surface roughness index RSm ( ⁇ m) in the horizontal direction (the plane direction of the surface protective layer 5, and the horizontal direction in FIG. 2) and the vertical direction (the ridged portion 5B).
  • the surface roughness index Ra ( ⁇ m) in the depth direction of the surface protective layer 5 (in the vertical direction in FIG. 2) can be expressed as the ratio RSm/Ra, It is 10 or more and 300 or less. More preferably, it is 50 or more and 300 or less.
  • RSm/Ra is less than 10
  • the shape of the ridged portions 5B is too small, making it difficult to wipe off dirt, resulting in poor stain resistance.
  • RSm/Ra is greater than 300, the intervals between the ridges are too wide, resulting in poor gloss.
  • RSm/Ra is more preferably 100 or more and 300 or less.
  • the spacing between the ridges is appropriately wide, and the affinity for water or cleaning agents (water containing surfactant or alcohol) is improved. Therefore, if the decorative sheet has RSm/Ra within the numerical range, even if the surface of the decorative sheet becomes dirty, the stain can be easily wiped off using water or a detergent.
  • RSm/Ra is most preferably 100 or more and 250 or less. If RSm/Ra is within this numerical range, commonly commercially available cleaning sponges will easily penetrate between the ridges, and even if the surface of the decorative sheet is dirty, it will be easier to use commercially available cleaning sponges. It becomes easy to wipe off dirt using the cleaning sponge provided.
  • RSm ( ⁇ m) may be 50 or more and 400 or less, preferably 80 or more and 300 or less. If RSm ( ⁇ m) is within this numerical range, the spacing between the ridges is appropriately wide, so the affinity for water or detergent (water containing surfactant or alcohol) is improved. Therefore, if the decorative sheet has RSm ( ⁇ m) within the numerical range, even if the surface of the decorative sheet becomes dirty, the stain can be easily wiped off using water or a detergent.
  • Ra ( ⁇ m) may be 0.3 or more and 10 or less, preferably 0.5 or more and 10 or less, and more preferably 0.8 or more and 5 or less.
  • Ra ( ⁇ m) is within this numerical range, commonly commercially available cleaning sponges will easily penetrate between the ridges, and even if the surface of the decorative sheet is dirty, it will generally be difficult to clean. It becomes easy to wipe off dirt using a commercially available cleaning sponge.
  • Ra and RSm are measured values using a line roughness meter (based on JIS B0601).
  • the cross-sectional shape of the ridged portion 5B in the thickness direction of the surface protective layer 5 may be a sine wave shape.
  • the "sine wave shape” refers to a shape in which a line from the lowest position C to the highest position (apex) D of the ridged portion 5B can be expressed as a sine wave, as shown in FIG.
  • acrylate When acrylate is irradiated with light having a wavelength of 200 nm or less as the first irradiation light, acrylate can be self-excited. Therefore, by irradiating the acrylate with light of 200 nm or less, it becomes possible to crosslink the acrylate. Light of 200 nm or less reaches a depth of several tens to hundreds of nm in acrylate. As a result, only the surface is crosslinked, and the underlying portion has fluidity, resulting in a fine uneven shape that is continuous in a wavy manner, such as folding wrinkles.
  • the core portion 5A and the ridged portion 5B are formed in an integral and continuous state.
  • Light of 200 nm or less is absorbed by oxygen in the atmosphere and is greatly attenuated. Therefore, when processing acrylate, it is necessary to control the reaction atmosphere by introducing nitrogen gas.
  • the residual oxygen concentration in the reaction atmosphere is preferably suppressed to 2000 ppm or less. More preferably, the residual oxygen concentration in the reaction atmosphere is 1000 ppm or less.
  • the integrated light amount of the first irradiation light is 0.5 mJ/cm 2 or more and 200 mJ/cm 2 or less. More preferably, the integrated light amount is 1 mJ/cm 2 or more and 100 mJ/cm 2 or less. More preferably, the integrated light amount is 3 mJ/cm 2 or more and 50 mJ/cm 2 or less. Most preferably, the integrated light amount is 5 mJ/cm 2 or more and 30 mJ/cm 2 or less.
  • the curing shrinkage reaction When the cumulative light amount is less than 0.5 mJ/cm 2 , the curing shrinkage reaction is weak and the uneven shape is not sufficiently formed, so that the gloss does not decrease. When the cumulative light amount is more than 200 mJ/cm 2 , the curing and shrinkage reaction becomes too strong and the surface condition deteriorates.
  • Excimer VUV light can be produced from noble gas or noble gas halide compound lamps.
  • 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.
  • 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).
  • the first irradiation light which has a wavelength of 200 nm or less, reaches only a few tens to several hundred nm from the outermost surface of the acrylate, so the ridges formed by the irradiation with light of 200 nm or less
  • the inside of the surface protective layer 5 containing 5B has fluidity, and the curing reaction must proceed further.
  • UV light with a longer wavelength than ionizing radiation or the first irradiation light with a wavelength of 200 nm or less as the second irradiation light. I can do it.
  • the third irradiation light for example, after irradiation with the second irradiation light, a type of ionizing radiation different from the second irradiation light or UV light having a longer wavelength than the second irradiation light is used as the third irradiation light.
  • the third irradiation light may be applied when the strength of the surface protective layer 5 is not sufficient only by irradiation with the second irradiation light.
  • the cumulative amount of the second irradiation light be 10 mJ/cm 2 or more and 500 mJ/cm 2 or less. More preferably, the integrated light amount is 50 mJ/cm 2 or more and 400 mJ/cm 2 or less. More preferably, the integrated light amount is 100 mJ/cm 2 or more and 300 mJ/cm 2 or less.
  • the cumulative light amount is less than 10 mJ/cm 2 , the curing reaction is weak and sufficient strength cannot be imparted to the entire surface protective layer 5, so the scratch resistance tends to decrease. Furthermore, if the cumulative amount of light is more than 500 mJ/cm 2 , the curing reaction becomes too strong and the surface condition tends to deteriorate.
  • the cumulative amount of light of the second irradiation light is larger than the cumulative amount of light of the first irradiation light.
  • the integrated light amount of the second irradiation light is preferably 1.1 times or more and 50.0 times or less, more preferably 5.0 times or more and 30.0 times or less, than the integrated light amount of the first irradiation light.
  • the cumulative amount of light of the second irradiation light is less than 1.1 times the cumulative amount of light of the first irradiation light, the curing reaction is weak and it may not be possible to impart sufficient strength to the entire surface protection layer 5.
  • the curing reaction for the entire surface protective layer 5 will become too strong, and the shape of the ridged portion 5B will change. May be deformed.
  • FIG. 5 is a diagram schematically showing a temporal change in the amount of irradiation light of the first irradiation light and a time change of the amount of irradiation light of the second irradiation light.
  • FIGS. 5(a), (c), (e), (g), and (i) are diagrams schematically showing temporal changes in the amount of irradiation light of the first irradiation light.
  • FIGS. 5(b), (d), (f), (h), and (j) are diagrams schematically showing temporal changes in the amount of irradiation light of the second irradiation light.
  • the irradiation light amount of the first irradiation light may gradually increase as the irradiation time passes, and then gradually decrease as the irradiation time passes, as shown in FIG. 5(a). Moreover, the irradiation light amount of the first irradiation light may gradually decrease as the irradiation time elapses, as shown in FIG. 5(c). Moreover, the irradiation light amount of the first irradiation light may gradually increase as the irradiation time elapses, as shown in FIG. 5(e).
  • the irradiation light amount of the first irradiation light may gradually decrease as the irradiation time passes, and then gradually increase as the irradiation time passes, as shown in FIG. 5(g).
  • the irradiation light amount of the first irradiation light may be constant from the start of irradiation to the end of irradiation, as shown in FIG. 5(i).
  • the irradiation light amount of the second irradiation light may gradually increase as the irradiation time passes, and then gradually decrease as the irradiation time passes, as shown in FIG. 5(b). Moreover, the irradiation light amount of the second irradiation light may gradually decrease as the irradiation time elapses, as shown in FIG. 5(d). Moreover, the irradiation light amount of the second irradiation light may gradually increase as the irradiation time elapses, as shown in FIG. 5(f).
  • the irradiation light amount of the second irradiation light may gradually decrease as the irradiation time passes, and then gradually increase as the irradiation time passes, as shown in FIG. 5(h).
  • the irradiation light amount of the second irradiation light may be constant from the start of irradiation to the end of irradiation, as shown in FIG. 5(j).
  • the irradiation forms of the first irradiation light shown in FIGS. 5(a), (c), (e), (g), and (i), and the ), (f), (h), and (j) can be used in appropriate combinations with the irradiation forms of the second irradiation light.
  • the irradiation form of the first irradiation light shown in FIG. 5(a) and the irradiation form of the second irradiation light shown in FIG. 5(f) may be used in combination.
  • the irradiation form of the first irradiation light shown in FIG. 5(c) and the second irradiation form shown in FIG. 5(f) It is more preferable to use it in combination with the light irradiation mode.
  • the ridged portions 5B formed by irradiation with light of 200 nm or less have a finer structure than the uneven shapes formed on the surface of the surface protective layer 5 by mechanical processing such as embossing. It has become.
  • the surface protective layer 5 is a resin layer having a Martens hardness of 20 N/mm 2 or more and 200 N/mm 2 or less. More preferably, it is 50 N/mm 2 or more and 150 N/mm 2 or less, and even more preferably 80 N/mm 2 or more and 150 N/mm 2 or less.
  • the Martens hardness of the surface protective layer 5 is less than 20 N/mm 2 , the scratch resistance decreases, which is not preferable.
  • the Martens hardness of the surface protective layer 5 is made larger than 200 N/ mm2 , the sheet may curl significantly due to curing shrinkage, making it difficult to laminate to the base material during processing, or the coating may be hard, making it difficult to laminate the sheet during processing.
  • the Martens hardness may be the Martens hardness of the ionizing radiation curable resin that constitutes the surface protective layer 5. That is, as the ionizing radiation-curable resin constituting the surface protective layer 5, it is preferable to use a resin having a Martens hardness of 20 N/mm 2 or more and 200 N/mm 2 or less, and a resin that has a Martens hardness of 50 N/mm 2 or more and 150 N/mm 2 or less.
  • a resin having a force of 80 N/mm 2 or more and 150 N/mm 2 or less for example, a tetrafunctional acrylic resin containing any one of the repeating structures of ethylene oxide, propylene oxide, and ⁇ -caprolactone is used.
  • the Martens hardness of the surface protective layer 5 is preferably 20 N/mm 2 or more and 200 N/mm 2 or less, more preferably 50 N/mm 2 or more and 150 N/mm 2 or less, and 80 N/mm 2 or more and 150 N/mm 2 or less. It is more preferable if it is less than mm 2 .
  • the value of the Martens hardness can be arbitrarily adjusted by selecting the type and molecular weight of the ionizing radiation-curable resin constituting the surface protective layer 5. Furthermore, when the surface protective layer 5 is composed of a plurality of types of resins, the value of the Martens hardness can be arbitrarily adjusted by adjusting the content ratio of the constituent resins. In addition, when the surface protective layer 5 is formed of a plurality of layers, the Martens hardness of the uppermost layer of the surface protective layer 5 may be within the above numerical range, and the Martens hardness of the lowermost layer of the surface protective layer 5 may be set within the above numerical range. It may be a numerical range. Alternatively, the value of Martens hardness may be gradually decreased or increased from the uppermost layer to the lowermost layer of the surface protective layer 5.
  • the thickness of the surface protective layer 5 is preferably in the range of 2 ⁇ m or more and 20 ⁇ m or less. More preferably, the layer thickness of the surface protective layer 5 is in the range of 3 ⁇ m or more and 20 ⁇ m or less. More preferably, the layer thickness of the surface protective layer 5 is in the range of 5 ⁇ m or more and 15 ⁇ m or less. Most preferably, the layer thickness of the surface protective layer 5 is in the range of 5 ⁇ m or more and 12 ⁇ m or less.
  • the layer thickness of the surface protective layer 5 is less than 2 ⁇ m, shaping by vacuum ultraviolet light does not penetrate deeply, and low gloss cannot be achieved. Moreover, if the layer thickness of the surface protective layer 5 is made thicker than 20 ⁇ m, the workability will be lowered and whitening will occur during bending.
  • the layer thickness of the surface protective layer 5 is such that the ratio of the layer thickness of the ridged portion 5B to the layer thickness of the core portion 5A (layer thickness of the ridged portion 5B/layer thickness of the core portion 5A) is 0.01 or more. It is preferable to set it to .0 or less, and more preferably to set it to 0.1 or more and 1.0 or less.
  • the pattern layer 3 and the surface protection layer 5 can be formed by various printing methods such as a gravure printing method, an offset printing method, a screen printing method, an electrostatic printing method, and an inkjet printing method.
  • the surface protective layer 5 covers the entire surface of the surface side of the raw fabric layer 2, it can also be coated with various coating methods such as roll coating, knife coating, microgravure coating, and die coating. can be formed. These printing methods or coating methods may be selected separately depending on the layer to be formed, or the same method may be selected for batch processing.
  • the pattern layer 3 and the surface protection layer 5 may be synchronized from the viewpoint of design.
  • the gravure printing method is advantageous in terms of cost since it can be applied at relatively high speeds.
  • synchronization means that 50% or more, preferably 70% or more, and most preferably 90% or more of the area on which the surface protective layer 5 is formed overlaps with the pattern part of the pattern layer 3 in plan view. do.
  • the coating amount may be adjusted in the above-described printing method and coating method. The coating amount can be calculated from the difference in mass between two types of substrates (original fabric layers) with and without a surface protective layer formed thereon, using various printing methods and coating methods.
  • the main material of the surface protective layer 5 is an ionizing radiation curable resin.
  • the main material refers to a material containing 60 parts by mass or more, more preferably 70 parts by mass or more, and most preferably 80 parts by mass or more, based on 100 parts by mass of the surface protective layer.
  • known resins such as various monomers and commercially available oligomers can be used, such as (meth)acrylic resins, silicone resins, and polyester resins. , urethane resin, amide 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 constituting the surface protective layer 5 is a tetrafunctional acrylate resin containing a repeating structure.
  • the tetrafunctional acrylate resin for example, pentaerythritol tetraacrylate can be used.
  • the main component refers to 60 parts by mass or more, more preferably 70 parts by mass or more, and most preferably 80 parts by mass or more, based on 100 parts by mass of the constituent resin components.
  • trifunctional or less acrylate resins the degree of crosslinking is insufficient and the scratch resistance decreases, which is not preferable.
  • the degree of crosslinking becomes too high, which reduces processability, which is not preferable.
  • the ionizing radiation curable resin has a suitable viscosity range of 10 to 500 mPa ⁇ s, and an optimum viscosity range of 50 to 300 mPa ⁇ s.
  • an organic solvent or a bifunctional acrylate resin with low viscosity can be added.
  • organic solvents it is preferable not to use organic solvents.
  • Bifunctional acrylate resin is not preferable because scratch resistance decreases if the amount added is large.
  • the content of the bifunctional acrylate resin is within the range of 10% by mass or more and 30% by mass or less of the content (mass) of the tetrafunctional acrylate resin. is preferable, and more preferably within the range of 15% by mass or more and 20% by mass or less.
  • the viscosity range of the ionizing radiation-curable resin may be 10 to 80 mPa ⁇ s, preferably 10 to 50 mPa ⁇ s. If the viscosity range of the ionizing radiation-curable resin is within this numerical range, the versatility of the coating method will increase. Further, the viscosity range of the ionizing radiation-curable resin may be 200 to 250 mPa ⁇ s, preferably 220 to 250 mPa ⁇ s. If the viscosity range of the ionizing radiation-curable resin is within this numerical range, fine uneven shapes are likely to be formed.
  • the above repeating structure is preferably any one of an ethylene oxide (EO) structure, a propylene oxide (PO) structure, and an ⁇ -caprolactone (CL) structure. More preferably, the repeating structure is ethylene oxide or propylene oxide.
  • the ethylene oxide structure, propylene oxide structure, and ⁇ -caprolactone structure are preferable because the molecules can freely rotate and have high flexibility, so the molecules are easily folded by light of 200 nm or less and a fine uneven shape is easily formed. Further, the number of times this repeating structure is repeated is 12 or more. More preferably, it is 12 or more and 50 or less, most preferably 20 or more and 50 or less.
  • the ionizing radiation-curable resin constituting the surface protective layer 5 will not sufficiently shrink when vacuum ultraviolet light (VUV light) is irradiated, and the surface protective layer 5 will not have low gloss.
  • VUV light vacuum ultraviolet light
  • the number of repetitions is greater than 50, the crosslinking density decreases and the scratch resistance of the surface protective layer 5 deteriorates.
  • the number of repetitions of the above-mentioned repeating structure can be analyzed using MALDI-TOF-MS.
  • Ionizing radiation-curable resins may have a molecular weight distribution. When there is a molecular weight distribution, the number of repetitions is the number of repetitions corresponding to the molecular weight having the strongest peak in the MALDI-TOF-MS mass spectrum.
  • the surface protective layer 5 may contain particles. By adding particles of optimum particle size and optimum content, a uniform surface can be formed.
  • the particles for example, organic materials such as PE wax, PP wax, and resin beads, or inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate can be used.
  • the average particle diameter (D50) of the particles is preferably 10 ⁇ m or less. More preferably, it is 1 ⁇ m or more and 8 ⁇ m or less, still more preferably 2 ⁇ m or more and 6 ⁇ m or less, and most preferably 3 ⁇ m or more and 5 ⁇ m or less. If it is larger than 10 ⁇ m, it is not preferable because the scratch resistance decreases due to particles falling off. If it is less than 1 ⁇ m, it is not preferable because the effect of making the surface uniform is small.
  • the amount of particles added is preferably 0.5 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the ionizing radiation curable resin. More preferably, the amount of particles added is 2 parts by mass or more and 8 parts by mass or less, still more preferably 2 parts by mass or more and 6 parts by mass or less, and most preferably 4 parts by mass or more and 5 parts by mass or less. It is preferable that the surface protective layer 5 contains particles in the above-mentioned amount since it can form a uniform surface condition.
  • the "particle size (average particle size)" may be the value (average value) obtained by measuring the particle size distribution of the particles used, or the particle size of multiple particles may be determined from cross-sectional observation of the obtained decorative material.
  • the average particle diameter of the particles added to the surface protective layer 5 may be the median diameter (D50) measured with a laser diffraction/scattering particle size distribution measuring device.
  • a photoinitiator When the entire surface protective layer 5 is cured by UV light, it is necessary to add a photoinitiator to the surface protective layer 5.
  • the photoinitiator include, but are not limited to, benzophenone, acetophenone, benzoin ether, thioxanthone, and the like.
  • Functional additives such as antibacterial agents and antifungal agents may be optionally added to the surface protective layer 5 in order to impart required functions.
  • an ultraviolet absorber and a light stabilizer can be added to the surface protective layer 5 as necessary.
  • ultraviolet absorbers for example, benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, etc. are added, and as light stabilizers, for example, hindered amine-based, etc. are generally added in any combination.
  • Such a decorative sheet 1 has a gloss level of 15 or less even though it does not contain a gloss adjuster (matting additive).
  • a gloss adjuster matrix additive
  • the content of the gloss modifier in the surface protective layer is high, and the surface protective layer becomes cloudy. For this reason, there was a risk that the color and pattern of the colored pattern layer would not be clearly expressed, or that the design of the decorative sheet would deteriorate.
  • the content of the gloss modifier in the surface protective layer is even higher, so the surface can be smoothed without streaks or unevenness during the formation of the surface protective layer. It was difficult to form a smooth surface protective layer.
  • the decorative sheet 1 can provide a decorative sheet with a gloss level of 15 or less while maintaining performance comparable to that of a decorative sheet with a gloss level of 20 or higher.
  • glossiness is a measured value when measured at an incident angle of 60 degrees using a glossmeter based on JIS Z8741.
  • the hiding layer 8 can basically be made of the same material as the pattern layer 3, but since the purpose is to provide hiding properties, for example, opaque pigments, titanium oxide, iron oxide, etc. are used as the pigment. It is preferable. Furthermore, in order to improve the hiding property, it is also possible to add metals such as gold, silver, copper, and aluminum. Generally, aluminum flakes are often added.
  • a resin film is used as the raw fabric layer 2, and a surface protective layer 5 is formed on the upper surface of the raw fabric layer 2 by printing.
  • the surface protective layer 5 irradiates the surface of the applied ionizing radiation curable resin with light (first irradiation light) having a wavelength of 200 nm or less to shrink the surface of the ionizing radiation curable resin.
  • first irradiation light having a wavelength of 200 nm or less
  • UV light having a longer wavelength than the ionizing radiation or the first irradiation light, which has a wavelength of 200 nm or less, is irradiated.
  • the decorative sheet 1 is formed, which includes the surface protection layer 5 having the core portion 5A and the ridged portion 5B provided in a ridge-like manner protruding from one surface (upper surface) of the core portion 5A.
  • the decorative sheet 1 according to the present embodiment includes a surface protective layer 5 having an uneven shape formed on the surface.
  • the gloss (gloss level) of the surface protective layer can be adjusted even if the surface protective layer does not contain a gloss adjusting agent (matting additive).
  • the gloss modifier reduces the oil repellency of the layer formed from the resin material, making it more susceptible to fingerprints. Since the surface protective layer 5 according to this embodiment does not contain a gloss modifier, it does not absorb oil and has relatively improved oil repellency. Therefore, fingerprints are less likely to adhere to the decorative sheet 1 having the surface protective layer 5 in various situations such as on-site construction, furniture assembly, and residents' daily life. Furthermore, according to the structure of the surface protective layer 5 having an uneven shape formed on the surface, the oil repellency of the surface protective layer 5 is improved, and it is possible to suppress the adsorption of oil stains and contaminants to the surface of the decorative sheet 1. Become.
  • the surface protective layer 5 that does not contain a gloss adjusting agent, when the surface of the decorative sheet 1 is scratched, the particles of the gloss adjusting agent do not fall off, causing a change in gloss or scratches on the surface of the decorative sheet 1. It is possible to make it more difficult. Further, according to the structure of the surface protective layer 5 having a Martens hardness within the range of 20 N/mm 2 or more and 200 N/mm 2 or less, the surface protective layer 5 itself has a certain hardness, and the surface protective layer 5 shrinks when cured. Curling of the decorative sheet 1 caused by this is reduced, and lamination onto a base material becomes easier.
  • the surface protective layer 5 having a Martens hardness within the range of 20 N/mm 2 or more and 200 N/mm 2 or less, it is possible to impart appropriate flexibility to the surface protective layer 5 itself.
  • the sheet 1 becomes difficult to tear (damage to the decorative sheet 1 is reduced).
  • the surface protective layer 5 is formed of a single layer, but the structure is not limited to this.
  • the surface protective layer 5 may have a multilayer structure. That is, the surface protective layer 5 may be formed by laminating a plurality of layers of the same ionizing radiation curable resin or by laminating a plurality of layers of different ionizing radiation curable resins to form an uneven shape on the surface.
  • the outermost layer of the surface protective layer 5 has a Martens hardness in the range of 20 N/mm 2 to 200 N/mm 2 and the main material is ionizing radiation-curable resin.
  • the ionizing radiation-curable resin is a tetrafunctional acrylic resin whose main component is a repeating structure, and the repeating structure is one of ethylene oxide, propylene oxide, and ⁇ -caprolactone structures. Either one is preferable, and the number of repetitions of the repeating structure is 12 or more, and the layer located on the raw layer 2 side of the surface protective layer 5 (i.e., the layer located below the outermost layer of the surface protective layer 5) ) is not particularly limited.
  • the lowest layer of the surface protective layer 5 (the layer located on the raw fabric layer 2 side of the surface protective layer 5) has a Martens hardness in the range of 20 N/mm 2 or more and 200 N/mm 2 or less
  • the material is an ionizing radiation-curable resin
  • the main component of the ionizing radiation-curable resin is a tetrafunctional acrylic resin containing a repeating structure, and the repeating structure consists of each of ethylene oxide, propylene oxide, and ⁇ -caprolactone. Any one of these structures is preferable, and the number of repetitions of the repeating structure is 12 or more, and the outermost layer of the surface protective layer 5 does not need to be particularly limited.
  • Example 1 Impregnated paper (GFR-506, manufactured by Kojin Co., Ltd.) with a basis weight of 50 g/m 2 was used as the base layer 2, and one side was coated with oil-based nitrified cotton resin-based gravure printing ink (PCNT (PCRNT) for each color: After forming the pattern layer 3 using Toyo Ink Co., Ltd., the following coating liquid for surface protective layer was applied. The layer thickness of the surface protective layer coating liquid was 5 ⁇ m.
  • PCNT gravure printing ink
  • the surface of the surface protective layer coating liquid was irradiated with a Xe excimer lamp having a wavelength of 172 nm so that the cumulative amount of light was 100 mJ/cm 2 to shrink the surface.
  • the surface protective layer 5 was formed by irradiating with ionizing radiation and curing the surface protective layer coating liquid, thereby obtaining the decorative sheet of Example 1 having a total thickness of 60 ⁇ m.
  • the coating liquid for the surface protective layer was composed of the following ionizing radiation curable resin and the following particles mixed therein.
  • ⁇ Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added)
  • Blend 100 parts by mass/particles
  • Particle size 5 ⁇ m
  • Blend 0.5 parts by mass
  • Example 2 A decorative sheet of Example 2 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (50 moles of EO added)
  • ⁇ Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (addition of 20 moles of EO)
  • Example 4 A decorative sheet of Example 4 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Propoxylated pentaerythritol tetraacrylate (35 moles of PO added)
  • ⁇ Ionizing radiation curable resin Type Caprolactone-modified pentaerythritol tetraacrylate (30 moles of caprolactone (CL) added)
  • Example 6> A decorative sheet of Example 6 having a total thickness of 56 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the surface protective layer coating liquid of Example 1 was 1 ⁇ m.
  • Example 7> A decorative sheet of Example 7 having a total thickness of 57 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the surface protective layer coating liquid of Example 1 was changed to 2 ⁇ m.
  • Example 8> A decorative sheet of Example 8 having a total thickness of 75 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the surface protective layer coating liquid of Example 1 was changed to 20 ⁇ m.
  • Example 9> A decorative sheet of Example 9 having a total thickness of 80 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the surface protective layer coating liquid of Example 1 was changed to 25 ⁇ m.
  • Example 10> A decorative sheet of Example 10 was obtained in the same manner as in Example 9 except that the particles of Example 9 were not blended.
  • Example 11> A decorative sheet of Example 11 was obtained in the same manner as in Example 3 except that the particles of Example 3 were not blended.
  • Example 12> A decorative sheet of Example 12 was obtained in the same manner as in Example 1 except that the particles of Example 1 were replaced with the following particles.
  • Example 14> A decorative sheet of Example 14 was obtained in the same manner as in Example 1 except that the amount of particles of Example 1 was changed to 10 parts by mass.
  • Example 15> A decorative sheet of Example 15 was obtained in the same manner as in Example 1 except that the amount of particles of Example 1 was changed to 11 parts by mass.
  • Example 16> A decorative sheet of Example 16 having a total thickness of 56 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the surface protective layer coating liquid of Example 1 was 1 ⁇ m and no particles were used.
  • Example 17> A decorative sheet of Example 17 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin of Example 1 was replaced with the following.
  • Example 18> A decorative sheet of Example 18 having a total thickness of 80 ⁇ m was obtained in the same manner as in Example 2 except that the layer thickness of the surface protective layer coating liquid of Example 2 was changed to 25 ⁇ m.
  • Example 19 A decorative sheet of Example 19 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin 1 (main component) Type: Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added)
  • Blend 60 parts by mass/ionizing radiation curable resin 2
  • Type Dipentaerythritol hexaacrylate
  • ⁇ Comparative example 1> A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the excimer lamp irradiation of Example 1 was omitted and the amount of particles was changed to 15 parts by mass.
  • ⁇ Comparative example 2> A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (6 moles of EO added)
  • ⁇ Comparative example 3> A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Ethoxylated dipentaerythritol polyacrylate (12 moles of EO added)
  • ⁇ Comparative example 4> A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Pentaerythritol tetraacrylate
  • Product name: NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
  • ⁇ Surface condition> The uniformity of the surface was evaluated visually. The evaluation criteria were as follows. ⁇ : Uniform surface condition ⁇ : Some uneven surfaces ⁇ : Uneven surface condition over the entire surface
  • the Martens hardness of each decorative sheet was measured using a Martens hardness measuring device (Fisherscope HM2000; manufactured by Fisher Instruments Co., Ltd.) based on ISO14577.
  • the decorative sheet 1 of the sample is embedded in a resin such as a cold-curable epoxy resin or a UV-curable resin, and after it is sufficiently cured, a cross section of the decorative sheet 1 is exposed.
  • a measurement surface was obtained by cutting the sample into 100% and mechanically polishing it.
  • a specific measurement method is to press an indenter against the measurement surface of each sample, and calculate the Martens hardness from the indentation depth and load.
  • the measurement conditions were a test force of 10 mN, a test force loading time of 10 seconds, and a test force holding time of 5 seconds.
  • ⁇ Fingerprint resistance Wipeability evaluation>
  • a fingerprint wiping property evaluation was conducted. The 60 degree glossiness of the surface of each decorative sheet was measured and defined as [initial glossiness]. Subsequently, a fingerprint resistance evaluation liquid was applied onto the surface protective layer, and then the fingerprint resistance evaluation liquid adhering to the surface of the decorative sheet was wiped off. Thereafter, the 60 degree glossiness of the portion where the fingerprint resistance evaluation liquid was wiped off was measured and defined as the [glossiness after wiping]. Here, higher fatty acids were used as the fingerprint resistance evaluation liquid.
  • the evaluation criteria were as follows. ⁇ : 70% or more and less than 250% ⁇ : 50% or more and less than 70%, or 250% or more and less than 300% ⁇ : Less than 50%, or 300% or more
  • ⁇ Stain resistance> As a stain resistance evaluation, a line with a width of 10 mm was drawn using blue ink, black quick-drying ink, and red crayon, respectively, using a stain A test specified in the Japanese Agricultural Standards (JAS), and after leaving it for 4 hours, ethanol was applied. was soaked in a cloth and wiped off the lines of blue ink, black quick-drying ink, and red crayon to evaluate the resistance to ink staining.
  • the evaluation criteria were as follows. ⁇ : The lines of each color could be easily wiped off. ⁇ : The lines of each color could be partially wiped off, but dirt remained in some areas. ⁇ : The lines of each color could not be wiped off.
  • ⁇ Scratch resistance test steel wool rubbing test> After the obtained decorative sheet was attached to the wooden substrate B using a urethane adhesive, a steel wool rubbing test was conducted to evaluate the scratch resistance. A load of 100 g was applied to each sheet of steel wool, and the sheets were rubbed back and forth 20 times, and scratches on the surface of the decorative sheet and changes in gloss were visually confirmed. The evaluation criteria were as follows. ⁇ : No scratches or changes in gloss occurred on the surface ⁇ : Minor scratches or changes in gloss occurred on the surface ⁇ : Significant scratches or changes in gloss occurred on the surface
  • the decorative sheets of Examples 1 to 19 can provide decorative sheets that have a gloss of 15 or less, yet have fingerprint resistance, scratch resistance, stain resistance, and processability. .
  • further performance improvement is possible by optimizing the layer thickness of the surface protective layer, and the particle size and addition amount of the particles to be blended.

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PCT/JP2023/013562 2022-03-31 2023-03-31 化粧シート、及び化粧シートの製造方法 Ceased WO2023191052A1 (ja)

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EP4501632A1 (en) 2025-02-05

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