WO2024147318A1 - 化粧シート - Google Patents

化粧シート Download PDF

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Publication number
WO2024147318A1
WO2024147318A1 PCT/JP2023/046694 JP2023046694W WO2024147318A1 WO 2024147318 A1 WO2024147318 A1 WO 2024147318A1 JP 2023046694 W JP2023046694 W JP 2023046694W WO 2024147318 A1 WO2024147318 A1 WO 2024147318A1
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WO
WIPO (PCT)
Prior art keywords
decorative sheet
protective layer
surface protective
layer
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/046694
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
祥美 山崎
まち子 森田
絵理佳 阿久津
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Holdings Inc
Original Assignee
Toppan Holdings Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to JP2024522413A priority Critical patent/JP7582561B1/ja
Priority to CN202380089601.1A priority patent/CN120435382A/zh
Priority to KR1020257021098A priority patent/KR20250133654A/ko
Priority to EP23914804.2A priority patent/EP4647250A4/en
Publication of WO2024147318A1 publication Critical patent/WO2024147318A1/ja
Priority to JP2024192141A priority patent/JP2025010355A/ja
Priority to US19/258,511 priority patent/US20250333908A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D21H19/826—Paper comprising more than one coating superposed two superposed coatings, the first applied being pigmented and the second applied being non-pigmented
    • 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
    • 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
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31F—MECHANICAL WORKING OR DEFORMATION OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31F1/00—Mechanical deformation without removing material, e.g. in combination with laminating
    • B31F1/07—Embossing, i.e. producing impressions formed by locally deep-drawing, e.g. using rolls provided with complementary profiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/06—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • 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
    • D21H27/002—Tissue paper; Absorbent paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles

Definitions

  • the present invention relates to a decorative sheet.
  • Decorative sheets are used to decorate the surfaces of interior and exterior materials such as building fixtures, furniture, construction materials, and flooring, for the purpose of imparting design and durability to these materials.
  • Decorative sheets are generally widely used as decorative panels that are attached to the surfaces of substrates such as wood, wood boards, metal plates, non-flammable boards, paper substrates, and resin substrates via adhesives or the like.
  • Designs can be added by forming patterns such as wood grain or stone using various printing methods. Plain, pattern-free decorative sheets are sometimes preferred. The choice of whether or not to have a pattern and the type of pattern vary according to the application and preference.
  • the glossiness of the surface is also important in the design of decorative sheets.
  • decorative sheets There are a variety of decorative sheets to choose from, ranging from mirror-like high gloss to low gloss with no reflections at all, depending on the application and preference.
  • Durability is a comprehensive assessment of scratch resistance, stain resistance, and whether these can be maintained over the long term. Requirements vary depending on the environment and situation in which the decorative sheet is used, but there is always a demand for decorative sheets with high performance.
  • a surface protective layer on the outermost surface of the decorative sheet. Also, to adjust the gloss mentioned above, and in particular to achieve a low gloss, it is common to add a gloss adjuster (matte additive) to the surface protective layer.
  • decorative sheets are generally processed, such as by cutting and bending, to form decorative materials such as decorative panels, so it is preferable that the sheets have processability that can withstand these processes.
  • the objective of the present invention is to provide a decorative sheet that has a rough texture and excellent uniformity of texture.
  • an original fabric layer and a surface protective layer provided on one surface of the original fabric layer, and an uneven structure including a plurality of ridge-like portions each protruding in a ridge shape is provided on the surface of the surface protective layer, and the uneven structure of the surface protective layer has a protruding peak height Rpk of 3.5 ⁇ m or more, and the surface protective layer has a mass concentration C (mass %) of carbon atoms, a mass concentration O (mass %) of oxygen atoms, and a mass concentration Si (mass %) of silicon atoms that satisfy the following relationship formula: 0.5 ⁇ Si/(C+O+Si) ⁇ 100 A decorative sheet that satisfies the above requirements is provided.
  • a decorative sheet is provided for the above-mentioned side, in which the protruding peak height Rpk is 25 ⁇ m or less.
  • the surface protective layer has a mass concentration C (mass %) of carbon atoms, a mass concentration O (mass %) of oxygen atoms, and a mass concentration Si (mass %) of silicon atoms that satisfy the following relationship: 0.5 ⁇ Si/(C+O+Si) ⁇ 100 ⁇ 5.0
  • a decorative sheet according to any of the above aspects which satisfies the above.
  • a decorative sheet according to any of the above aspects, in which the uneven structure of the surface protection layer has an average length RSm of the roughness curve element of 150 ⁇ m or more.
  • a decorative sheet according to the above aspect in which the average length RSm is 600 ⁇ m or less.
  • a decorative sheet according to any of the above aspects, in which the thickness of the surface protective layer is 8 ⁇ m or more.
  • a decorative sheet according to any of the above aspects, in which the gloss of the surface protective layer is 10.0 or less.
  • a decorative sheet relating to any of the above aspects, in which at least some of the ridge portions are adjacent to each other in the width direction, and in a cross section parallel to the width direction and the thickness direction of the surface protection layer at a position where the at least some of the ridge portions are adjacent to each other in the width direction, the portion in which the uneven structure is provided has a sinusoidal shape.
  • the surface protective layer includes a cured product of an ionizing radiation curable resin.
  • the ionizing radiation curable resin is an acrylate whose main component contains a repeating structure, the repeating structure is any one of ethylene oxide, propylene oxide, and ⁇ -caprolactone, and the number of repetitions of the repeating structure is 3 or more.
  • a decorative material comprising a decorative sheet according to any of the above aspects and a substrate to which the decorative sheet is attached.
  • the present invention makes it possible to provide a decorative sheet that has a rough feel and excellent uniformity of feel.
  • FIG. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a surface protective layer included in the decorative sheet of FIG.
  • FIG. 3 is a microscope image of a surface protective layer included in a decorative sheet according to one example of the present invention.
  • the resin for the transparent resin layer 4.
  • various additives such as heat stabilizers, light stabilizers, antiblocking agents, catalyst scatterers, colorants, light scattering agents, and gloss adjusters can also be added to the transparent resin layer 4 as necessary.
  • heat stabilizers heat stabilizers, light stabilizers, antiblocking agents, catalyst scatterers, colorants, light scattering agents, and gloss adjusters can also be added to the transparent resin layer 4 as necessary.
  • phenol-based, sulfur-based, phosphorus-based, and hydrazine-based heat stabilizers and hindered amine-based light stabilizers are added in any combination.
  • 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 ridge portion 5B is imaged. Next, from this cross-sectional image, the dimension of the surface protective layer 5 in the width direction of the ridge portion 5B and the area of the cross section 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 coating liquid for the surface protection layer may further contain particles other than silica particles.
  • the particles other than silica particles that can be used include particles made of organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads, and particles made of inorganic materials such as glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.
  • the average particle size (D50) of the above particles, including silica particles, is preferably 10 ⁇ m or less.
  • the average particle size (D50) of the particles is more preferably 1 ⁇ m or more and 8 ⁇ m or less, and even more preferably 2 ⁇ m or more and 6 ⁇ m or less.
  • the particles are likely to fall off from the surface protective layer 5, which may make it difficult to achieve high scratch resistance.
  • the particles are small, the effect of generating wrinkles uniformly is small.
  • the "average particle size (D50)" is the median size (D50) measured by a laser diffraction/scattering type particle size distribution measuring device. If the coating liquid for the surface protective layer contains particles, the surface protective layer 5 obtained from this coating liquid will also contain particles. The average particle size of the particles contained in the surface protective layer 5 can be determined by observing the cross section of the layer and averaging the particle sizes of multiple particles. The value obtained in this manner is substantially the same as the median size (D50) measured by a laser diffraction/scattering type particle size distribution measuring device. Therefore, the above-mentioned range of average particle sizes can also be interpreted as the range of average particle sizes of the particles contained in the surface protective layer 5.
  • the coating liquid for the surface protective layer may further contain a solvent and additives for improving the functionality of the final product, such as antibacterial agents and antifungal agents.
  • the coating liquid for the surface protective layer may further contain other additives such as an ultraviolet absorber and a light stabilizer.
  • an ultraviolet absorber for example, a benzotriazole-based, benzoate-based, benzophenone-based, or triazine-based agent may be used.
  • a hindered amine-based agent may be used. According to the method described herein, a surface protective layer 5 having a low gloss level can be formed without a gloss adjuster (matte additive).
  • the coating liquid for the surface protective layer further contains a photoinitiator.
  • the photoinitiator is not particularly limited, but examples include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based photoinitiators.
  • the amount of photoinitiator added is preferably 0.1 to 10 parts by mass, more preferably 0.25 to 8 parts by mass, and even more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of ionizing radiation curable resin. If the amount of photoinitiator is less than 0.1 parts by mass, the effect of the first irradiation step described above is less likely to be achieved. If the amount of photoinitiator is more than 10 parts by mass, the coating film will be completely cured, making it difficult for wrinkles to form in the subsequent second irradiation step.
  • a high-pressure mercury lamp, a metal halide lamp, or a single-wavelength LED lamp with a wavelength of 200 nm or more and 400 nm or less can be selected and used.
  • the cumulative light amount of the first irradiation light is preferably 2 mJ/cm2 or more and 100 mJ/cm2 or less, more preferably 10 mJ/cm2 or more and 80 mJ/ cm2 or less, and even more preferably 20 mJ/ cm2 or more and 60 mJ/ cm2 or less. If the cumulative light amount is small, the effect of the first irradiation step described above is difficult to appear. If the cumulative light amount is large, the coating film is completely cured, and wrinkles are difficult to form in the subsequent second irradiation step.
  • the second irradiation step is carried out.
  • the coating film is irradiated with light having a wavelength of 200 nm or less (hereinafter referred to as the second irradiation light).
  • the ionizing radiation curable resin contained in the coating liquid for the surface protective layer has a large absorption coefficient for the second irradiation light. Therefore, the second irradiation light incident on the coating film can only reach a position that is several tens to several hundreds of nm away from the outermost surface. Therefore, in the second irradiation step, the crosslinking reaction proceeds in the surface region of the coating film to form an extremely thin cured film, while in other regions, the crosslinking reaction does not proceed and the coating film remains uncured.
  • the second irradiation light does not reach monomers that are located away from the surface of the coating film, so no crosslinking reaction occurs there. However, some of the monomers that are located away from the surface of the coating film migrate to the cured film, where they undergo a crosslinking reaction. In this way, the number of molecules involved in the crosslinking reaction increases.
  • the volume of the cured film increases. Since the crosslinking reaction only occurs on the surface of the coating, the cured film cannot increase in volume in the thickness direction, but expands in the in-plane direction. As a result, wrinkles appear on the surface of the coating.
  • the gas used in the excimer lamp may be any conventional gas that emits light of 200 nm or less.
  • the gas may be a rare gas such as Xe, Ar, or Kr, or a mixed gas of a rare gas such as ArBr or ArF with a halogen gas.
  • the wavelength (center wavelength) of the excimer lamp varies depending on the gas, and may be, for example, about 172 nm (Xe), about 126 nm (Ar), about 146 nm (Kr), about 165 nm (ArBr), or about 193 nm (ArF).
  • a xenon lamp that emits excimer light with a central wavelength of 172 nm as the light source. Also, considering the cost of maintaining the equipment and the availability of materials, it is preferable to use a xenon lamp as the light source.
  • the second irradiation step is carried out in an atmosphere with a low oxygen concentration.
  • Oxygen has a large absorption coefficient for light of 200 nm or less. Therefore, it is preferable to carry out the second irradiation step in, for example, a nitrogen gas atmosphere.
  • the oxygen concentration in the gas phase in the second irradiation step i.e., the residual oxygen concentration in the reaction atmosphere, is preferably 2000 ppm or less, and more preferably 1000 ppm or less.
  • oxygen in the atmosphere inhibits radical polymerization. Therefore, the residual oxygen concentration in the reaction atmosphere affects the formation of wrinkles on the coating surface. Therefore, changing the residual oxygen concentration in the reaction atmosphere can also change the surface properties of the surface protective layer 5.
  • the third radiation or irradiation light is ionizing radiation such as an electron beam, or ultraviolet light having a longer wavelength than the second irradiation light.
  • the integrated light amount of the third irradiation light is preferably 10 mJ/ cm2 or more and 500 mJ/ cm2 or less, more preferably 50 mJ/ cm2 or more and 400 mJ/ cm2 or less, and even more preferably 100 mJ/ cm2 or more and 300 mJ/ cm2 or less.
  • the decorative sheet 1 has the above-mentioned surface properties in the surface protective layer 5.
  • Such a decorative sheet 1 provides the user with a rough and uniform tactile sensation when the user slides his/her skin over the surface of the surface protective layer 5. In other words, this decorative sheet 1 allows the user to sense the presence of large irregularities over the entire surface of the surface protective layer 5.
  • the decorative sheet 1 which gives the user a rough feel to the touch, is suitable for use when the item whose appearance is to be reproduced with the decorative sheet 1 is one that has a rough feel to the touch and is likely to come into contact with the user's skin.
  • the decorative sheet 1 is suitable for use on furniture, etc.
  • the surface protective layer 5 of the decorative sheet 1 has the above-mentioned surface properties, and therefore can achieve a low gloss even without containing a gloss regulator (matt additive).
  • Gloss regulators reduce the oil repellency of the layer formed from the resin material, so a surface protective layer containing a gloss regulator is prone to fingerprints.
  • a surface protective layer 5 that does not contain a gloss regulator is less likely to absorb oil, and therefore fingerprints are less likely to adhere to it.
  • a surface protective layer 5 with excellent oil repellency is less likely to cause oil stains or adsorb contaminants.
  • the gloss regulator particles do not fall off, and therefore a decorative sheet 1 containing such a surface protective layer 5 is less likely to cause gloss changes or scratches.
  • Oxygen in the gas phase not only absorbs short-wavelength ultraviolet light, but also inhibits radical polymerization.
  • the effect of oxygen contained in the gas phase on radical polymerization is greatest in the portion of the coating film made of ionizing radiation curable resin adjacent to the gas phase, and decreases as the distance from the coating film surface increases. Therefore, by changing the oxygen concentration in the gas phase in the second irradiation step, it is possible to change the relationship between the distance from the coating film surface and the progress of the crosslinking reaction.
  • the thickness of the cured film formed on the surface of the coating by the second irradiation process and the degree of expansion of the cured film in the in-plane direction according to the progress of the crosslinking reaction change.
  • the thickness of the cured film and the degree of expansion of the cured film in the in-plane direction are also affected by the integrated light amount in the second irradiation process.
  • the thickness of the cured film and the degree of expansion of the cured film in the in-plane direction also affect the surface properties of the surface protective layer. Furthermore, the thickness of the coating also affects the formation of wrinkles.
  • Example 1 The decorative sheet 1 described with reference to Figures 1 to 3 was produced by the following method.
  • the transparent resin layer 4, the primer layer 6, the adhesive layer 7 and the concealing layer 8 were omitted.
  • an impregnated paper (GFR-506: manufactured by Kohjin Co., Ltd.) with a basis weight of 50 g/ m2 was prepared as the original fabric layer 2.
  • a design layer 3 was formed using an oil-based nitrocellulose resin-based gravure printing ink (PCNT (PCRNT) various colors: manufactured by Toyo Ink Co., Ltd.).
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 6 moles added)
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm under atmospheric pressure, so that the accumulated light amount was 150 mJ/ cm2 .
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (EO 15 moles added)
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm under atmospheric pressure, so that the accumulated light amount was 150 mJ/ cm2 .
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Caprolactone modified tris-(2-acryloxyethyl) isocyanurate (3 moles of caprolactone (CL) added)
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, so that the accumulated light amount was 200 mJ/ cm2 .
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm under atmospheric pressure, so that the accumulated light amount was 150 mJ/ cm2 .
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following ionizing radiation curable resin was used. The coating film made of the coating liquid for the surface protective layer was formed to a thickness of 15 ⁇ m.
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (EO 50 moles added)
  • EO 50 moles added Ethoxylated pentaerythritol tetraacrylate
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, so that the accumulated light amount was 150 mJ/ cm2 .
  • Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points: That is, in this example, the following ionizing radiation curable resin was used.
  • - Ionizing radiation curable resin Type Ethoxylated pentaerythritol tetraacrylate (EO 20 moles added)
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm under atmospheric pressure, so that the accumulated light amount was 200 mJ/ cm2 .
  • the surface of the coating film made of the coating liquid for the surface protective layer was irradiated with ultraviolet light having a wavelength of 172 nm using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, so that the accumulated light amount was 150 mJ/ cm2 .
  • 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 (EO 35 moles added)
  • Particle size 5 ⁇ m Blending ratio: 15 parts by mass
  • the first and second irradiation steps were not carried out, and the coating film made of the coating liquid for forming a surface protective layer was cured only by the third irradiation step.
  • the 20 evaluators evaluated the uniformity of the texture by the following method. A test piece measuring 10 cm long x 10 cm wide was cut from each decorative sheet. Each of the 20 evaluators was blindfolded and asked to freely slide their finger over the entire surface of the surface protective layer of each test piece, and to classify the uniformity of the texture into the following three groups based on the presence or absence or the degree of change in the texture (rough texture).
  • Group 1 There was no area where the skin texture (roughness) felt different.
  • Group 2 There were some areas where the skin texture (roughness) felt different, but the degree of change was slight.
  • Group 3 There were some areas where the texture (roughness) felt clearly different.
  • the evaluation criteria were as follows. AA: No scratches or changes in gloss occurred on the surface. A: Minor scratches or changes in gloss occurred on the surface. B: Significant scratches or changes in gloss occurred on the surface.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Floor Finish (AREA)
PCT/JP2023/046694 2023-01-04 2023-12-26 化粧シート Ceased WO2024147318A1 (ja)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2024522413A JP7582561B1 (ja) 2023-01-04 2023-12-26 化粧シート
CN202380089601.1A CN120435382A (zh) 2023-01-04 2023-12-26 装饰片
KR1020257021098A KR20250133654A (ko) 2023-01-04 2023-12-26 화장 시트
EP23914804.2A EP4647250A4 (en) 2023-01-04 2023-12-26 Decorative sheet
JP2024192141A JP2025010355A (ja) 2023-01-04 2024-10-31 化粧シート
US19/258,511 US20250333908A1 (en) 2023-01-04 2025-07-02 Decorative sheet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023000275 2023-01-04
JP2023-000275 2023-01-04

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US19/258,511 Continuation US20250333908A1 (en) 2023-01-04 2025-07-02 Decorative sheet

Publications (1)

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WO2024147318A1 true WO2024147318A1 (ja) 2024-07-11

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PCT/JP2023/046694 Ceased WO2024147318A1 (ja) 2023-01-04 2023-12-26 化粧シート

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US (1) US20250333908A1 (https=)
EP (1) EP4647250A4 (https=)
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KR (1) KR20250133654A (https=)
CN (1) CN120435382A (https=)
WO (1) WO2024147318A1 (https=)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007185606A (ja) * 2006-01-13 2007-07-26 Nippon Paint Co Ltd 意匠性塗膜の形成方法、建材用ボード及び水性塗料組成物
WO2017033972A1 (ja) * 2015-08-24 2017-03-02 凸版印刷株式会社 化粧シート
JP2018144437A (ja) * 2017-03-08 2018-09-20 凸版印刷株式会社 化粧シートおよび化粧シートの製造方法
JP2020075420A (ja) * 2018-11-08 2020-05-21 凸版印刷株式会社 化粧シート及びその製造方法
JP2021137990A (ja) * 2020-03-03 2021-09-16 凸版印刷株式会社 化粧シート、化粧板及び化粧シートの製造方法
WO2022239270A1 (ja) * 2021-05-12 2022-11-17 凸版印刷株式会社 化粧シート、及び化粧シートの製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7003667B2 (ja) 2018-01-05 2022-02-10 凸版印刷株式会社 化粧材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007185606A (ja) * 2006-01-13 2007-07-26 Nippon Paint Co Ltd 意匠性塗膜の形成方法、建材用ボード及び水性塗料組成物
WO2017033972A1 (ja) * 2015-08-24 2017-03-02 凸版印刷株式会社 化粧シート
JP2018144437A (ja) * 2017-03-08 2018-09-20 凸版印刷株式会社 化粧シートおよび化粧シートの製造方法
JP2020075420A (ja) * 2018-11-08 2020-05-21 凸版印刷株式会社 化粧シート及びその製造方法
JP2021137990A (ja) * 2020-03-03 2021-09-16 凸版印刷株式会社 化粧シート、化粧板及び化粧シートの製造方法
WO2022239270A1 (ja) * 2021-05-12 2022-11-17 凸版印刷株式会社 化粧シート、及び化粧シートの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4647250A1 *

Also Published As

Publication number Publication date
CN120435382A (zh) 2025-08-05
JP7582561B1 (ja) 2024-11-13
JP2025010355A (ja) 2025-01-20
JPWO2024147318A1 (https=) 2024-07-11
EP4647250A1 (en) 2025-11-12
EP4647250A4 (en) 2026-04-29
US20250333908A1 (en) 2025-10-30
KR20250133654A (ko) 2025-09-08

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