WO2017034021A1 - Feuille décorative et procédé de production de feuille décorative - Google Patents

Feuille décorative et procédé de production de feuille décorative Download PDF

Info

Publication number
WO2017034021A1
WO2017034021A1 PCT/JP2016/074968 JP2016074968W WO2017034021A1 WO 2017034021 A1 WO2017034021 A1 WO 2017034021A1 JP 2016074968 W JP2016074968 W JP 2016074968W WO 2017034021 A1 WO2017034021 A1 WO 2017034021A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
decorative sheet
dispersant
vesicle
surface protective
Prior art date
Application number
PCT/JP2016/074968
Other languages
English (en)
Japanese (ja)
Inventor
恵 柏女
正光 長濱
佐藤　彰
高橋　昌利
Original Assignee
凸版印刷株式会社
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 凸版印刷株式会社 filed Critical 凸版印刷株式会社
Publication of WO2017034021A1 publication Critical patent/WO2017034021A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a decorative sheet and a method for manufacturing the decorative sheet.
  • Examples of techniques for adding sodium calcium aluminosilicate particles and colloidal silica to the surface protective layer forming the surface layer of the decorative sheet include those described in Patent Documents 1 and 2.
  • these decorative sheets are provided with a surface protective layer having high transparency from the viewpoint of design and excellent post-processing resistance that is not affected by post-processing such as surface scratch resistance and V-groove bending. There is a problem that there are few things to have.
  • the present invention focuses on the above points, and provides a decorative sheet excellent in scratch resistance and post-processing resistance and a method for manufacturing the decorative sheet while ensuring transparency in the surface protective layer. Objective.
  • the decorative sheet which is one embodiment of the present invention has one or two or more intermediate layers on one surface of the base material layer, and one or two layers on the intermediate layer.
  • a dispersant and inorganic nanoparticles to the surface protective layer, it is possible to ensure high transparency and further improve scratch resistance and post-processability. It becomes possible.
  • both the dispersant and the inorganic nanoparticles are in a vesicle state by being encapsulated in a liposome having an outer membrane made of phospholipid, the dispersibility of the dispersant and the inorganic nanoparticles is significantly improved. Therefore, higher transparency can be secured. Further, since the inorganic particles are nano-sized, deterioration of the matte appearance over time can be suppressed.
  • the decorative sheet 1 of the present embodiment has a pattern layer 5, a transparent resin layer 3, and a surface on one surface (front surface) of the base material layer 6 constituting the raw fabric layer.
  • the protective layer 2 is laminated in this order.
  • Reference numeral 4 denotes an adhesive layer.
  • the pattern layer 5 and the transparent resin layer 3 constitute an intermediate layer.
  • the concealing layer 7 and the primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6.
  • the concealing layer 7 may be formed between the base layer 6 and the pattern layer 5 or may be omitted.
  • the decorative sheet 1 of this embodiment has illustrated the case where the embossed pattern 3a is formed between the surface protective layer 2 and the transparent resin layer 3.
  • the embossed pattern 3 a may be formed on the upper surface of the surface protective layer 2.
  • the layer thickness of the decorative sheet 1 having the above configuration is 3 to 20 ⁇ m for the surface protective layer 2, 20 to 200 ⁇ m for the transparent resin layer 3, and 1 to 1 for the adhesive layer 4 in consideration of printing workability and cost.
  • the pattern layer 5 is 3 to 20 ⁇ m
  • the base layer 6 is 20 to 150 ⁇ m
  • the masking layer 7 is 2 to 20 ⁇ m
  • the primer layer 8 is 0.1 to 20 ⁇ m
  • the total thickness of the decorative sheet 1 is 49 Within the range of 450 ⁇ m.
  • FIG. 1 the case where the decorative sheet 1 of this embodiment is affixed on the base material B and the decorative board is comprised is illustrated.
  • the base material layer 6 is comprised from paper, a resin sheet, foil, etc., for example.
  • paper include thin paper, titanium paper, resin-impregnated paper, organic or inorganic nonwoven fabric, and synthetic paper.
  • the resin of the resin sheet include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and other synthetic resins, foams of these synthetic resins, ethylene-
  • the rubber include 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.
  • the foil include metal foils such as aluminum, iron, gold
  • the pattern pattern layer 5 can be provided using a known printing method.
  • printing for forming the pattern layer 5 can be performed with a roll-to-roll printing apparatus.
  • the printing method is not particularly limited, but for example, a gravure printing method can be used in consideration of productivity and picture quality.
  • the design pattern it is sufficient to adopt an arbitrary design pattern in consideration of the design properties according to the use place such as flooring or wall material, and various wood grain is often used if it is a wood type design, In addition to the grain, cork can be used as a pattern. For example, if it is an image of a stone floor such as marble, it may be used as a pattern such as a marble stone.
  • an artificial pattern such as an artificial pattern or a geometric pattern using these as a motif can also be used.
  • the ink corresponding to a printing system can be selected suitably.
  • a colorant such as a pigment or a dye, an extender pigment, a solvent, and a binder, which are contained in a normal ink, are appropriately added.
  • the pigment include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.
  • the binder may be water-based, solvent-based, or emulsion type, and the curing method is particularly limited, such as a one-component type, a two-component type consisting of a main agent and a curing agent, or a type that is cured by ultraviolet rays or electron beams. Not what you want. Among them, the most common method is a two-component type, which uses a urethane-based main agent and a curing agent made of isocyanate. In addition, the design may be applied by vapor deposition or sputtering of various metals.
  • the adhesive layer 4 is provided for the purpose of strengthening the adhesion between the base material layer 6 and the pattern / pattern layer 5 and the transparent resin layer 3. When this adhesion is strong, it is possible to give the decorative sheet 1 bending workability that follows a curved surface or a right angle surface.
  • the adhesive layer 4 is preferably transparent.
  • any material can be selected as an adhesion method, for example, a lamination method such as thermal lamination, extrusion lamination, dry lamination, etc., and the adhesive is, for example, acrylic, polyester, polyurethane, epoxy It can select suitably from systems etc.
  • a urethane-based material obtained by a reaction with a polyol using an isocyanate as a two-component curing type because of its cohesive strength.
  • the adhesive layer 4 may be omitted when the adhesive strength between the transparent resin layer 3 and the pattern layer 5 is sufficiently obtained.
  • the transparent resin layer 3 is made of a transparent thermoplastic resin, and for example, a vinyl chloride resin, an acrylic resin, a polyolefin resin, or the like can be used. Of these, polyolefin resins can be preferably used in terms of environmental compatibility, processability, and cost.
  • the transparent resin layer 3 allows the decorative sheet 1 to have an effect of increasing the thickness and depth in design, and can improve the weather resistance and wear resistance of the decorative sheet 1.
  • ⁇ -olefin for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-de
  • ⁇ -olefin for example, propylene, 1-butene, 1-pentene, 1-hexene,
  • a nucleating agent nucleating agent vesicle
  • a nucleating agent vesicle encapsulated in vesicles
  • a transparent resin layer 3 having better transparency, scratch resistance and post-processing property is obtained. be able to.
  • the nucleating agent vesicle can be prepared by the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method and the like.
  • the nucleating agent examples include phosphoric acid ester metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue and talc.
  • a phosphoric acid ester metal salt, a benzoic acid metal salt, a pimelic acid metal salt, and a rosin metal salt that can be expected to be non-molten and have good transparency.
  • colored quinacridone, cyanine blue, talc and the like can also be used.
  • a molten benzylidene sorbitol may be appropriately mixed and used with a non-melting nucleating agent.
  • the transparent resin layer 3 may be provided with, for example, an existing heat stabilizer, ultraviolet absorber, light stabilizer, anti-blocking agent, catalyst scavenger, colorant, light scattering agent, and gloss adjusting agent, if necessary. These various additives can also be added.
  • an existing heat stabilizer ultraviolet absorber, light stabilizer, anti-blocking agent, catalyst scavenger, colorant, light scattering agent, and gloss adjusting agent.
  • These various additives can also be added.
  • methods using hot pressure such as extrusion laminating and dry laminating, are common.
  • embossing pattern there are a method of embossing a sheet once laminated by various methods by hot pressure later, and a method of providing an uneven pattern on a cooling roll and embossing at the same time as extrusion lamination.
  • the embossing method is not particularly limited.
  • a known single-wafer or rotary embossing machine is used.
  • the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like.
  • the position where the pattern layer 5 and the adhesive layer 4 are applied may be on the base material layer 6 side as usual, or on the transparent resin layer 3 side.
  • the surface protective layer 2 may be a single layer, or a plurality of layers may be stacked to form the surface protective layer 2.
  • the surface protective layer 2 has an important role in determining the superiority or inferiority in terms of surface protection, gloss adjustment, cleanability, and the like.
  • the surface protective layer 2 contains a curable resin as a main component. That is, it is preferable that the resin component is substantially composed of a curable resin. “Substantially” means, for example, 80 parts by mass or more when the total resin is 100 parts by mass.
  • coating and hardening of a coating film can be performed using a known coating apparatus, a heat drying apparatus, and an ultraviolet irradiation device.
  • the surface protective layer 2 may contain, for example, an anti-mold agent, a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye and a pigment, a solvent, and the like as necessary.
  • unevenness may be formed on the surface protective layer 2 in order to impart a given design property.
  • an uneven pattern is formed by embossing.
  • the material of the surface protective layer 2 can be appropriately selected from polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like.
  • the form of the material is not particularly limited, such as aqueous, emulsion, solvent type.
  • the curing method can be appropriately selected from a one-component type, a two-component type, an ultraviolet curing method, and the like.
  • a urethane-based one using isocyanate is preferable from the viewpoint of workability, cost, cohesion of the resin itself, and the like.
  • the isocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), and methylhexane diisocyanate (HTDI).
  • HXDI Methylcyclohexanone diisocyanate
  • TMDI trimethylhexamethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • the surface protective layer 2 contains a dispersant and inorganic nanoparticles.
  • a dispersant and inorganic nanoparticles are added to at least one of the plurality of layers.
  • the dispersant and the inorganic nanoparticles are preferably added to the outermost surface protective layer.
  • both the dispersant and the inorganic nanoparticles are included in the vesicle.
  • the dispersant and the inorganic nanoparticles are encapsulated in liposomes having an outer membrane made of phospholipid and are in a vesicle state.
  • the dispersant preferably has a hydroxyl group or an amino group.
  • a dispersing agent has an unsaturated double bond.
  • the inorganic nanoparticles may be any inorganic particles that can be nanosized, and examples thereof include spherical particles such as ⁇ -alumina, silica, boehmite, iron oxide, and diamond.
  • examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like, and are not particularly limited.
  • the particle diameter of the inorganic nanoparticles those having a primary particle diameter of 1 to 1000 nm are preferable, and those having a particle diameter of 10 to 50 nm are more preferable.
  • the primary particle diameter is larger than 1000 nm, there is a concern that transparency may deteriorate due to light scattering caused by inorganic nanoparticles.
  • the primary particle size of the inorganic nanoparticles is no need for the primary particle size of the inorganic nanoparticles to be used, and inorganic nanoparticles having different primary particle sizes can be mixed and used.
  • a plurality of different types of inorganic nanoparticles may be mixed and used.
  • the amount of inorganic nanoparticles added is, for example, 0.005 to 20 parts by mass with respect to 100 parts by mass of the resin composition that is the main component of the surface protective layer 2.
  • the amount of the vesicle is 0.00535 to 21.4 parts by mass with respect to 100 parts by mass of the resin composition.
  • the nano-ization of the inorganic particles can be obtained by a nano-ization method such as a sol-gel method, a reverse micelle method, or a hot soap method.
  • the sol-gel method is a method of making nanoparticles by performing a chemical reaction such as hydrolysis or polycondensation after making an alkoxide precursor into a sol state by heating or the like.
  • reverse micelles are produced by injecting one or two types of reactive raw material aqueous solutions together with a surfactant into an organic solvent, and a chemical reaction such as thermal decomposition is performed in the micelles. It is a method of making particles.
  • the hot soap method uses a surfactant as a solvent, injects an aqueous metal solution and vigorously stirs it to form minute water droplet micelles, and then performs thermal decomposition or reaction between two types of reactive raw materials to form nanoparticles. Is a method of synthesizing. The nanoparticles thus produced are covered and protected with a surfactant.
  • the dispersant is used for the surface treatment of inorganic nanoparticles.
  • a dispersant having an unsaturated bond, a dispersant having a hydroxyl group, or a dispersant having an amino group is preferable.
  • Two or more kinds of inorganic nanoparticles treated with the respective dispersants can be mixed and used.
  • the dispersant having a hydroxyl group include 12-hydroxystearic acid, ricinoleic acid and the like combined with lithium, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, sorbitan fatty acid ester, alcohol-modified silicone oil, alcohol Examples include modified wax, oxidized wax, and carnauba wax.
  • dispersant having an amino group examples include polycarboxylic acid alkylamine, alkylpolyamine, stearic acid amide, oleic acid amide, erucic acid amide, n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, n- 2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, di-n-butoxy bis (triethanolaminato) titanium, bis (4-aminobenzoato-O) (isooctadecanoato-O) (propan-2-olato) titanium, bis [2-[(tri
  • dispersant having an unsaturated double bond examples include aliphatic surfactants such as aliphatic polyvalent polycarboxylic acids, polycarboxylic acid alkylamines, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, and olein.
  • aliphatic surfactants such as aliphatic polyvalent polycarboxylic acids, polycarboxylic acid alkylamines, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, and olein.
  • thermosetting resin particularly an isocyanate compound
  • the isocyanate compound and the hydroxyl group or amino group of the dispersant react to form a surface protective layer 2. Since a structure in which inorganic nanoparticles are immobilized on the surface is formed, the scratch resistance of the surface of the surface protective layer 2 can be dramatically improved.
  • a dispersant having an unsaturated double bond it is preferable to use a photocurable resin alone or a mixed resin of a thermosetting resin and a photocurable resin.
  • the vesicle formation of the dispersant and the inorganic nanoparticles in this embodiment is performed by, for example, the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, and the supercritical reverse phase evaporation method. Is called.
  • the form of the vesicle is a capsule form in which an object (dispersant and inorganic nanoparticles) is encapsulated with the vesicle.
  • the film constituting the vesicle may be broken and the inorganic nanoparticles may be in contact with the resin.
  • chloroform or a chloroform / methanol mixed solvent is placed in a container such as a flask, and phospholipid is further added to dissolve. Thereafter, the solvent is removed using an evaporator to form a thin film made of lipid, and after adding a dispersant and a dispersion of inorganic nanoparticles, the vesicle is obtained by hydrating and dispersing with a vortex mixer.
  • the extrusion method is a method of preparing a vesicle by preparing a thin phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method.
  • the hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining vesicles by gently stirring and dispersing without using a mixer.
  • a phospholipid is dissolved in diethyl ether or chloroform, a solution containing a dispersant and inorganic nanoparticles is added to form a W / O emulsion, and the organic solvent is removed from the emulsion under reduced pressure.
  • vesicles are obtained by adding water.
  • the freeze-thaw method is a method using cooling / heating as external perturbation, and is a method of obtaining vesicles by repeating this cooling / heating.
  • Vesicleization by the supercritical reverse phase evaporation method means that the encapsulated substance is dissolved in a mixture in which the substance that forms the outer membrane of the vesicle is uniformly dissolved in carbon dioxide in a supercritical state or at a temperature or pressure condition above the critical point. And adding an aqueous phase containing inorganic nanoparticles and a dispersant as a capsule to form a capsule-like vesicle including the inorganic nanoparticles and the dispersant as an encapsulating material in a single layer.
  • a vesicle refers to a vesicle having a membrane structure closed like a spherical shell and containing a liquid phase inside.
  • Phospholipids form stable vesicles (also called liposomes) consisting of a lipid bilayer phase in the aqueous phase.
  • the carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ⁇ 0.0030 MPa) or higher.
  • the carbon dioxide under the temperature condition or pressure condition above the critical point means carbon dioxide under the condition that only the critical temperature or the critical pressure exceeds the critical condition.
  • Examples of the phospholipid constituting the vesicle include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin.
  • Glycerophospholipids such as sphingomyelin, sphingophospholipids such as ceramide phosphorylethanolamine and ceramide phosphorylglycerol.
  • the concealing layer 7 is formed by printing, for example, in the same manner as the picture pattern layer 5 for the purpose of maintaining concealment.
  • the pigment to be included in the ink it is preferable to use an opaque pigment, titanium oxide, iron oxide or the like. It is also possible to add metals such as gold, silver, copper, and aluminum in order to improve the concealing property. In general, flaky aluminum is often added.
  • the masking layer 7 can be omitted when the base material layer 6 is opaque and has masking properties.
  • the primer layer 8 is formed in order to improve the adhesion with the base material B.
  • the primer layer 8 is, for example, an ester resin, a urethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride-vinyl acetate copolymer, a polyvinyl butyral resin. And nitrocellulose-based resins. These resins can be used alone or mixed to form an adhesive composition, which can be formed using an appropriate application means such as a roll coating method or a gravure printing method.
  • the resin constituting the primer layer 8 is preferably a urethane-acrylate resin. That is, it is particularly preferable to form the resin made of a copolymer of an acrylic resin and a urethane resin and an isocyanate.
  • Base material B examples include wooden boards (woody base materials), inorganic boards (composite plates), metal plates, and the like.
  • a transparent resin sheet 3 as the transparent resin layer 3 is formed by melt extrusion molding, and both surfaces of the obtained transparent resin sheet 3 are subjected to corona treatment to obtain a wetting tension. Is assumed to be 40 dyn / cm or more.
  • pattern printing is performed on one surface by a gravure printing method to form the pattern pattern layer 5.
  • the masking layer 7 and the primer layer 8 are sequentially stacked on the other surface.
  • an adhesive layer 4 is provided so as to overlap with the pattern layer 5, and the raw fabric resin sheet 6 and the transparent resin sheet 3 are bonded together via the adhesive layer 4 by a dry laminating method.
  • embossed pattern 3a is applied to the surface of transparent resin sheet 3
  • decorative sheet 1 is obtained by applying surface protective layer 2 so as to cover embossed pattern 3a.
  • the production method of the decorative sheet 1 is not limited to the above method.
  • the offset printing method, the screen printing method, the flexographic printing method, the ink jet printing method in addition to the gravure printing method. Etc. can be formed.
  • a method using hot pressure or an extrusion laminating method can be used.
  • the decorative sheet 1 is composed of a single layer or a plurality of layers, and has at least one surface protective layer 2 to which a vesicle-dispersed dispersant and inorganic nanoparticles are added.
  • a vesicle-dispersed dispersant and inorganic nanoparticles are added.
  • Both the dispersant and the inorganic nanoparticles are vesicles such as encapsulated in liposomes. According to this configuration, scratch resistance can be imparted by adding inorganic fine particles to the surface protective layer 2.
  • both the dispersant and the inorganic nanoparticles are in a vesicle state by being encapsulated in a liposome having an outer membrane made of phospholipid, fine particles made of a nano-sized dispersant and inorganic nanoparticles Is significantly improved, and secondary aggregation of the inorganic nanoparticles can be suppressed and uniformly dispersed in the resin constituting the surface protective layer 2. As a result, higher transparency can be secured.
  • the inorganic particles are nano-sized and uniformly dispersed, deterioration of the matte appearance over time can be suppressed.
  • the dispersibility in the surface protective layer 2 is improved. It is possible to significantly improve. Thereby, the surface protective layer 2 excellent in scratch resistance can be obtained without impairing the transparency of the surface protective layer 2.
  • the dispersant may have a hydroxyl group or an amino group. According to this configuration, since the hydroxyl group or amino group of the dispersant is firmly bonded to the thermosetting resin, the inorganic nanoparticles in the surface protective layer 2 are immobilized on the surface protective layer 2, whereby inorganic nanoparticles are obtained. It is possible to improve the deterioration of the scratch resistance due to the omission.
  • the dispersant preferably has an unsaturated double bond. According to this configuration, since the unsaturated double bond of the dispersant is firmly bonded to the photocurable resin, the inorganic nanoparticle of the surface protective layer 2 is immobilized on the surface protective layer 2, and thus the inorganic nanoparticle is fixed. It is possible to improve the deterioration of the scratch resistance due to the lack of particles.
  • the resin composition that is the main component of the surface protective layer 2 is a curable resin. According to this configuration, it is possible to provide a decorative sheet 1 including the surface protective layer 2 having high scratch resistance and flexibility optimal for post-processing by crosslinking of the resin composition constituting the surface protective layer 2. .
  • Vesicle formation may be performed by nano-processing by a supercritical reverse phase evaporation method. According to this configuration, by performing nano-treatment using the supercritical reverse phase evaporation method, the dispersibility of the inorganic nanoparticles contained in the surface protective layer 2 and the nucleating agent contained in the transparent resin layer 3 can be obtained. By significantly improving dispersibility, it is possible to impart scratch resistance performance while maintaining transparency.
  • Example 1-1 Examples of the first embodiment will be described below.
  • the layer structure of the decorative sheet 1 described below is the same as that of the above-described embodiment.
  • Example 1-1 both the dispersant having no reactive group and inorganic nanoparticles were nano-treated by the Bangham method on the surface of the transparent resin layer 3 to which the nucleating agent liposome was not added.
  • the surface protective layer 2 was formed by adding 0.05 parts by mass of liposomes encapsulated in phospholipid capsules to 100 parts by mass of the thermosetting resin constituting the surface protective layer 2.
  • a highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, an MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3, Hindered phenol-based antioxidant (Irganox 1010: manufactured by BASF) 500 ppm, benzotriazole-based UV absorber (Tinuvin 328: manufactured by BASF) 2000 ppm, hindered amine-based light stabilizer (Kimasorb 944: manufactured by BASF)
  • the resin added with 2000 ppm was extruded using a melt extruder to form a 100 ⁇ m thick transparent resin sheet made of highly crystalline polypropylene used as the transparent resin layer 3. Subsequently, both surfaces of the formed transparent resin sheet were subjected to corona treatment so that the surface wetting tension was 40 dyn / cm or more.
  • a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) is used with respect to the binder resin content of the ink.
  • the pattern printing layer 5 was provided by performing pattern printing by a gravure printing method using an ink to which 0.5% by mass of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) was added.
  • a primer layer 8 was provided on the other surface of the base material layer 6.
  • a transparent resin sheet is applied to one surface side of the base material layer 6 via an adhesive for dry laminating as an adhesive layer 4 (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m 2 ). Bonding was performed by a dry laminating method. And after giving the embossed pattern 3a to the surface of a transparent resin sheet, the liposome containing the above-mentioned dispersing agent and inorganic nanoparticles with respect to 100 parts by mass of a two-component curable urethane topcoat (W184; manufactured by DIC Graphics) The surface protective layer 2 was formed by applying an ink containing 0.05 part by mass at an application thickness of 15 g / m 2 . The total thickness of the decorative sheet 1 is 200 ⁇ m.
  • Example 1-2 the surface of the transparent resin layer 3 to which the nucleating agent liposomes were not added, both the dispersant having an amino group and the inorganic nanoparticles were nanonized by the Bangham method.
  • the surface protective layer 2 was formed by adding 0.05 parts by mass of the liposomes encapsulated in the capsules composed of 100 parts by mass of the thermosetting resin constituting the surface resin layer. Others were produced in the same manner as in Example 1-1 to obtain the decorative sheet 1 of Example 1-2.
  • Example 1-3 the surface of the transparent resin layer 3 to which the nucleating agent liposome was not added was both nanodispersed by the Bangham method with both the dispersant having an unsaturated double bond and inorganic nanoparticles.
  • the surface protective layer 2 was formed by adding 0.05 parts by mass of liposomes encapsulated in phospholipid capsules to 100 parts by mass of the curable resin constituting the surface resin layer.
  • the curable resin a mixed resin of a thermosetting resin and a photocurable resin was employed. Others were produced in the same manner as Example 1-1 to obtain a decorative sheet 1 of Example 1-3.
  • Example 1-4 the surface of the transparent resin layer 3 to which the nucleating agent liposomes are added is composed of a phospholipid in which both the dispersant having an amino group and the inorganic nanoparticles are nanonized by the Bangham method.
  • the liposome contained in the capsule was added to 0.05 part by mass with respect to 100 parts by mass of the thermosetting resin constituting the surface resin layer to form the surface protective layer 2.
  • a resin composition for forming the transparent resin layer 3 described below was melt-extruded using an extruder to form a transparent resin sheet as a transparent highly crystalline polypropylene sheet having a thickness of 100 ⁇ m.
  • Example 1-4 the decorative sheet 1 of Example 1-4 was obtained in the same manner as Example 1-2.
  • nucleation of the nucleating agent was performed as follows. "Preparation of nucleating agent liposomes"
  • vesicle formation of the nucleating agent added to the transparent resin layer 3 in the present embodiment will be described.
  • the nucleating agent is vesicled by supercritical reverse phase evaporation, first 100 parts by mass of methanol and 82 parts by mass of a phosphate ester metal salt nucleating agent (ADK STAB NA-11, manufactured by ADEKA) as a nucleating agent. After putting 5 parts by mass of phosphatidylcholine as a substance constituting the outer membrane of the vesicle in a high-pressure stainless steel container kept at 60 ° C.
  • a supercritical state is obtained.
  • 100 parts by mass of ion-exchanged water is injected with vigorous stirring and mixing.
  • a nucleating agent for a vesicle having a monolayer outer membrane made of phospholipid by stirring for 15 minutes while maintaining the temperature and pressure in a supercritical state and then discharging carbon dioxide to return to atmospheric pressure.
  • a vesicle-containing nucleating agent (nucleating agent liposome) was obtained.
  • the resin composition forming the transparent resin layer 3 has a high pentad fraction of 97.8%, MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and molecular weight distribution MWD (Mw / Mn) of 2.3.
  • Hindered phenolic antioxidant (Irganox 1010: manufactured by BASF) 500 ppm, benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) 2000 ppm, and hindered amine light stabilization for crystalline homopolypropylene resin
  • An agent (Kimasorb 944: manufactured by BASF) 2000 ppm and the above nucleating agent liposome 1000 ppm are used. Then, the resin composition was melted and extruded using a melt extruder to form a transparent resin sheet having a thickness of 100 ⁇ m to be used as the transparent resin layer 3.
  • Example 1-5 the surface of the transparent resin layer 3 to which the nucleating agent liposomes were added, both the dispersant having an amino group and the inorganic nanoparticles were nanonized by the supercritical reverse phase evaporation method.
  • the surface protective layer 2 was formed by adding 0.05 parts by mass of liposomes encapsulated in phospholipid capsules to 100 parts by mass of the thermosetting resin constituting the surface resin layer.
  • the decorative sheet 1 of Example 1-5 was obtained in the same manner as Example 1-4.
  • the vesicle formation of the inorganic nanoparticles and the dispersant was performed as follows.
  • vesicles were prepared by adding 100 parts by mass of hexane, 70 parts by mass of inorganic nanoparticles, 0.07 parts by mass of a dispersant, and 5 parts by mass of phosphatidylcholine as a phospholipid to a high-pressure stainless steel container maintained at 60 ° C.
  • Comparative Example 1-1 A decorative sheet of Comparative Example 1-1 was produced in the same manner as in Example 1-1, except that the dispersant and inorganic nanoparticles not having a vesicle were not used.
  • a decorative sheet was prepared.
  • Comparative Example 1-3 was the same as Example 1-1 except that 4.5 ⁇ m silica particles (OK412: manufactured by Evonik) were used as inorganic particles encapsulated in phospholipid capsules (vesicles). A decorative sheet was prepared.
  • Example 1-4 Comparison was made in the same manner as in Example 1-1, except that 0.002 parts by mass of the liposome encapsulated in a phospholipid capsule (vesicle) was added to both the dispersant having no reactive group and the inorganic nanoparticles. A decorative sheet of Example 1-4 was prepared.
  • Comparative Example 1 Comparative Example 1 was carried out in the same manner as in Example 1-1, except that 50 parts by mass of the liposome encapsulated in the capsule (vesicle) made of phospholipid were added together with the dispersant having no reactive group and the inorganic nanoparticles. A decorative sheet of -5 was produced.
  • ⁇ Hoffman scratch test> The Hoffman scratch test was performed by scratching the surface of each decorative sheet 1 bonded to the wooden base material B at a constant speed with a load of 1200 g using a Hoffman scratch hard tester (BYK-Gardner). The presence or absence of scratches on the surface of 1 was visually determined.
  • Step 2 ⁇ Steel wool rubbing test>
  • the surface of each decorative sheet 1 bonded to the wooden base material B is fixed with a jig in a state where the steel wool is in contact, and a load of 500 g is applied to the jig.
  • the surface of the decorative sheet 1 was visually checked for scratches by rubbing at a constant speed and a distance of 50 mm under 50 reciprocating conditions.
  • Bonstar # 0 manufactured by Nippon Steel Wool Co., Ltd. was used for the steel wool.
  • each decorative sheet obtained by the above method is attached to one surface of a medium-quality fiberboard (MDF) as a base material using a urethane-based adhesive, With respect to the other surface of the base material, a V-shaped groove is inserted to the boundary where the base material and the decorative sheet are bonded together so that the opposite decorative sheet is not scratched.
  • MDF medium-quality fiberboard
  • the base material B is bent to 90 degrees along the V-shaped groove so that the face of the decorative sheet is mountain-folded, and whether or not the bent portion of the surface of the decorative sheet has been whitened or cracked is observed. Observe with an optical microscope and evaluate the superiority or inferiority of post-processing resistance.
  • the transparency was good, and good results were also obtained in the Hoffman scratch test, the steel wool test, and the V-groove bending test. Obtained.
  • the inorganic nanoparticles are uniformly dispersed by adding the vesicle encapsulating both the inorganic nanoparticles and the dispersant to the surface protective layer 2. Therefore, it is considered that the surface hardness is improved due to the inorganic nanoparticles while maintaining good transparency and suitability for post-processing required for the decorative sheet 1.
  • the decorative sheet 1 of Comparative Example 1-1 has the post-processing suitability required for the decorative sheet 1, but the reactive group in which the surface protective layer 2 is not vesicled. It is considered that the dispersibility of the inorganic nanoparticles was not sufficiently obtained due to the use of the dispersant and the inorganic nanoparticles having no odor, and the transparency and scratch resistance required for the decorative sheet could not be obtained.
  • the decorative sheet 1 of Comparative Example 1-2 has a post-processing suitability required for the decorative sheet 1, but because a dispersant that is not subjected to vesicle formation on the surface protective layer 2 is used.
  • the dispersibility of the inorganic nanoparticles was not sufficiently obtained, and the transparency and scratch resistance required for the decorative sheet could not be obtained.
  • the decorative sheet 1 of Comparative Example 1-3 since the particle size of the inorganic particles is too large, irregularities are formed on the surface of the surface protective layer 2 and the transparency is impaired. It is considered that the fine particles were not sufficiently bonded, resulting in poor scratch resistance and post-working resistance.
  • the decorative sheet 1 of Comparative Example 1-4 has the transparency and post-processing suitability required for the decorative sheet 1, but the vesicle encapsulates the dispersant and the inorganic nanoparticles in the capsule made of phospholipid. It was considered that the result was inferior in scratch resistance because the addition amount of was very small.
  • the amount of vesicles encapsulating the dispersant and the inorganic nanoparticles in the phospholipid capsule was very large, resulting in poor transparency and scratch resistance. It is considered that the property was inferior because the inorganic nanoparticles dropped off during friction and caused abrasive wear. In addition, it is considered that the thermosetting resin and the inorganic fine particles were not sufficiently bonded, resulting in poor post-processability.
  • the decorative sheet 1 of the present invention shown in Examples 1-1 to 1-5 has the transparency required for the decorative sheet 1, and is extremely excellent in scratch resistance and post-processing resistance. It became clear that it was the decorative sheet 1.
  • thermosetting resin for example, a two-component curable resin
  • a curable resin typified by an ionizing radiation curable resin that is cured by ionizing radiation such as ultraviolet rays or electron beams is used as a main component.
  • a matting agent such as silica fine particles is also contained in the surface protective layer.
  • Patent Document 1 contains a matting agent and sodium calcium aluminosilicate particles in the surface protective layer in order to prevent wear of the matting agent exposed on the surface of the surface protective layer over time.
  • a matting agent and sodium calcium aluminosilicate particles in the surface protective layer in order to prevent wear of the matting agent exposed on the surface of the surface protective layer over time.
  • the matting agent and sodium calcium aluminosilicate particles are exposed on the surface of the surface protective layer. As time passes, the exposed part is worn out, and the matte appearance at the start of use may be impaired.
  • Patent Document 2 proposes a decorative sheet in which colloidal silica is added to the surface protective layer.
  • the use of the decorative sheet is expanding more and more, and improvement in scratch resistance, wear resistance and post-processing resistance is demanded.
  • the decorative sheet 1 of the present embodiment has a pattern layer 5, a transparent resin layer 3, and a surface on one surface (front surface) of the base material layer 6 constituting the raw fabric layer.
  • the protective layer 2 is laminated in this order.
  • Reference numeral 4 denotes an adhesive layer.
  • the pattern layer 5 and the transparent resin layer 3 constitute an intermediate layer.
  • the concealing layer 7 and the primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6.
  • the concealing layer 7 may be formed between the base layer 6 and the pattern layer 5 or may be omitted.
  • the decorative sheet 1 of this embodiment has illustrated the case where the embossed pattern 3a is formed between the surface protective layer 2 and the transparent resin layer 3.
  • FIG. The embossed pattern 3 a may be formed on the upper surface of the surface protective layer 2. That is, the decorative sheet 1 of the present embodiment has the same configuration as the decorative sheet 1 described in the first embodiment.
  • each of the above layers will be described.
  • the base material layer 6 of the present embodiment is the same as the base material layer 6 described in the first embodiment. Therefore, description of the base material layer 6 is omitted here.
  • the pattern pattern layer 5 of this embodiment is substantially the same as the pattern pattern layer 5 described in the first embodiment. Therefore, description of the pattern layer 5 is omitted here.
  • the binder contained in the pattern layer 5 may be a material such as nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, or the like alone or each modified product. .
  • the adhesive layer 4 of the present embodiment is the same as the adhesive layer 4 described in the first embodiment. Therefore, description of the adhesive layer 4 is omitted here.
  • the transparent resin layer 3 of the present embodiment is the same as the transparent resin layer 3 described in the first embodiment. Therefore, description of the transparent resin layer 3 is omitted here.
  • the surface protective layer 2 of the present embodiment contains a dispersant having a hydroxyl group, an amino group or an unsaturated double bond, and inorganic nanoparticles having a particle diameter in the range of 10 nm to 50 nm.
  • the inorganic nanoparticles are encapsulated in a vesicle having a single-layer outer membrane containing the dispersant. That is, the surface protective layer 2 of the present embodiment contains so-called “inorganic nanoparticle vesicles”.
  • the inorganic nanoparticle vesicle can be prepared, for example, using the supercritical reverse phase evaporation method described in the first embodiment.
  • the form is a capsule shape and the outer membrane
  • such an inorganic nanoparticle vesicle breaks the outer membrane containing the dispersant, and the encapsulated inorganic nanoparticles are exposed to form a resin composition. In some cases, they may exist in contact.
  • the said inorganic nanoparticle is as substantially the same as the inorganic nanoparticle demonstrated in 1st Embodiment, the description is abbreviate
  • the dispersant is substantially the same as the dispersant described in the first embodiment. Therefore, description of the dispersant is omitted here.
  • a curable resin as the main component of the surface protective layer 2 of the present embodiment.
  • a thermosetting resin and a photocurable resin can be used, but it is particularly preferable to use only a thermosetting resin or a mixed resin of a thermosetting resin and a photocurable resin.
  • a curable resin surface hardness can be improved, curing shrinkage can be suppressed, and adhesion with inorganic fine particles can be improved.
  • thermosetting resin can be appropriately selected from, for example, polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aluminoalkyd, urea, etc. It is preferable to use a two-component curable urethane-based one. Urethane-based thermosetting resins are suitable from the viewpoints of workability, cost, cohesive strength of the resin itself, and the like.
  • a urethane resin obtained by reacting acrylic polyol and isocyanate may be used.
  • the said isocyanate is substantially the same as the isocyanate demonstrated in 1st Embodiment, the description is abbreviate
  • the photocurable resin for example, a polyester acrylate type, an epoxy acrylate type, a urethane acrylate type, an acrylic acrylate type, and the like can be appropriately selected and used.
  • a urethane acrylate having good weather resistance (light) resistance It is preferable to use a system and an acrylic acrylate system.
  • the mixed resin of the thermosetting resin and the photocurable resin for example, a two-component curable urethane resin using isocyanate as the thermosetting resin, and a urethane-acrylate resin as the photocurable resin; It is preferable to mix and use. This is because an improvement in surface hardness, suppression of curing shrinkage, and post-processing resistance can be imparted.
  • the form of the resin material is not particularly limited as in the first embodiment, such as aqueous, emulsion, and solvent systems.
  • the preferable combination of the said curable resin and the said dispersing agent is the same as the preferable combination of curable resin and a dispersing agent demonstrated in 1st Embodiment, the description is abbreviate
  • the decorative sheet according to the present embodiment as described above, light scattering caused by adding particles is suppressed by using inorganic nanoparticles having a minimum size of 10 to 50 nm. Further, the inorganic nanoparticles are added as inorganic nanoparticle vesicles encapsulated in a vesicle having a single-layer outer membrane containing a dispersant. For this reason, secondary aggregation of inorganic nanoparticles can be suppressed in the resin composition, and inorganic nanoparticles can be uniformly dispersed. By carrying out like this, the decorative sheet provided with the surface protection layer excellent in the outstanding transparency, scratch resistance, and post-processing property can be provided.
  • the decorative sheet 1 of the present embodiment has a pattern layer 5, a transparent resin layer 3, and a surface on one surface (front surface) of the base material layer 6 constituting the raw fabric layer.
  • the protective layer 2 is laminated in this order.
  • Reference numeral 4 denotes an adhesive layer.
  • the pattern layer 5 and the transparent resin layer 3 constitute an intermediate layer.
  • the concealing layer 7 and the primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6.
  • the concealing layer 7 may be formed between the base layer 6 and the pattern layer 5 or may be omitted.
  • the decorative sheet 1 of this embodiment has illustrated the case where the embossed pattern 3a is formed between the surface protective layer 2 and the transparent resin layer 3.
  • FIG. The embossed pattern 3 a may be formed on the upper surface of the surface protective layer 2. That is, the decorative sheet 1 of the present embodiment has the same configuration as the decorative sheet 1 described in the first embodiment and the second embodiment.
  • the decorative sheet 1 of the present embodiment is different from the decorative sheet 1 of the second embodiment only in the surface protective layer 2. Therefore, only the surface protective layer 2 of this embodiment will be described here.
  • the surface protective layer 2 of the present embodiment contains a dispersant having a hydroxyl group, an amino group or an unsaturated double bond, and inorganic nanoparticles having a particle diameter in the range of 10 nm to 50 nm.
  • the dispersant is encapsulated in a vesicle having a monolayer outer membrane made of phospholipid. That is, the surface protective layer 2 of this embodiment contains a so-called “dispersant vesicle”.
  • the dispersant vesicle can be prepared, for example, using the supercritical reverse phase evaporation method described in the first embodiment.
  • the outer membrane which is the outer shell of the capsule, is a monolayer membrane made of phospholipid, and the monolayer membrane contains the dispersant.
  • the resin composition forming the surface protective layer such a dispersant vesicle is formed so that the outer membrane made of phospholipid is broken and the encapsulated dispersant is exposed to come into contact with the resin composition. It may exist.
  • the thing similar to 1st Embodiment can be used. Therefore, the description thereof is omitted here.
  • the decorative sheet according to the present embodiment as described above light scattering caused by adding particles is suppressed by using extremely small inorganic nanoparticles of 10 to 50 nm.
  • the dispersant is added together with the inorganic nanoparticles as a dispersant vesicle encapsulated in a vesicle having a monolayer outer membrane made of phospholipid.
  • the dispersing agent vesicle is uniformly dispersed in the resin composition, secondary aggregation of the inorganic nanoparticles in the resin composition can be suppressed and the inorganic nanoparticles can be uniformly dispersed in the resin composition.
  • the decorative sheet provided with the surface protection layer excellent in the outstanding transparency, scratch resistance, and post-processing property can be provided.
  • the transparent resin sheet 3 as the transparent resin layer 3 is formed by melt extrusion molding, and both surfaces of the obtained transparent resin sheet 3 are subjected to corona treatment to obtain a wetting tension. Is assumed to be 40 dyn / cm or more.
  • pattern printing is performed on one surface by a gravure printing method to form the pattern pattern layer 5.
  • the masking layer 7 and the primer layer 8 are sequentially stacked on the other surface.
  • an adhesive layer 4 is provided so as to overlap with the pattern layer 5, and the raw fabric resin sheet 6 and the transparent resin sheet 3 are bonded together via the adhesive layer 4 by a dry laminating method.
  • embossed pattern 3a is applied to the surface of transparent resin sheet 3
  • decorative sheet 1 is obtained by applying surface protective layer 2 so as to cover embossed pattern 3a.
  • the production method of the decorative sheet 1 is not limited to the above method.
  • the offset printing method, the screen printing method, the flexographic printing method, the ink jet printing method in addition to the gravure printing method. Etc. can be formed.
  • a method using hot pressure or an extrusion laminating method can be used.
  • the resin composition which forms the transparent resin layer 3 in the decorative sheet 1 of each embodiment is prepared by the following method.
  • a method for preparing a nucleating agent vesicle by the supercritical reverse phase evaporation method is as follows: methanol 100 parts by weight, phosphate metal salt nucleating agent (Adeka Stub NA-11, manufactured by ADEKA) as a nucleating agent 82 parts by weight After placing 5 parts by weight of phosphatidylcholine as a substance constituting the outer membrane of the vesicle in a high-pressure stainless steel container kept at 60 ° C. and injecting carbon dioxide so that the pressure becomes 20 MPa, a supercritical state is obtained.
  • phosphate metal salt nucleating agent Adeka Stub NA-11, manufactured by ADEKA
  • nucleating agent vesicle having a single-layer outer membrane by discharging carbon dioxide and returning to atmospheric pressure.
  • the pentad fraction is 97.8%
  • the MFR melting flow rate
  • the MFR melting flow rate
  • the MFR melting flow rate
  • the MWD molecular weight distribution MWD (Mw / Mn ) Is 2.3 in a highly crystalline homopolypropylene resin
  • hindered phenol antioxidant Irganox 1010: manufactured by BASF
  • benzotriazole ultraviolet absorber Tinuvin 328: manufactured by BASF
  • a high crystal having a thickness of 80 ⁇ m is used as a transparent resin layer 3 by extruding a resin added with 2000 ppm of a hindered amine light stabilizer (Kimasorb 944: manufactured by BASF) and 1000 ppm of the nucleating agent vesicle using a melt extruder.
  • a transparent resin sheet 3 made of conductive polypropylene is obtained.
  • the decorative sheet 1 has one or more intermediate layers on one surface of the base material layer B, and has one or more surface protective layers 2 on the intermediate layer. At least one of the surface protective layers 2 contains a dispersant having a hydroxyl group, an amino group or an unsaturated double bond, and inorganic nanoparticles having a particle size in the range of 10 nm to 50 nm, and is inorganic. The nanoparticles are encapsulated in a vesicle having a single layer outer membrane containing a dispersant.
  • the inorganic nanoparticles are uniformly dispersed in the resin composition that is the main component of the surface protective layer 2 by suppressing secondary aggregation of extremely small inorganic nanoparticles having a particle size of 10 nm to 50 nm. Therefore, excellent transparency, scratch resistance and post-processability can be imparted. Further, since the dispersant has a hydroxyl group, amino group or unsaturated double bond, the hydroxyl group, amino group or unsaturated double bond and the resin composition which is the main component of the surface protective layer 2 are strong. And the inorganic nanoparticles can be immobilized on the surface of the surface protective layer 2. For this reason, it is possible to provide a decorative sheet 1 that is excellent in scratch resistance by preventing the inorganic nanoparticles from falling off.
  • the decorative sheet 1 has one or more intermediate layers on one surface of the base material layer, and has one or two or more surface protective layers on the intermediate layer. At least one of the protective layers contains a dispersant having a hydroxyl group, an amino group, or an unsaturated double bond, and inorganic nanoparticles having a particle diameter in the range of 10 nm to 50 nm. It is encapsulated in a vesicle having a monolayer outer membrane made of lipid.
  • the dispersant vesicle because of the high dispersibility of the dispersant vesicle, it is possible to uniformly disperse inorganic nanoparticles having a particle size of 10 nm or more and 50 nm or less, so that excellent transparency, scratch resistance, and resistance to scratches can be obtained. Post workability can be imparted. Further, since the dispersant has a hydroxyl group, amino group or unsaturated double bond, the hydroxyl group, amino group or unsaturated double bond and the resin composition which is the main component of the surface protective layer 2 are strong. And the inorganic nanoparticles can be immobilized on the surface of the surface protective layer 2. For this reason, it is possible to provide a decorative sheet 1 that is excellent in scratch resistance by preventing the inorganic nanoparticles from falling off.
  • the main component of the surface protective layer is a curable resin. According to this configuration, the scratch resistance of the surface protective layer 2 can be improved by curing by crosslinking of the curable resin, and the makeup also has flexibility with excellent post-processing resistance such as V-cut bending. Sheet 1 can be provided.
  • the decorative sheet 1 has a transparent resin layer mainly composed of crystalline polypropylene resin as a layer constituting the intermediate layer, and the transparent resin layer is included in a vesicle having an outer film of a single layer film. Containing a nucleating agent. According to this structure, the decorative sheet 1 provided with the transparent resin layer 3 having excellent transparency, scratch resistance, and post-processing resistance can be provided.
  • Inorganic nanoparticle vesicles are prepared by supercritical reverse phase evaporation. First, 100 parts by weight of methanol, 64 parts by weight of silica nanoparticles having a particle diameter of 40 nm as inorganic nanoparticles (AEROSIL OX50, manufactured by Evonik), and a dispersant having a hydroxyl group.
  • AEROSIL OX50 silica nanoparticles having a particle diameter of 40 nm as inorganic nanoparticles
  • Inorganic nanoparticle vesicles containing inorganic nanoparticles in vesicles were obtained.
  • the above dispersant is 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group, or 3-aminopropyl as a dispersant having an unsaturated double bond.
  • methacryloxypropyltrimethoxysilane KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.
  • an inorganic nanoparticle vesicle encapsulated in a vesicle having an outer membrane containing a dispersant having each reactive group is obtained. Can do.
  • Dispersant vesicles were prepared by supercritical reverse phase evaporation. First, 100 parts by weight of methanol, 70 parts by weight of alcohol-modified silicone oil (XF42-B0970, manufactured by Momentive Performance Materials) as a dispersant having a hydroxyl group, 5 parts by weight of phosphatidylcholine as a phospholipid constituting the outer membrane is put in a high-pressure stainless steel container kept at 60 ° C. and sealed, and carbon dioxide is injected into the container so that the pressure becomes 20 MPa. To do.
  • Dispersant vesicles containing the agent were obtained.
  • the above dispersant is 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group, or 3-aminopropyl as a dispersant having an unsaturated double bond.
  • the nucleating agent vesicle is prepared by supercritical reverse phase evaporation, first 100 parts by weight of methanol, 82 parts by weight of a phosphate ester metal salt nucleating agent (Adeka Stub NA-11, manufactured by ADEKA) as a nucleating agent, After placing 5 parts by weight of phosphatidylcholine as a substance constituting the outer membrane in a high-pressure stainless steel container kept at 60 ° C.
  • a phosphate ester metal salt nucleating agent Adeka Stub NA-11, manufactured by ADEKA
  • a nucleating agent for a vesicle having a monolayer outer membrane made of phospholipid by stirring for 15 minutes while maintaining the temperature and pressure in a supercritical state and then discharging carbon dioxide to return to atmospheric pressure.
  • a nucleating agent vesicle encapsulating is obtained.
  • the resin composition forming the transparent resin layer 3 has a high pentad fraction of 97.8%, MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and molecular weight distribution MWD (Mw / Mn) of 2.3.
  • Hindered phenolic antioxidant (Irganox 1010: manufactured by BASF) 500 ppm, benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) 2000 ppm, and hindered amine light stabilization for crystalline homopolypropylene resin
  • An agent (Kimasorb 944: manufactured by BASF) 2000 ppm and the nucleating agent vesicle 1000 ppm are used.
  • the resin composition was melted and extruded using a melt extruder to form a transparent resin sheet 3 having a thickness of 100 ⁇ m to be used as the transparent resin layer 3.
  • Example 2-1 the particle size of the vesicle having a monolayer film containing a dispersant having an amino group with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle was added.
  • the decorative sheet 1 was provided with a surface protective layer 2 formed of a resin composition in which 0.05 part by weight of inorganic nanoparticle vesicles containing 40 nm inorganic nanoparticles was added to 100 parts by weight of a thermosetting resin.
  • both surfaces of the transparent resin sheet 3 as the transparent resin layer 3 to which the above-described nucleating agent vesicle is added are subjected to corona treatment so that the wetting tension becomes 40 dyn / cm or more.
  • a base material layer (raw fabric resin sheet) 6 as a concealing 70 ⁇ m original fabric layer the binder resin content of a two-component urethane ink (V180, manufactured by Toyo Ink Manufacturing Co., Ltd.)
  • the pattern layer 5 was formed by a gravure printing method using an ink added with 0.5 part by weight of a hindered amine light stabilizer (Kimasorb 944, manufactured by BASF).
  • a primer layer 8 was formed on the other surface of the raw fabric resin sheet 6.
  • an adhesive for dry lamination (Takelac A540, manufactured by Mitsui Chemicals, Inc .; application amount 2 g / m 2 ) as an adhesive layer 4 is laminated so as to overlap the pattern layer 5, and the adhesive layer 4 is interposed therebetween.
  • the raw fabric resin sheet 6 and the transparent resin sheet 3 were bonded together by a dry laminating method.
  • embossing pattern 3a is given to the surface of the transparent resin sheet 3, it is an inorganic nanoparticle with respect to 100 weight part of 2 liquid-curing-type urethane topcoats (W184, the product made by DIC graphics) which is a thermosetting resin.
  • the embossed pattern 3a is covered at a coating amount of 15 g / m 2 with a resin composition containing 0.05 parts by weight of the inorganic nanoparticle vesicle prepared using silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik).
  • AEROSIL OX50 silica nanoparticles having a particle diameter of 40 nm
  • Example 2-2 a vesicle comprising a single layer film containing a dispersant having an unsaturated double bond on the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added. Formed by adding a resin composition in which 0.05 part by weight of an inorganic nanoparticle vesicle encapsulating inorganic nanoparticles having a particle diameter of 40 nm is added to a mixed resin of 60 parts by weight of a thermosetting resin and 40 parts by weight of a photocurable resin. A decorative sheet 1 having a surface protective layer 2 was obtained.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • DIC graphics 60 parts by weight and photocurable urethane acrylate (Unidic 17-824-9, manufactured by DIC Graphics) 40 parts by weight, which is a photocurable resin.
  • the resin composition containing 0.05 part by weight of the inorganic nanoparticle vesicle prepared using silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik Co., Ltd.) as nanoparticles is shown in FIG. A decorative sheet 1 was obtained.
  • Example 2-3 a vesicle having a monolayer film containing a dispersant having an amino group on the surface of the transparent resin layer 3 (transparent resin sheet 3) to which no nucleating agent is added has a particle diameter of 40 nm.
  • the decorative sheet 1 was provided with a surface protective layer 2 formed of a resin composition in which 0.05 part by weight of inorganic nanoparticle vesicles containing inorganic nanoparticles was added to 100 parts by weight of a thermosetting resin.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the transparent resin sheet 3 has a pentad fraction of 97.8%, MFR (melt flow rate).
  • MWD molecular weight distribution
  • Miw / Mn molecular weight distribution MWD
  • Karlasorb 944 2000 ppm of a hindered amine light stabilizer
  • Example 2-4 a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added.
  • a surface protective layer 2 formed of a resin composition in which 0.005 part by weight of a dispersant vesicle encapsulating and 0.05 part by weight of inorganic nanoparticles having a particle diameter of 40 nm are added to 100 parts by weight of a thermosetting resin.
  • a decorative sheet 1 was obtained.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • the above-mentioned dispersant vesicle prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of DIC Graphics)
  • a decorative sheet 1 of this example shown in FIG. 1 was obtained using a resin composition to which 0.005 parts by weight and 0.05 parts by weight of silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik) were added.
  • Example 2-5 an unsaturated double bond was formed on the vesicle having a monolayer film made of phospholipid on the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle was added.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • W184 a thermosetting resin.
  • DIC Graphics Co., Ltd. and 60 parts by weight of photocurable urethane acrylate (Unidic 17-824-9, manufactured by DIC Graphics Co., Ltd.), which is a photocurable resin, are mixed.
  • KBM-503 3-methacryloxypropyltrimethoxysilane
  • Example 2-6 a dispersant having an amino group is included in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which no nucleating agent is added.
  • a decorative sheet comprising a surface protective layer 2 formed of a resin composition obtained by adding 0.005 part by weight of the dispersant vesicle and 0.05 part by weight of inorganic nanoparticles having a particle diameter of 40 nm to 100 parts by weight of a thermosetting resin It was set to 1.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • the above-mentioned dispersant vesicle prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of DIC Graphics)
  • a decorative sheet 1 of this example shown in FIG. 1 was obtained using a resin composition to which 0.005 parts by weight and 0.05 parts by weight of silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik) were added.
  • Comparative Example 2-1 In Comparative Example 2-1, the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle was added, 0.005 parts by weight of a dispersant having an amino group and an inorganic nanoparticle having a particle diameter of 40 nm.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • W184 a two-component curable urethane topcoat
  • W184 thermosetting resin.
  • KBM-903 3-aminopropyltrimethoxysilane
  • a decorative sheet 1 of this comparative example shown in FIG. 1 was obtained using a resin composition to which 0.05 parts by weight of 40 nm silica nanoparticles (AEROSIL OX50, manufactured by Evonik) was added.
  • Comparative Example 2-2 a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added.
  • a surface protective layer 2 formed of a resin composition in which 0.005 part by weight of a dispersant vesicle encapsulating and 0.05 part by weight of inorganic fine particles having a particle diameter of 4.5 ⁇ m are added to 100 parts by weight of a thermosetting resin. It was set as the decorative sheet 1 provided.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • W184 two-component curable urethane topcoat
  • the above-mentioned dispersant prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of 100 parts by weight of DIC Graphics)
  • KBM-903 3-aminopropyltrimethoxysilane
  • DIC Graphics A decorative sheet 1 of this comparative example shown in FIG.
  • AEROSIL OX50 silica fine particles having a particle diameter of 4.5 ⁇ m are added. Obtained.
  • Comparative Example 2-3 a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added.
  • the surface protective layer 2 is formed of a resin composition in which 0.0001 part by weight of a dispersant vesicle encapsulating and 0.001 part by weight of inorganic nanoparticles having a particle diameter of 40 nm are added to 100 parts by weight of a thermosetting resin. A decorative sheet 1 was obtained.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • W184 two-component curable urethane topcoat
  • the above-mentioned dispersant prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of 100 parts by weight of DIC Graphics)
  • KBM-903 3-aminopropyltrimethoxysilane
  • DIC Graphics A decorative sheet 1 of this comparative example shown in FIG.
  • Comparative Example 2-4 a dispersant having an amino group in a vesicle having a monolayer film made of phospholipid with respect to the surface of the transparent resin layer 3 (transparent resin sheet 3) to which the nucleating agent vesicle is added.
  • each resin layer is the same as that of the decorative sheet 1 of Example 2-1, but the surface protective layer 2 is a two-component curable urethane topcoat (W184) that is a thermosetting resin.
  • the above-mentioned dispersant prepared using 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant having an amino group with respect to 100 parts by weight of 100 parts by weight of DIC Graphics)
  • KBM-903 3-aminopropyltrimethoxysilane
  • DIC Graphics A decorative sheet 1 of this comparative example shown in FIG. 1 was obtained using a resin composition to which 2.5 parts by weight of vesicles and 25 parts by weight of silica nanoparticles having a particle diameter of 40 nm (AEROSIL OX50, manufactured by Evonik) were added.
  • ⁇ Hoffman scratch test> The Hoffman scratch test of the present example is the same as the Hoffman scratch test described in the example of the first embodiment. Therefore, the description of this test is omitted here.
  • ⁇ Steel wool rubbing test> The steel wool rubbing test of this example is the same as the steel wool rubbing test described in the example of the first embodiment. Therefore, the description of this test is omitted here.
  • ⁇ V-groove bending test> The V-groove bending test of the present example is the same as the V-groove bending test described in the example of the first embodiment. Therefore, the description of this test is omitted here.
  • the transparency was good, and good results were also obtained in the Hoffman scratch test, the steel wool test, and the V-groove bending test. Obtained.
  • the inorganic nanoparticles can be uniformly dispersed by adding inorganic nanoparticle vesicles or dispersant vesicles to the surface protective layer 2. This is probably because the surface hardness was improved due to the inorganic nanoparticles while maintaining good transparency and post-processing suitability required for the decorative sheet.
  • the decorative sheet 1 of Comparative Example 2-1 has a post-processing suitability required for the decorative sheet 1, but uses a non-vesicle dispersant for the surface protective layer 2. Further, it is considered that the dispersibility of the inorganic nanoparticles was not sufficiently obtained, and the transparency and scratch resistance required for the decorative sheet could not be obtained. Further, in the decorative sheet 1 of Comparative Example 2-2, since the particle diameter of the inorganic fine particles is too large, irregularities are formed on the surface of the surface protective layer 2 and the transparency is impaired. It is considered that the fine particles were not sufficiently bonded, resulting in poor scratch resistance and post-working resistance.
  • the decorative sheet 1 of Comparative Example 2-3 has the transparency and post-processing suitability required for the decorative sheet 1, but the amount of dispersant vesicle added and the amount of inorganic nanoparticles added are extremely small. Therefore, it is considered that the result was inferior in scratch resistance.
  • the decorative sheet 1 of Comparative Example 2-4 has post-processing suitability required for the decorative sheet 1, but the addition amount of the dispersant vesicle and inorganic nanoparticles was extremely large. The result is inferior in transparency, and the scratch resistance is considered to be inferior because the abrasive wear occurs due to the inorganic nanoparticles falling off during friction.
  • the decorative sheet 1 of the present invention shown in Examples 2-1 to 2-6 has the transparency required for the decorative sheet, and is extremely excellent in scratch resistance and post-processing resistance. It became clear that it was a sheet.
  • the present inventors have proposed a decorative sheet having excellent surface scratch resistance and post-processing resistance described in Japanese Patent No. 3772634 in order to eliminate these drawbacks. Thereafter, the use of the decorative sheet using the decorative sheet having the structure as shown in the above-mentioned Japanese Patent No. 3772634 has been increasingly expanded, and further improvement in post-process resistance such as surface scratch resistance and V-groove bending. It has been demanded. Moreover, since consumers' consciousness about quality has also advanced, not only the above-mentioned functionality but high designability is also required.
  • the decorative sheet of the present invention is not limited to the above embodiments and examples, and various modifications can be made without departing from the characteristics of the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne : une feuille décorative présentant une excellente résistance à l'abrasion et une résistance au post-traitement tout en assurant une grande transparence d'une couche protectrice de surface ; et un procédé de fabrication de la feuille décorative. Une feuille décorative (1), selon un mode de la présente invention, comporte : une ou plusieurs couches d'une couche intermédiaire sur l'une des surfaces d'une couche de matériau de base (6) ; et une ou plusieurs couches d'une couche protectrice (2) de surface sur la couche intermédiaire, le composant principal de chaque couche de ladite couche protectrice (2) de surface étant une résine durcissable, la couche unique ou au moins l'une desdites couches de ladite couche protectrice (2) de surface contenant un dispersant et des nanoparticules inorganiques, et le dispersant et les nanoparticules inorganiques étant enfermés ensembles dans des vésicules.
PCT/JP2016/074968 2015-08-26 2016-08-26 Feuille décorative et procédé de production de feuille décorative WO2017034021A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015166616 2015-08-26
JP2015-166616 2015-08-26
JP2016066100 2016-03-29
JP2016-066100 2016-03-29

Publications (1)

Publication Number Publication Date
WO2017034021A1 true WO2017034021A1 (fr) 2017-03-02

Family

ID=58100396

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/074968 WO2017034021A1 (fr) 2015-08-26 2016-08-26 Feuille décorative et procédé de production de feuille décorative

Country Status (2)

Country Link
TW (1) TW201718264A (fr)
WO (1) WO2017034021A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7524634B2 (ja) 2020-06-30 2024-07-30 Ｔｏｐｐａｎホールディングス株式会社 化粧シート及びその製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270054A (ja) * 2000-03-23 2001-10-02 Toppan Printing Co Ltd 化粧シート
JP2007100045A (ja) * 2005-10-07 2007-04-19 Masamitsu Nagahama ポリオレフィン樹脂製品、ポリオレフィン樹脂製品の製造方法、粒状物の使用
JP2007204666A (ja) * 2006-02-03 2007-08-16 Kanenori Fujita 耐熱性樹脂製品、耐熱性樹脂製品の製造方法、粒状物の使用
JP2011201323A (ja) * 2006-09-28 2011-10-13 Dainippon Printing Co Ltd 化粧シート
WO2016076360A1 (fr) * 2014-11-11 2016-05-19 株式会社トッパン・コスモ Feuille décorée
JP2016165807A (ja) * 2015-03-09 2016-09-15 株式会社トッパン・コスモ 化粧シート
JP2016175363A (ja) * 2015-03-23 2016-10-06 株式会社トッパン・コスモ 化粧シート

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270054A (ja) * 2000-03-23 2001-10-02 Toppan Printing Co Ltd 化粧シート
JP2007100045A (ja) * 2005-10-07 2007-04-19 Masamitsu Nagahama ポリオレフィン樹脂製品、ポリオレフィン樹脂製品の製造方法、粒状物の使用
JP2007204666A (ja) * 2006-02-03 2007-08-16 Kanenori Fujita 耐熱性樹脂製品、耐熱性樹脂製品の製造方法、粒状物の使用
JP2011201323A (ja) * 2006-09-28 2011-10-13 Dainippon Printing Co Ltd 化粧シート
WO2016076360A1 (fr) * 2014-11-11 2016-05-19 株式会社トッパン・コスモ Feuille décorée
JP2016168830A (ja) * 2014-11-11 2016-09-23 凸版印刷株式会社 化粧シート
JP2016165807A (ja) * 2015-03-09 2016-09-15 株式会社トッパン・コスモ 化粧シート
JP2016175363A (ja) * 2015-03-23 2016-10-06 株式会社トッパン・コスモ 化粧シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7524634B2 (ja) 2020-06-30 2024-07-30 Ｔｏｐｐａｎホールディングス株式会社 化粧シート及びその製造方法

Also Published As

Publication number Publication date
TW201718264A (zh) 2017-06-01

Similar Documents

Publication Publication Date Title
JP6861941B2 (ja) 化粧シートおよび化粧シートの製造方法
JP6709611B2 (ja) 化粧シートおよび化粧シートの製造方法
JP6603468B2 (ja) 化粧シートおよび化粧シートの製造方法
JP6622468B2 (ja) 化粧シートおよび化粧シートの製造方法
JP6997915B2 (ja) 化粧シート、及び化粧シートの製造方法
JP6928929B2 (ja) 化粧シート、及び化粧シートの製造方法
JP7006191B2 (ja) 化粧シート及び化粧シートの製造方法
JP7528543B2 (ja) 化粧シート
JP2016190465A (ja) 化粧シート
JP6643823B2 (ja) 化粧シートおよび化粧シートの製造方法
JP6622487B2 (ja) 化粧シートおよび化粧シートの製造方法
JP6576096B2 (ja) 化粧シートおよび化粧シートの製造方法
JP6537306B2 (ja) 化粧シートおよび化粧シートの製造方法
JP2016190466A (ja) 化粧シート
JP7031126B2 (ja) 化粧シート及び化粧シートの製造方法
JP7322381B2 (ja) 化粧シート及びその製造方法
WO2017034021A1 (fr) Feuille décorative et procédé de production de feuille décorative
JP6781516B2 (ja) 化粧シート
JP6537314B2 (ja) 化粧シートおよび化粧シートの製造方法
JP7331626B2 (ja) 化粧シート及びその製造方法
JP7404771B2 (ja) 化粧シート及びその製造方法
JP2021194903A (ja) 化粧シート

Legal Events

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

Ref document number: 16839368

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16839368

Country of ref document: EP

Kind code of ref document: A1