WO2024019096A1 - 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
WO2024019096A1
WO2024019096A1 PCT/JP2023/026471 JP2023026471W WO2024019096A1 WO 2024019096 A1 WO2024019096 A1 WO 2024019096A1 JP 2023026471 W JP2023026471 W JP 2023026471W WO 2024019096 A1 WO2024019096 A1 WO 2024019096A1
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WIPO (PCT)
Prior art keywords
protective layer
decorative sheet
less
surface protective
light
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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/JP2023/026471
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English (en)
French (fr)
Japanese (ja)
Inventor
祥美 山崎
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
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Toppan Holdings Inc
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Filing date
Publication date
Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to JP2024535119A priority Critical patent/JPWO2024019096A1/ja
Priority to EP23843019.3A priority patent/EP4559675A4/en
Publication of WO2024019096A1 publication Critical patent/WO2024019096A1/ja
Priority to US19/021,353 priority patent/US20250205991A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • 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
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • 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

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 used in the above-mentioned buildings by attaching adhesives to the surfaces of wood, wood boards, metal plates, noncombustible boards, paper substrates, or resin substrates in order to add design and durability to the surfaces. It is generally widely used by laminating it together to form a decorative board.
  • 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. Furthermore, decorative sheets are required to have water resistance in order to prevent deterioration due to water intrusion from the surface of the sheet when used around water. As described above, the decorative sheet described in Patent Document 1, for example, has been proposed as a decorative sheet in which design (low gloss), scratch resistance, and stain resistance are taken into consideration.
  • the present invention has an excellent design with low gloss, and also has fingerprint resistance, high durability (especially scratch resistance and stain resistance), processability, and water resistance.
  • the purpose of the present invention is to provide a decorative sheet that has the following properties.
  • the present inventor optimized the uneven shape of the surface protective layer in order to achieve low gloss, and further experimented to find the necessary structural elements for the material used for the surface protective layer. It has been discovered that it is possible to provide a decorative sheet that exhibits fingerprint resistance, high durability (particularly scratch resistance and stain resistance), processability, and water resistance.
  • a raw fabric layer, a water-resistant protective layer, and a surface protective layer are laminated in this order, and the surface protective layer has ridged portions projecting in a ridge shape on its surface.
  • the ratio RSm/Ra of the surface roughness index RSm of the uneven shape of the surface protective layer to the surface roughness index Ra is within the range of 10 to 300, and the surface
  • the main material of the protective layer is an ionizing radiation-curable resin
  • the main component of the ionizing radiation-curable resin is a trifunctional acrylic resin containing a repeating structure, and the number of repetitions of the repeating structure is 3 or more. It is characterized by
  • a method for manufacturing a decorative sheet according to another aspect of the present invention is a method for manufacturing a decorative sheet according to the above aspect, in which the surface of the applied ionizing radiation curable resin is irradiated with light having a wavelength of 200 nm or less. After that, by irradiating with ionizing radiation or UV light having a wavelength longer than the light having a wavelength of 200 nm or less, a surface protective layer having protruding ridged portions is formed.
  • a decorative sheet that has low gloss, fingerprint resistance, scratch resistance, stain resistance, bending workability, and water resistance.
  • FIG. 1 is a cross-sectional view schematically showing an example of a decorative sheet according to an embodiment of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing an example 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 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 one embodiment of the present invention. It is a schematic diagram explaining the time change of the irradiation light quantity of each irradiation light in the manufacturing process of the decorative sheet concerning one embodiment of the present invention.
  • the decorative sheet 1 of this embodiment has a pattern layer 3, an adhesive layer 7 (for example, a heat-sensitive adhesive layer, an anchor A coating layer, a dry laminate adhesive layer), a transparent resin layer 4, a water-resistant protective layer 9, and a surface protective layer 5 are laminated in this order. Furthermore, a concealing layer 8 and a primer layer 6 are provided in this order on the other surface of the raw fabric layer 2, that is, the back surface side.
  • the pattern layer 3, the adhesive layer 7, the transparent resin layer 4, the hiding layer 8, and the primer layer 6 may not be provided.
  • a decorative sheet 1 according to an embodiment of the present invention 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 plate 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. Since 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 may be appropriately selected from acrylic, polyester, polyurethane, epoxy, and other 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 resin material for the water-resistant protective layer 9 is not particularly limited, and for example, ionizing radiation-curable resins and thermosetting resins are preferably used.
  • ionizing radiation curable resin known ones such as various monomers and commercially available oligomers can be used, such as pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4A), trimethylolpropane, etc.
  • polyfunctional monomers such as triacrylate (TMPTA) and dipentaerythritol hexaacrylate (DPHA), polyfunctional oligomers such as Shiko UV-1700B (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.), or a mixture thereof. .
  • thermosetting resin is preferably one formed by curing a polymer containing a carboxyl group described below with an epoxy compound or a carbodiimide compound by heat, for example.
  • Polymers containing carboxylic groups are not particularly limited, but may be used, for example, to impart mechanical properties by elongation of the molecular structure, such as various acrylic polymers, various polyesters, and various polyethers. , various polycarbonates, various polyurethanes, and the like.
  • Epoxy group is a general term for compounds that have a three-membered ring ether, oxacyclopropane (oxirane), in its structural formula, and has excellent reactivity and is used in a variety of applications. Additionally, epoxy compounds have the effect of suppressing hydrolysis, which is a major problem for general-purpose resins, by supplementing the acid in the polymer that serves as a catalyst for the decomposition reaction, so they are effective in improving water resistance.
  • oxirane oxacyclopropane
  • epoxy compounds include, but are not particularly limited to, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and pentaerystol.
  • N-tert-butyl-N'-ethylcarbodiimide N-cyclohexyl-N'-2-morpholinoethylcarbodiimide, meso-p-toluenesulfonic acid, N,N'-di-tert-butylcarbodiimide, and the like.
  • a major product of carbodiimide compounds is "Carbodilite V-02-L2" manufactured by Nisshinbo Chemical Co., Ltd.
  • the resin constituting the waterproof protective layer 9 in this embodiment it is preferable that an acrylic copolymer having an acid value of 15 mgKOH/g or more is crosslinked with a curing agent.
  • the acid value is 15 mgKOH/g or less, the crosslinking density after curing will be low, so there is a risk that the water resistance will deteriorate.
  • the acrylic resin contained in the water-resistant protective layer 9 is an aqueous emulsion. If the acrylic resin contained in the top coat layer 15 is an aqueous emulsion, a resin film with a high molecular weight can be obtained and water resistance will be improved.
  • the thickness of the water-resistant protective layer 9 is preferably in the range of 2 ⁇ m or more and 10 ⁇ m or less.
  • the film thickness is 2 ⁇ m or less, water resistance will be insufficiently imparted.
  • the film thickness is 10 ⁇ m or more, drying will be insufficient when using an aqueous emulsion, and sufficient performance will be achieved with a film thickness of 10 ⁇ m or less, so making the film thicker than this takes into consideration cost. It is decided that there is no need to do so.
  • 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 shown.
  • FIG. 3 is a plane photograph obtained using a laser microscope (OLS-4000 manufactured by Olympus Corporation).
  • 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). and the thickness direction of the surface protective layer 5, which is the vertical direction in FIG. , preferably 10 or more and 300 or less. More preferably, RSm/Ra is 10 or more and 250 or less. When 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. When RSm/Ra is greater than 300, the intervals between the ridges are too wide, resulting in poor gloss.
  • RSm/Ra is more preferably 50 or more and 200 or less. When RSm/Ra is within this numerical range, 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. Moreover, RSm/Ra is most preferably 80 or more and 150 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.
  • 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.
  • the shape between adjacent ridged portions 5B may be a concave curved shape. That is, the shape of the lowest position C of the ridged portion 5B may be a concave curved shape.
  • 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 having a wavelength of 200 nm or less, it is possible to crosslink the acrylate. Light with a wavelength of 200 nm or less reaches a depth of several tens to several hundred 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 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.
  • the first irradiation light which has a wavelength of 200 nm or less, can be extracted by excimer VUV light.
  • Excimer VUV light can be produced from noble gas or noble gas halide compound lamps. When high-energy electrons are applied from the outside to a lamp filled with a gas such as a rare gas or a rare gas halide compound, a large amount of discharge plasma (dielectric barrier discharge) is generated. This plasma discharge excites the atoms of the discharge gas (rare gas) and instantaneously becomes an excimer state. When returning from this excimer state to the ground state, it emits light in a wavelength range unique to that excimer.
  • a gas such as a rare gas or a rare gas halide compound
  • the gas used in the excimer lamp may be any conventionally used gas as long as it emits light of 200 nm or less.
  • a rare gas such as Xe, Ar, or Kr
  • a mixed gas of a rare gas such as ArBr or ArF and a halogen gas
  • Excimer lamps have different wavelengths (center wavelengths) depending on the gas, such as approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), and approximately 193 nm (ArF).
  • a xenon lamp that emits excimer light with a center wavelength of 172 nm as the light source. Furthermore, when considering the cost of equipment maintenance and the availability of materials, it is preferable to use a xenon lamp as the light source.
  • the first irradiation 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.
  • 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 irradiated 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 200 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 irradiation form shown in FIG. 5(f) may be used. It is preferable to use the irradiation mode in combination with the irradiation form of the second irradiation light.
  • the ridged portions 5B formed by irradiating light with a wavelength of 200 nm or less have a fine structure compared to the uneven shape formed on the surface of the surface protective layer 5 by mechanical processing such as embossing. It becomes.
  • 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. When 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.
  • 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 layer thickness of the surface protective layer 5 refers to the distance in the thickness direction of the surface protective layer 5 from the position in contact with the water-resistant protective layer 9 to the highest position of the uneven shape.
  • the layer thickness of the ridged portion 5B refers to the distance in the thickness direction of the ridged portion 5B from the lowest position of the uneven shape, that is, the upper surface of the core portion 5A to the highest position of the uneven shape.
  • 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 because 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 protection layer 5 is an ionizing radiation curable resin.
  • the main material 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 surface protective layer.
  • the ionizing radiation-curable resin constituting the surface protective layer 5 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 trifunctional acrylate resin containing a repeating structure.
  • the trifunctional acrylate resin for example, trimethylolpropane triacrylate, glycerin triacrylate, isocyanurate triacrylate, pentaerythritol triacrylate, etc. 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.
  • the degree of crosslinking is insufficient and the scratch resistance decreases, which is not preferable.
  • the degree of crosslinking becomes too high, resulting in poor processability, which is undesirable.
  • the ionizing radiation curable resin has a suitable viscosity range of 10 mPa ⁇ s or more and 500 mPa ⁇ s or less, and an optimal viscosity range of 50 mPa ⁇ s or more and 300 mPa ⁇ s or less. Therefore, it is preferable to use trimethylolpropane triacrylate or glycerin triacrylate as the trifunctional acrylate resin because it is possible to keep the viscosity within a suitable or optimum viscosity range. Resins having skeletons that cause hydrogen bonding or ⁇ - ⁇ stacking often have a high viscosity of 500 mPa ⁇ s or more, which is not preferable.
  • 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. Therefore, when using a bifunctional acrylate resin by adding it to a trifunctional acrylate resin, 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 trifunctional acrylate resin. is preferable, and more preferably within the range of 15% by mass or more and 20% by mass or less.
  • the repeating structure is preferably 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 with a wavelength of 200 nm or less, and fine uneven shapes are easily formed. Further, the number of repetitions of this repeating structure is 3 or more. More preferably, it is 3 or more and 30 or less, most preferably 3 or more and 20 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 30, 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.
  • the ionizing radiation-curable resin constituting the surface protective layer 5 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.
  • organic materials such as PE wax, PP wax, and resin beads
  • inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate can be used.
  • the average particle size 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. Further, 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.
  • 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. It may be a value that is actually measured and averaged. Although the measurement methods for both methods are different, the obtained particle size values are substantially the same.
  • 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 5.0 or less even though it does not contain a gloss adjuster (matting additive), resulting in a decorative sheet with an extremely low gloss level.
  • a gloss adjuster such 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.
  • the decorative sheet 1 makes it possible to obtain a decorative sheet with a low gloss level of 5.0 or less while maintaining the same performance as 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 waterproof protective layer 9 is formed on the upper surface of the raw fabric layer 2 by printing. Furthermore, a surface protective layer 5 is formed by printing on the upper surface of the waterproof protective layer.
  • 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.
  • 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.
  • this embodiment is not limited to the embodiment described above, and for example, in order to cure the contracted ionizing radiation-curable resin, ionizing radiation or light with a wavelength of 200 nm or less, which is the first irradiation light, is used. You may irradiate UV light with a longer wavelength only once. Further, in this case, the cumulative amount of light having a wavelength of 200 nm or less, which is the first irradiation light, may be set to 0.5 mJ/cm 2 or more and 200 mJ/cm 2 or less.
  • 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.
  • 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. Furthermore, according to the structure of 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.
  • 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 is mainly composed of an ionizing radiation-curable resin, and the ionizing radiation-curable resin has a repeating structure as a main component.
  • the repeating structure is preferably one of ethylene oxide, propylene oxide, and ⁇ -caprolactone structures, and the number of repeats of the repeating structure is 3 or more, and the surface
  • the layer located on the raw fabric layer 2 side of the protective layer 5 (that is, the layer located below the outermost layer of the surface protective layer 5) is not particularly limited.
  • Example 1 An olefin film (manufactured by RIKEN TECHNOS Co., Ltd.) having a thickness of 55 ⁇ m was used as the raw layer, one side of the raw layer was subjected to corona treatment, and the following water-resistant protective layer coating liquid was applied to the other side. Thereafter, the water-resistant protective layer 9 was formed by drying and curing the water-resistant protective layer coating liquid. Subsequently, the following surface protective layer coating liquid was applied onto the top of the water-resistant protective layer 9. The layer thickness of the surface protective layer coating liquid was 5 ⁇ m.
  • 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 100 kGy of ionizing radiation to cure 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 water-resistant protective layer was composed of the following water-based emulsion resin and the following curing components.
  • ⁇ Water-based emulsion resin Type Acrylic resin Product name: SETAQUA6776 (manufactured by Allnex) Composition: 100 parts by weight / Curing component Type: Epoxy resin Product name: EX-810 (manufactured by Nagase ChemteX Co., Ltd.) Blend: 5 parts by weight
  • 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 Trimethylolpropane EO-modified triacrylate (6 moles of EO added)
  • 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 contained in the surface protective layer coating liquid of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (15 moles of EO added)
  • Example 3 A decorative sheet of Example 3 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin contained in the surface protective layer coating liquid of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO modified triacrylate (3 moles of EO added)
  • 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 contained in the surface protective layer coating liquid of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane PO modified triacrylate (addition of 6 moles of PO)
  • Example 5 A decorative sheet of Example 5 was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin contained in the surface protective layer coating liquid of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Caprolactone-modified tris(2-acryloxyethyl) isocyanurate (3 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 13 A decorative sheet of Example 13 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 thickness of the water-resistant protective layer of Example 1 was changed to 1 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (50 moles of EO added)
  • Comparative Example 1 was carried out in the same manner as in Example 1 except that the step of irradiating the surface of the surface protective layer coating liquid of Example 1 with the Xe excimer lamp was not provided and the amount of particles was 15 parts by mass. I got a cosmetic sheet.
  • ⁇ Ionizing radiation curable resin Type Ethylene glycol diacrylate (9 moles of EO added)
  • Product name Light acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.)
  • ⁇ 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 contained in the surface protective layer coating liquid of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Pentaerythritol tetraacrylate (35 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 contained in the surface protective layer coating liquid of Example 1 was replaced with the following.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane triacrylate Product name: NK Ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • ⁇ Comparative example 5> A decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the water-resistant protective layer of Example 1 was not provided.
  • ⁇ Comparative example 6> A decorative sheet of Comparative Example 6 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 and the film thickness was changed to 20 ⁇ m.
  • ⁇ Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (60 moles of EO added)
  • ⁇ 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
  • ⁇ Fingerprint resistance Wipeability evaluation>
  • a fingerprint wiping property evaluation was conducted. The gloss level at 60 degrees on the surface of each decorative sheet was measured and defined as [initial gloss level]. 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 glossiness at 60 degrees of the portion where the fingerprint resistance evaluation liquid was wiped off was measured and defined as [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 steel wool and the sheet was rubbed back and forth 20 times, and scratches and changes in gloss on the surface of the decorative sheet 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
  • ⁇ Bending workability test> The obtained decorative sheet was attached to the wooden substrate B using a urethane adhesive with the surface on the raw fabric layer side (i.e., the back side of the decorative sheet) facing the wooden substrate B, and then the decorative sheet was applied. A V-shaped groove is inserted to the boundary where the wooden substrate B and the decorative sheet 1 are pasted together to prevent the sheet from being damaged. Next, the wooden substrate B is bent to 90 degrees along the V-shaped groove so that the surface of the decorative sheet on the surface protection layer side (that is, the surface of the decorative sheet) becomes a mountain fold. The condition of bendability was evaluated by observing using an optical microscope whether there were any whitening or cracks. The evaluation criteria were as follows. ⁇ : No whitening or cracks are observed ⁇ : Whitening is observed in some areas ⁇ : Whitening is observed on the entire surface or cracks are observed in some areas
  • the decorative sheets of Examples 1 to 18 provide decorative sheets having low gloss, fingerprint resistance, scratch resistance, stain resistance, bending workability, and water resistance. Can be done.
  • further performance improvement is possible by optimizing the layer thickness of the surface protective layer, and the particle size and amount of the particles to be blended.
  • the present invention can take the following configuration, for example.
  • a raw fabric layer, a water-resistant protective layer, and a surface protective layer are laminated in this order,
  • the surface protective layer has an uneven shape having protruding ridged portions on its surface,
  • the ratio RSm/Ra of the surface roughness index RSm of the uneven shape of the surface protective layer to the surface roughness index Ra is within the range of 10 to 300
  • the main material of the surface protective layer is an ionizing radiation curable resin
  • the ionizing radiation curable resin is a trifunctional acrylic resin whose main component includes a repeating structure,
  • a decorative sheet characterized in that the number of repetitions of the repeating structure is 3 or more.
  • thermosetting resin The main material of the resin component constituting the water-resistant protective layer is a thermosetting resin
  • the thermosetting resin includes a resin having a crosslinked structure formed by a coating liquid containing an acrylic resin as a resin component and an epoxy compound as a curing component. sheet.
  • the repeating structure is any one of ethylene oxide, propylene oxide, and ⁇ -caprolactone structures.
  • the thickness of the surface protective layer is within a range of 2 ⁇ m or more and 20 ⁇ m or less.
  • the surface protective layer contains particles having an average particle size of 10 ⁇ m or less.
  • the amount of the particles added is within a range of 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.
  • the surface protective layer has a glossiness of 5.0 or less.
  • the surface protective layer includes a core portion and the ridged portion formed on the core portion,
  • the ratio of the layer thickness of the ridged portion to the layer thickness of the core portion is within a range of 0.01 or more and 2.0 or less.
  • the ratio of the layer thickness of the ridged portion to the layer thickness of the core portion is within a range of 0.1 or more and 1.0 or less.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/026471 2022-07-20 2023-07-19 化粧シート及び化粧シートの製造方法 Ceased WO2024019096A1 (ja)

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EP23843019.3A EP4559675A4 (en) 2022-07-20 2023-07-19 DECORATIVE SHEET AND METHOD FOR MANUFACTURING DECORATIVE SHEET
US19/021,353 US20250205991A1 (en) 2022-07-20 2025-01-15 Decorative sheet and method for manufacturing decorative sheet

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JP2022115514 2022-07-20

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JP2005119297A (ja) * 2004-09-27 2005-05-12 Toyo Kohan Co Ltd 化粧板積層用樹脂フィルム、その樹脂フィルムを積層した化粧板、およびその化粧板を用いたユニットバス
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WO2025220703A1 (ja) * 2024-04-19 2025-10-23 Ｔｏｐｐａｎホールディングス株式会社 化粧シート
WO2026038502A1 (ja) * 2024-08-14 2026-02-19 Ｔｏｐｐａｎホールディングス株式会社 化粧シート

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EP4559675A4 (en) 2025-10-22

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