WO2016158903A1 - Decorative sheet and decorative board - Google Patents

Decorative sheet and decorative board Download PDF

Info

Publication number
WO2016158903A1
WO2016158903A1 PCT/JP2016/060021 JP2016060021W WO2016158903A1 WO 2016158903 A1 WO2016158903 A1 WO 2016158903A1 JP 2016060021 W JP2016060021 W JP 2016060021W WO 2016158903 A1 WO2016158903 A1 WO 2016158903A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
decorative sheet
decorative
sheet
layer
Prior art date
Application number
PCT/JP2016/060021
Other languages
French (fr)
Japanese (ja)
Inventor
陽子 鷹野
千草 栗山
小林　武
明彦 片島
達也 米崎
Original Assignee
大日本印刷株式会社
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 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Publication of WO2016158903A1 publication Critical patent/WO2016158903A1/en

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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin

Definitions

  • the present invention relates to a decorative sheet and a decorative board.
  • decorative sheets are laminated on the surfaces of various articles in order to impart design properties.
  • decorative sheets are laminated and used on the surfaces of wall covering materials used for the wall surfaces of buildings, floor decorative materials used for floor surfaces, furniture, and the like.
  • the decorative sheet laminated on the surface of the article as described above is required to exhibit a three-dimensional design and an excellent tactile sensation.
  • a decorative sheet exhibiting such a three-dimensional design and tactile sensation
  • a printed layer on at least one side of the base material, and a transparent resin layer is provided on the entire surface.
  • a decorative material provided with a convex portion by thick printing mainly composed of a curable resin see, for example, Patent Document 1.
  • the surface has convex portions made of an ionizing radiation curable resin in synchronization with the pattern, and the height and interval of the convex portions are in a specific range, and a specific amount of granular particles having a particle size of 3 to 10 ⁇ m is contained.
  • a decorative sheet has been proposed (see, for example, Patent Document 2).
  • the wear-resistant material is projected from the surface of the coating film by adding an abrasion-resistant material having a particle size defined with respect to the thickness of the coating film. .
  • the coating suitability of the resin composition (ink) for forming the convex portion is lowered depending on the type of the abrasion-resistant material, and a desired There is a problem that it is difficult to stably manufacture a decorative sheet including a convex portion having a shape or a pattern.
  • the present invention provides a decorative sheet that exhibits excellent tactile sensation, excellent scratch resistance, and excellent coating suitability during production, and a decorative board formed by attaching the decorative sheet to an adherend. For the purpose.
  • the inventor has found that, on a base sheet, at least a convex portion including a resin is formed, the height of the convex portion, the content of inorganic particles in the convex portion, and the inorganic
  • the above object can be achieved by setting the average particle diameter of the particles within a specific range, and have completed the present invention.
  • the present invention relates to the following decorative sheet and decorative plate.
  • a decorative sheet in which at least convex portions containing resin are formed, (1) The height of the convex portion is 10 ⁇ m or more, (2) The convex portion contains 10 to 30 parts by mass of inorganic particles having an average particle diameter of 11 to 30 ⁇ m with respect to 100 parts by mass of the resin.
  • a decorative sheet characterized by that. 2. Item 2. The decorative sheet according to Item 1, wherein the resin is an ionizing radiation curable resin. 3. Item 3. The item 1 or 2, wherein at least a pattern layer and a transparent resin layer are laminated in this order on the substrate sheet, and a convex portion containing the resin is formed on the transparent resin layer. Makeup sheet. 4). Item 4. The decorative sheet according to Item 3, wherein the pattern pattern layer and the convex portion including the resin are synchronized. 5. Item 5. A decorative board obtained by adhering the decorative sheet according to any one of Items 1 to 4 to an adherend.
  • the decorative sheet of the present invention is formed with at least convex portions containing a resin, and the height of the convex portions, the content of the inorganic particles in the convex portions, and the average particle diameter of the inorganic particles are in a specific range, so that it is excellent. It exhibits excellent tactile sensation, excellent scratch resistance, and excellent coating suitability during production.
  • the decorative sheet of the present invention has at least a convex portion containing a resin on the base sheet, (1) the height of the convex portion is 10 ⁇ m or more, and (2) the convex portion is The inorganic particle having an average particle diameter of 11 to 30 ⁇ m is contained in an amount of 10 to 30 parts by mass with respect to 100 parts by mass of the resin.
  • the decorative sheet of the present invention having the above characteristics can exhibit excellent tactile sensation because the height of the convex portion is 10 ⁇ m or more.
  • the convex portion contains inorganic particles having a specific average particle diameter in a specific range, it has excellent scratch resistance while maintaining excellent tactile sensation, and forms a convex portion during manufacturing. In this process, wear of equipment such as a doctor blade is suppressed, so that stable production can be achieved, so-called coating suitability is excellent, and production efficiency is excellent.
  • the direction in which the convex portion is formed as viewed from the base sheet is referred to as “upper” or “front surface”, and the direction in which the convex portion is formed as viewed from the base sheet. Refers to the opposite side as “bottom” or “back”.
  • the base sheet is not limited, and a fibrous sheet, a plastic base, a metal base, a wood base, and the like can be used.
  • fiber sheet known fiber sheets such as thin paper, inter-paper reinforcing paper, impregnated paper, titanium paper, coated paper, corrugated paper, linter paper, craft paper, and fine paper can be used.
  • wallpaper general paper Pulp-based sheet sized with a known sizing agent
  • flame-retardant paper Pulp-based sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate
  • Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide
  • fine paper fine paper
  • thin paper fiber mixed paper (paper made by mixing pulp and synthetic fiber).
  • fiber mixed paper paper made by mixing pulp and synthetic fiber.
  • what corresponds to a nonwoven fabric is included in the fibrous sheet used for this invention on classification.
  • plastic substrate various plastic sheets and films such as polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene, and polyvinyl chloride can be used.
  • the plastic substrate is preferably colored.
  • a metal base material what made the undercoat of a coloring agent on a steel plate, aluminum, stainless steel etc. can be commercialized as a base material.
  • Examples of the wood-based substrate include plywood, particle board, medium density fiber board, and the like.
  • the basis weight of the base sheet is not critical, preferably about 20 ⁇ 300g / m 2, more preferably about 50 ⁇ 300g / m 2, more preferably about 50 ⁇ 130g / m 2.
  • the convex part containing resin is formed at least on the base material sheet. It is preferable that the convex part in this invention is formed by thick printing so that a desired design may be expressed as what is called a thick printing layer.
  • a convex part is a form shown by convex shape in a cross-sectional schematic diagram as shown in FIG.1 and 2, for example, the cone-shaped or cylindrical protrusion is formed in the decorative sheet surface. It includes not only a form but also a form in which protrusions are formed to extend linearly, such as a conduit pattern.
  • the height of the convex part is 10 ⁇ m or more. If the height of the convex portion is lower than 10 ⁇ m, a decorative sheet showing excellent tactile feeling cannot be obtained.
  • a preferable lower limit of the height of the convex portion is 15 ⁇ m.
  • the upper limit with the preferable height of a convex part is 50 micrometers, and a more preferable upper limit is 40 micrometers.
  • the height of the convex portion is measured using a stylus type roughness measuring instrument “SE-30K” (model number) manufactured by Kosaka Laboratory Co., Ltd. This is a value measured by measuring the surface shape of the decorative sheet under the condition No. 8, reading the height from the chart of the measurement part, and calculating the average value, excluding the part where the inorganic particles remarkably jumped out.
  • SE-30K stylus type roughness measuring instrument
  • the resin constituting the convex portion is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin).
  • a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin).
  • ionizing radiation curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.
  • thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines.
  • unsaturated polyester resins polyurethane resins (including two-component curable polyurethane)
  • epoxy resins include epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines.
  • -Urea cocondensation resin silicon resin, polysiloxane resin and the like.
  • a curing agent such as a crosslinking agent and a polymerization initiator and a polymerization accelerator can be added to the resin.
  • curing agents isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc.
  • a radical initiator can be added to the unsaturated polyester resin.
  • the method of forming the convex portion with the thermosetting resin includes, for example, applying a solution of the thermosetting resin by a coating method such as a roll coating method, a gravure coating method, a gravure printing method, a silk screen printing method, and drying and curing. A method is mentioned.
  • the ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure.
  • one or more prepolymers, oligomers and monomers having a polymerizable unsaturated bond or epoxy group that can be crosslinked by irradiation with ionizing radiation in the molecule can be used.
  • examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.
  • Ionizing radiation includes visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and / or electron beams are desirable.
  • an ultra-high pressure mercury lamp As the ultraviolet light source, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used.
  • the wavelength of ultraviolet light is about 190 to 380 nm.
  • the electron beam source for example, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.
  • the energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV.
  • the amount of electron beam irradiation is preferably about 1 to 15 Mrad, more preferably about 1 to 10 Mrad, and further preferably about 3 to 5 Mrad.
  • the ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when cured by irradiation with ultraviolet rays.
  • a photopolymerization initiator sensitizer
  • Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used.
  • a resin system having a cationic polymerizable functional group for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt.
  • an aromatic diazonium salt an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt.
  • the addition amount of the photopolymerization initiator is not particularly limited, but is generally about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
  • a solution of an ionizing radiation curable resin is applied by a coating method such as a gravure coating method, a roll coating method, a gravure printing method, a silk screen printing method, or the like. After drying by ionizing radiation.
  • the convex portion contains 10 to 30 parts by mass of inorganic particles having an average particle diameter of 11 to 30 ⁇ m with respect to 100 parts by mass of the resin. If the content of the inorganic particles is less than 10 parts by mass, sufficient scratch resistance cannot be obtained. Moreover, when content of the said inorganic particle exceeds 30 mass parts, it is inferior to coating suitability.
  • the content of the inorganic particles is preferably 15 to 30 parts by mass.
  • the inorganic particles are not particularly limited, and examples thereof include silica, alumina, chromium oxide, iron oxide, diamond, calcium carbonate, aluminum hydroxide, barium sulfate, and talc.
  • silica is preferable because it can impart scratch resistance and touch to the decorative sheet.
  • equipment such as a doctor blade is worn out in the coating process, and the coating suitability may be deteriorated.
  • the inorganic particles contained in the convex portions have an average particle diameter of 11 to 30 ⁇ m. If the average particle size of the inorganic particles is less than 11 ⁇ m, sufficient scratch resistance cannot be obtained. Moreover, when the average particle diameter of an inorganic particle exceeds 30 micrometers, it is inferior to workability.
  • the average particle size of the inorganic particles is preferably 11 to 20 ⁇ m. In the present specification, the average particle diameter is a value measured by a laser diffraction / scattering method.
  • the maximum particle size of the inorganic particles contained in the convex portions is preferably 30 to 50 ⁇ m, more preferably 35 to 45 ⁇ m.
  • the decorative sheet of the present invention exhibits better scratch resistance.
  • the maximum particle diameter is a value measured by a laser diffraction / scattering method.
  • the convex part is used for the purpose of adjusting the design of the convex part.
  • the matting agent is not particularly limited, and for example, organic particles and inorganic particles can be used.
  • organic particles urethane beads, acrylic beads, nylon beads and the like can be used.
  • inorganic particles silica, alumina, chromium oxide, iron oxide, diamond, calcium carbonate, aluminum hydroxide, barium sulfate, talc, or the like can be used.
  • inorganic particles are preferably used in terms of more excellent matting effect, silica is more preferably used, and surface-treated silica is more preferably used.
  • the average particle size of the matting agent is preferably 1 to 10 ⁇ m. When the average particle diameter of the matting agent is within the above range, the convex portion of the decorative sheet of the present invention exhibits low gloss and can exhibit excellent design.
  • the convex portion preferably contains 1 to 30 parts by mass, more preferably 5 to 20 parts by mass of the matting agent with respect to 100 parts by mass of the resin.
  • content of a matting agent By making content of a matting agent into the said range, the convex part of the decorative sheet of this invention can show low glossiness, and can show the outstanding designability.
  • the sum of the content of fine particles having an average particle diameter of less than 11 ⁇ m and the content of inorganic particles having an average particle diameter of 11 to 30 ⁇ m is 40 parts by mass or less, preferably 100 parts by mass or less, preferably Setting from 15 to 40 parts by mass is preferable from the viewpoint of improving the coating suitability of the resin composition forming the convex part.
  • the same pigments as those described later can be used.
  • the foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N'-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium hydrogen carbonate, potassium hydrogen carbonate and the like, or vinylidene chloride.
  • a capsule foaming agent microcapsule type in which a thermally expandable gas such as hexane or isobutane is enclosed in a resin spherical shell made of acrylonitrile or a copolymer thereof can be used.
  • the added amount is usually 1 to 20 parts by mass with respect to 100 parts by mass of the resin.
  • the foaming temperature is selected in the range of 100 to 180 ° C.
  • a foaming agent described in JP-A-57-193325, page 2, right column may be added.
  • the resin composition for forming the convex portion includes various additives such as solvents, dyes, pigments and other colorants, fillers such as extenders, antifoaming agents, leveling agents, and thixotropic agents. Can be added.
  • FIG. 1 shows the above example of the layer structure of the decorative sheet of the present invention.
  • the decorative sheet 1 of the present invention has a pattern layer 3 and a transparent resin layer 4 laminated in this order on a base sheet 2, and a convex portion 5 containing a resin on the transparent resin layer 4. Is formed.
  • a colored concealing layer 6 may be further formed between the base sheet 2 and the pattern layer 3 as shown in FIG.
  • a pattern pattern layer may be formed on the base sheet or the colored concealment layer described later, if necessary.
  • it becomes a decorative sheet excellent in the designability by setting it as the structure which the pattern pattern layer and the said convex part synchronize.
  • FIG. 1 and FIG. 2 a configuration in which convex portions are synchronized with a portion where the pattern of the pattern layer is formed, or conversely, a pattern of the pattern layer is formed.
  • the convex part may synchronize with the part which is not.
  • the pattern layer gives design to the decorative sheet.
  • Examples of the design pattern include a grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, an abstract pattern, a flower pattern, etc. You can choose according to your purpose.
  • the pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like.
  • a printing ink containing a colorant, a binder resin, and a solvent can be used as the printing ink. These inks may be known or commercially available.
  • the colorant is not particularly limited, and a known inorganic pigment or organic pigment can be used.
  • Inorganic pigments include, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), and cadmium. Examples thereof include red, ultramarine blue, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide.
  • organic pigment examples include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, Quinacridone, perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine).
  • the content of the pigment is preferably about 10 to 100 parts by mass, more preferably about 15 to 50 parts by mass with respect to 100 parts by mass of the resin component.
  • the binder resin can be set according to the type of the base sheet.
  • acrylic resin styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like.
  • solvent examples include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon
  • the thickness of the pattern layer varies depending on the type of pattern, but is generally preferably about 0.1 to 20 ⁇ m.
  • a transparent resin layer may be formed on the pattern layer for the purpose of adjusting gloss.
  • the transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent.
  • the resin constituting the transparent resin layer include phenol resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensate.
  • Silicon resin polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polymethylpentene , Acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate and the like.
  • fine particles such as silica, alumina and kaolin, beads such as urethane beads and acrylic beads may be added for gloss adjustment.
  • the transparent resin layer may be colored as long as it has transparency, but it is particularly desirable not to add a colorant.
  • the thickness of the transparent resin layer is usually about 5 to 50 ⁇ m, but may exceed the above range depending on the use of the decorative sheet.
  • a colored concealment layer may be formed on the colored concealment layer base sheet as necessary.
  • the colored concealing layer is formed as a whole surface solid printing layer on the base material sheet.
  • the colored hiding layer can be, for example, a layer containing a pigment and a binder resin.
  • This colored hiding layer can be formed by a known printing method such as gravure printing, flexographic printing, silk screen printing, or offset printing using, for example, a printing ink containing a coloring material, a binder resin, and a solvent. These inks may be known or commercially available.
  • coloring material binder resin, and solvent, those used in the above-described pattern layer can be used.
  • the thickness of the colored hiding layer is preferably about 1 to 4 ⁇ m.
  • a primer layer may be formed as necessary on the primer layer substrate sheet, the color concealing property, the pattern layer or the transparent resin layer for the purpose of improving the adhesion to the convex portion, etc. .
  • acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like can be used.
  • acrylic, chlorinated polypropylene, etc. Is desirable.
  • the acryl examples include, for example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylate methyl- (meth) acrylic acid (Meth) such as butyl copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer An acrylic resin made of a homopolymer or a copolymer containing an acrylate ester may be mentioned.
  • Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).
  • polystyrene resin one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.
  • isocyanate a polyvalent isocyanate having two or more isocyanate groups in the molecule is used.
  • aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate ) Isocyanates are used.
  • the thickness of the primer layer is not limited, but is preferably about 0.1 to 10 ⁇ m, more preferably about 0.1 to 5 ⁇ m.
  • the back primer layer is effective when a decorative sheet is produced by laminating the decorative sheet of the present invention and the adherend.
  • the back primer layer can be formed by applying a known primer to the base material sheet.
  • the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix
  • the additive examples include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers.
  • the blending amount of the additive can be appropriately set according to the product characteristics.
  • the application amount of the primer agent is not particularly limited, but is usually about 0.1 to 100 g / m 2 , preferably about 0.1 to 50 g / m 2 .
  • the thickness of the back primer layer is not particularly limited, but is usually about 0.01 to 10 ⁇ m, preferably about 0.1 to 1 ⁇ m.
  • Decorative plate By adhering the decorative sheet to an adherend, a decorative plate can be obtained.
  • the adherend is not limited, and the same materials as those used for known decorative panels can be used.
  • the adherend include wood materials, metals, ceramics, plastics, and glass.
  • the decorative sheet can be suitably used for a wood material.
  • wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. , Chip boards, or composite substrates on which chip boards are laminated.
  • wood plywood, particle board, medium density fiber board (MDF) is preferably used as the wood material.
  • the method of sticking the decorative sheet on the adherend is not limited, and for example, a method of attaching the decorative sheet to the adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like. These adhesives are used alone or in combination of two or more.
  • the decorative board manufactured in this way includes, for example, interior materials for buildings such as walls, ceilings, and floors; exterior materials such as balconies and verandas; surface decorative boards and furniture for furniture such as window frames, doors, and handrails; Alternatively, it can be used for a surface decorative plate of a cabinet such as a light electric or OA device.
  • Manufacturing method of decorative sheet As a manufacturing method of a decorative sheet, for example, a manufacturing method of forming a convex part including at least a resin on a base sheet can be mentioned.
  • Examples of the method for forming the convex portion with the thermosetting resin include a method in which a solution of the thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method and then dried and cured. Moreover, as a method of forming a convex part with ionizing radiation curable resin, the method of apply
  • the resin composition for forming these layers is gravure printing, flexographic printing, silk screen printing, What is necessary is just to form a convex part on an outermost surface layer, after apply
  • Example 1 As a base material sheet, a general paper for building materials with a weight of 30 g / m 2 is prepared, and an acrylic resin and nitrified cotton are used as a binder on one side of the paper, and ink containing titanium white, petal, and chrome is used as a colorant. A (full-surface solid) layer having a coating amount of 5 g / m 2 was applied by gravure printing to form a colored concealment layer. A woodgrain pattern layer was formed by gravure printing using an ink containing nitrified cotton as a binder and a colorant mainly composed of a petiole.
  • a coating composition containing acrylic polyol resin as a binder, 10 parts by mass of silica particles with respect to 100 parts by mass of binder, and 5 parts by mass of urethane beads with respect to 100 parts by mass of binder is prepared.
  • a transparent resin layer was formed by gravure printing on the entire surface at m 2 .
  • an electron beam with an acceleration voltage of 125 kV and an irradiation dose of 30 kGy was irradiated to cure the convex portion forming composition to form a convex portion having a height of 13.5 ⁇ m.
  • Examples 2 to 4 and Comparative Examples 1 to 6 A decorative sheet was prepared in the same manner as in Example 1 except that the types and blending amounts of the inorganic particles contained in the convex portions were changed as shown in Table 1.
  • the height of the convex portion formed on the surface of the decorative sheet prepared in the above examples and comparative examples was measured by the following method. Specifically, the surface shape of a decorative sheet was measured using a stylus type roughness measuring instrument “SE-30K” (model number) manufactured by Kosaka Laboratory Ltd. under the conditions of a measurement length of 5 mm and a cutoff value of 0.8. Was measured. The height of the convex portion was measured by reading the height from the chart of the measurement portion and calculating the average value, except for the portion where the inorganic particles jumped out significantly.
  • the surface of the tactile sensation sheet was touched by 15 adult men and women in their 20s to 40s with their hands to determine the tactile sensation, and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is 4 or more, it can be judged that the outstanding tactile sense is shown. 5: More than 10 adult men and women felt tactile sensation 4: 8-9 adult men and women felt tactile sensation 3: 6-7 adult men and women felt tactile sensation 2: Adult 4-5 men and women felt that tactile sensation was good 1: Less than 3 adult men and women felt tactile sensation
  • a decorative sheet was prepared by sticking the decorative sheets prepared in the scratch-resistant Examples and Comparative Examples to the MDF.
  • the decorative plate is attached to a friction table of a Martindale abrasion tester (“Martindale 1300 series model 1302 (model number)” manufactured by James Heal), and a Scotch Bright industrial pad 7446 (Three M Japan Co., Ltd.) is mounted on the decorative plate. )) And a load of 6 N, and a friction test by Lissajous figure motion was performed under the condition of 100 times of friction.
  • the appearance after the test was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is 3 or more, it is judged that it is excellent in abrasion resistance. 5: No scratch 4: Minor gloss change 3: Slight scratch, but no problem in actual use 2: Scratch 1: Scratch
  • Coating suitability transition stability
  • the surface transition state was visually observed, and the coating suitability was evaluated according to the following evaluation criteria.

Landscapes

  • Laminated Bodies (AREA)

Abstract

The objective of the present invention is to provide: a decorative sheet which has excellent texture and excellent scratch resistance, while exhibiting excellent coating adequacy during the production; and a decorative board which is obtained by bonding this decorative sheet to a material to be bonded. The present invention provides a decorative sheet which is obtained by forming at least a projection on a base sheet, said projection containing a resin, and which is characterized in that: (1) the height of the projection is 10 μm or more; and (2) the projection contains 10-30 parts by mass of inorganic particles, which have an average particle diameter of 11-30 μm, per 100 parts by mass of the resin.

Description

化粧シート及び化粧板Decorative sheet and decorative board
　本発明は、化粧シート及び化粧板に関する。 The present invention relates to a decorative sheet and a decorative board.
　従来、様々な物品の表面には、意匠性を付与するために、化粧シートが積層されている。例えば、建築物の壁面に用いられる壁装材や、床面に用いられる床用化粧材、家具等の表面には、化粧シートが積層されて用いられている。 Conventionally, decorative sheets are laminated on the surfaces of various articles in order to impart design properties. For example, decorative sheets are laminated and used on the surfaces of wall covering materials used for the wall surfaces of buildings, floor decorative materials used for floor surfaces, furniture, and the like.
　上述のような物品の表面に積層される化粧シートには、立体的な意匠性や、優れた触感を示すことが要求される。 The decorative sheet laminated on the surface of the article as described above is required to exhibit a three-dimensional design and an excellent tactile sensation.
　このような立体的な意匠性や、触感を示す化粧シートとして、基材の少なくとも片面に印刷層があり、さらに透明樹脂層が全面にあり、その上に、前記印刷層に同調した、電離放射線硬化型樹脂を主体とした厚盛り印刷による凸部が設けられている化粧材が提案されている（例えば、特許文献１参照）。また、表面に前記絵柄模様と同調した電離放射線硬化型樹脂からなる凸部とを有し、凸部の高さ及び間隔が特定の範囲であり、粒径３～１０μｍの粒状粒子を特定量含有する化粧シートが提案されている（例えば、特許文献２参照）。 As a decorative sheet exhibiting such a three-dimensional design and tactile sensation, there is a printed layer on at least one side of the base material, and a transparent resin layer is provided on the entire surface. There has been proposed a decorative material provided with a convex portion by thick printing mainly composed of a curable resin (see, for example, Patent Document 1). Further, the surface has convex portions made of an ionizing radiation curable resin in synchronization with the pattern, and the height and interval of the convex portions are in a specific range, and a specific amount of granular particles having a particle size of 3 to 10 μm is contained. A decorative sheet has been proposed (see, for example, Patent Document 2).
　しかしながら、これらの化粧材等は、凸部の耐傷性が不十分であり、摩耗によって凸部の艶が変化し、意匠性が低下したり触感が低下したりするという問題がある。 However, these decorative materials and the like have a problem in that the scratch resistance of the convex portions is insufficient, and the gloss of the convex portions changes due to wear, resulting in a decrease in design and a touch feeling.
　一方、表面保護層に耐擦傷性を付与するため、塗膜の厚みに対して粒径を規定した耐摩耗材を添加することで、塗膜の表面から耐摩耗材を突出させることが行われている。 On the other hand, in order to impart scratch resistance to the surface protective layer, the wear-resistant material is projected from the surface of the coating film by adding an abrasion-resistant material having a particle size defined with respect to the thickness of the coating film. .
　しかしながら、上述のような表面に触感を付与するために形成される凸部の場合、平滑面を形成するよう均一に塗工される通常の塗膜の条件をそのまま適用することで同様の効果を得ることはできず、耐擦傷性が十分でないという問題がある。 However, in the case of a convex portion formed to give a tactile sensation to the surface as described above, the same effect can be obtained by directly applying the conditions of a normal coating film that is uniformly applied so as to form a smooth surface. There is a problem that it cannot be obtained and the scratch resistance is not sufficient.
　また、化粧シートに耐擦傷性を付与するために凸部に耐摩耗材を添加する場合、耐摩耗材の種類によっては凸部を形成する樹脂組成物（インキ）の塗工適性が低下し、所望の形状やパターンを有する凸部を備える化粧シートを安定して製造することが難しくなるという問題がある。 In addition, when an abrasion-resistant material is added to the convex portion in order to impart scratch resistance to the decorative sheet, the coating suitability of the resin composition (ink) for forming the convex portion is lowered depending on the type of the abrasion-resistant material, and a desired There is a problem that it is difficult to stably manufacture a decorative sheet including a convex portion having a shape or a pattern.
　従って、優れた触感を示し、耐擦傷性に優れ、且つ、製造の際の塗工適性に優れる化粧シートの開発が求められている。 Therefore, there is a demand for the development of a decorative sheet that exhibits excellent tactile sensation, excellent scratch resistance, and excellent coating suitability during production.
特開平１０－８６３１３号公報Japanese Patent Laid-Open No. 10-86313 特開２０１３－１２３８６３号公報JP 2013-123863 A
　本発明は、優れた触感を示し、耐擦傷性に優れ、且つ、製造の際の塗工適性に優れる化粧シート、及び、当該化粧シートを被着材に貼着してなる化粧板を提供することを目的とする。 The present invention provides a decorative sheet that exhibits excellent tactile sensation, excellent scratch resistance, and excellent coating suitability during production, and a decorative board formed by attaching the decorative sheet to an adherend. For the purpose.
　本発明者は、鋭意研究を重ねた結果、基材シート上に、樹脂を含む凸部が少なくとも形成されている化粧シートにおいて、凸部の高さ、凸部の無機粒子の含有量、及び無機粒子の平均粒子径を特定の範囲とすることにより上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive research, the inventor has found that, on a base sheet, at least a convex portion including a resin is formed, the height of the convex portion, the content of inorganic particles in the convex portion, and the inorganic The inventors have found that the above object can be achieved by setting the average particle diameter of the particles within a specific range, and have completed the present invention.
　即ち、本発明は、下記の化粧シート及び化粧板に関する。
１．基材シート上に、樹脂を含む凸部が少なくとも形成されている化粧シートであって、
（１）前記凸部の高さが１０μｍ以上であり、
（２）前記凸部は、平均粒子径が１１～３０μｍの無機粒子を、樹脂１００質量部に対して１０～３０質量部含有する、
ことを特徴とする化粧シート。
２．前記樹脂は、電離放射線硬化型樹脂である、項１に記載の化粧シート。
３．基材シート上に、少なくとも絵柄模様層及び透明性樹脂層がこの順に積層されており、前記透明性樹脂層上に、前記樹脂を含む凸部が形成されている、項１又は２に記載の化粧シート。
４．前記絵柄模様層と、前記樹脂を含む凸部とが同調している、項３に記載の化粧シート。
５．項１～４のいずれかに記載の化粧シートを被着材に貼着してなる化粧板。 That is, the present invention relates to the following decorative sheet and decorative plate.
1. On the base sheet is a decorative sheet in which at least convex portions containing resin are formed,
(1) The height of the convex portion is 10 μm or more,
(2) The convex portion contains 10 to 30 parts by mass of inorganic particles having an average particle diameter of 11 to 30 μm with respect to 100 parts by mass of the resin.
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the resin is an ionizing radiation curable resin.
3. Item 3. The item 1 or 2, wherein at least a pattern layer and a transparent resin layer are laminated in this order on the substrate sheet, and a convex portion containing the resin is formed on the transparent resin layer. Makeup sheet.
4). Item 4. The decorative sheet according to Item 3, wherein the pattern pattern layer and the convex portion including the resin are synchronized.
5. Item 5. A decorative board obtained by adhering the decorative sheet according to any one of Items 1 to 4 to an adherend.
　本発明の化粧シートは、樹脂を含む凸部が少なくとも形成されており、凸部の高さ、凸部の無機粒子の含有量、及び無機粒子の平均粒子径が特定の範囲であるので、優れた触感を示し、耐擦傷性に優れ、且つ、製造の際の塗工適性に優れている。 The decorative sheet of the present invention is formed with at least convex portions containing a resin, and the height of the convex portions, the content of the inorganic particles in the convex portions, and the average particle diameter of the inorganic particles are in a specific range, so that it is excellent. It exhibits excellent tactile sensation, excellent scratch resistance, and excellent coating suitability during production.
本発明の化粧シートの層構成の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the decorative sheet of this invention. 本発明の化粧シートの層構成の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the decorative sheet of this invention.
　以下、本発明の化粧シート及び化粧板について詳細に説明する。 Hereinafter, the decorative sheet and the decorative plate of the present invention will be described in detail.
　１．化粧シート
　本発明の化粧シートは、基材シート上に、樹脂を含む凸部が少なくとも形成されており、（１）前記凸部の高さが１０μｍ以上であり、（２）前記凸部は、平均粒子径が１１～３０μｍの無機粒子を、樹脂１００質量部に対して１０～３０質量部含有することを特徴とする。 1. The decorative sheet of the present invention has at least a convex portion containing a resin on the base sheet, (1) the height of the convex portion is 10 μm or more, and (2) the convex portion is The inorganic particle having an average particle diameter of 11 to 30 μm is contained in an amount of 10 to 30 parts by mass with respect to 100 parts by mass of the resin.
　上記特徴を有する本発明の化粧シートは、凸部の高さが１０μｍ以上であるので、優れた触感を示すことができる。また、上記凸部が特定の平均粒子径の無機粒子を特定の範囲の含有量で含有するので優れた触感を維持しつつ耐擦傷性に優れており、且つ、製造の際の凸部を形成する工程において、ドクターブレード等の設備の摩耗が抑制されており、安定して製造することができる、いわゆる塗工適性に優れており、生産効率に優れている。 The decorative sheet of the present invention having the above characteristics can exhibit excellent tactile sensation because the height of the convex portion is 10 μm or more. In addition, since the convex portion contains inorganic particles having a specific average particle diameter in a specific range, it has excellent scratch resistance while maintaining excellent tactile sensation, and forms a convex portion during manufacturing. In this process, wear of equipment such as a doctor blade is suppressed, so that stable production can be achieved, so-called coating suitability is excellent, and production efficiency is excellent.
　以下、化粧シートを構成する各層について説明する。なお、本明細書では、基材シートから見て凸部が形成されている方向を「上」又は「おもて面」と称し、基材シートから見て凸部が形成されている方向とは逆側を「下」又は「裏面」と称する。 Hereinafter, each layer constituting the decorative sheet will be described. In the present specification, the direction in which the convex portion is formed as viewed from the base sheet is referred to as “upper” or “front surface”, and the direction in which the convex portion is formed as viewed from the base sheet. Refers to the opposite side as “bottom” or “back”.
　基材シート
　基材シートとしては限定されず、繊維質シート、プラスチック基材、金属基材、木質系基材等を用いることができる。 The base sheet is not limited, and a fibrous sheet, a plastic base, a metal base, a wood base, and the like can be used.
　繊維質シートとしては、薄紙、紙間強化紙、含浸紙、チタン紙、コート紙、段ボール紙、リンター紙、クラフト紙、上質紙等の公知の繊維質シートなどが利用できる。 As the fiber sheet, known fiber sheets such as thin paper, inter-paper reinforcing paper, impregnated paper, titanium paper, coated paper, corrugated paper, linter paper, craft paper, and fine paper can be used.
　具体的には、壁紙用一般紙（パルプ主体のシートを既知のサイズ剤でサイズ処理したもの）；難燃紙（パルプ主体のシートをスルファミン酸グアニジン、リン酸グアジニン等の難燃剤で処理したもの）；水酸化アルミニウム、水酸化マグネシウム等の無機添加剤を含む無機質紙；上質紙；薄用紙；繊維混抄紙（パルプと合成繊維とを混合して抄紙したもの）などが挙げられる。なお、本発明に使用される繊維質シートには、分類上、不織布に該当しているものも包含される。 Specifically, wallpaper general paper (pulp-based sheet sized with a known sizing agent); flame-retardant paper (pulp-based sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate) ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; fiber mixed paper (paper made by mixing pulp and synthetic fiber). In addition, what corresponds to a nonwoven fabric is included in the fibrous sheet used for this invention on classification.
　プラスチック基材としては、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、アクリロニトリルブタジエンスチレン、ポリ塩化ビニル等の各種のプラスチックシート、フィルム等が使用できる。プラスチック基材は、着色してある事が望ましい。金属基材としては、鋼板、アルミニウム、ステンレス等の上に、着色剤のアンダーコートを行ったものを基材として製品化する事ができる。木質系基材としては、合板、パーティクルボード、中密度ファイバーボード等が挙げられる。 As the plastic substrate, various plastic sheets and films such as polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene, and polyvinyl chloride can be used. The plastic substrate is preferably colored. As a metal base material, what made the undercoat of a coloring agent on a steel plate, aluminum, stainless steel etc. can be commercialized as a base material. Examples of the wood-based substrate include plywood, particle board, medium density fiber board, and the like.
　基材シートの坪量は限定的ではないが、２０～３００ｇ／ｍ２程度が好ましく、５０～３００ｇ／ｍ２程度がより好ましく、５０～１３０ｇ／ｍ２程度が更に好ましい。 Although the basis weight of the base sheet is not critical, preferably about 20 ~ 300g / m 2, more preferably about 50 ~ 300g / m 2, more preferably about 50 ~ 130g / m 2.
　凸部
　本発明の化粧シートは、基材シート上に樹脂を含む凸部が少なくとも形成されている。本発明における凸部は、いわゆる厚盛り印刷層として、所望の意匠を表現するように厚盛り印刷によって形成されることが好ましい。なお、本発明において、凸部とは、図１及び２に示すような断面模式図において凸形状で示される形態であり、例えば、化粧シート表面において円錐形や円柱形の突起が形成されている形態だけでなく、導管模様のような、突起が線状に伸びて形成されている形態も含む。 Convex part As for the decorative sheet of this invention, the convex part containing resin is formed at least on the base material sheet. It is preferable that the convex part in this invention is formed by thick printing so that a desired design may be expressed as what is called a thick printing layer. In addition, in this invention, a convex part is a form shown by convex shape in a cross-sectional schematic diagram as shown in FIG.1 and 2, for example, the cone-shaped or cylindrical protrusion is formed in the decorative sheet surface. It includes not only a form but also a form in which protrusions are formed to extend linearly, such as a conduit pattern.
　凸部の高さは１０μｍ以上である。凸部の高さが１０μｍより低いと優れた触感を示す化粧シートが得られない。凸部の高さの好ましい下限は、１５μｍである。また、凸部の高さの好ましい上限は５０μｍであり、より好ましい上限は４０μｍである。凸部の高さの上限を上記範囲とすることにより、本発明の化粧シートが優れた触感を示し、且つ、より優れた耐擦傷性を示すことができる。なお、本明細書において、凸部の高さは、小坂研究所株式会社製触針式形状粗さ測定器「ＳＥ－３０Ｋ」（型番）を用いて、測定長さ５ｍｍ、カットオフ値０．８の条件で化粧シートの表面形状を測定し、無機粒子が著しく飛び出た部分を除いて、測定部分のチャートから高さを読み取り、平均値を算出することによって測定された値である。 The height of the convex part is 10 μm or more. If the height of the convex portion is lower than 10 μm, a decorative sheet showing excellent tactile feeling cannot be obtained. A preferable lower limit of the height of the convex portion is 15 μm. Moreover, the upper limit with the preferable height of a convex part is 50 micrometers, and a more preferable upper limit is 40 micrometers. By making the upper limit of the height of a convex part into the said range, the decorative sheet of this invention can show the outstanding tactile sense, and can show the more outstanding abrasion resistance. In the present specification, the height of the convex portion is measured using a stylus type roughness measuring instrument “SE-30K” (model number) manufactured by Kosaka Laboratory Co., Ltd. This is a value measured by measuring the surface shape of the decorative sheet under the condition No. 8, reading the height from the chart of the measurement part, and calculating the average value, excluding the part where the inorganic particles remarkably jumped out.
　凸部を構成する樹脂は、熱硬化型樹脂、電離放射線硬化型樹脂（例えば、電子線硬化型樹脂）等の硬化型樹脂が好ましい。特に電離放射線硬化型樹脂は、高い表面硬度、生産性等の観点から好ましい。 The resin constituting the convex portion is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin). In particular, ionizing radiation curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.
　熱硬化型樹脂としては、例えば、不飽和ポリエステル樹脂、ポリウレタン樹脂（２液硬化型ポリウレタンも含む）、エポキシ樹脂、アミノアルキッド樹脂、フェノール樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹脂、グアナミン樹脂、メラミン－尿素共縮合樹脂、珪素樹脂、ポリシロキサン樹脂等が挙げられる。 Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea cocondensation resin, silicon resin, polysiloxane resin and the like.
　上記樹脂には、架橋剤、重合開始剤等の硬化剤、重合促進剤を添加することができる。例えば、硬化剤としてはイソシアネート、有機スルホン酸塩等が不飽和ポリエステル樹脂やポリウレタン樹脂等に添加でき、有機アミン等がエポキシ樹脂に添加でき、メチルエチルケトンパーオキサイド等の過酸化物、アゾイソブチルニトリル等のラジカル開始剤が不飽和ポリエステル樹脂に添加できる。 A curing agent such as a crosslinking agent and a polymerization initiator and a polymerization accelerator can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.
　熱硬化型樹脂で凸部を形成する方法は、例えば、熱硬化型樹脂の溶液をロールコート法、グラビアコート法、グラビア印刷法、シルクスクリーン印刷法等の塗布法で塗布し、乾燥・硬化させる方法が挙げられる。 The method of forming the convex portion with the thermosetting resin includes, for example, applying a solution of the thermosetting resin by a coating method such as a roll coating method, a gravure coating method, a gravure printing method, a silk screen printing method, and drying and curing. A method is mentioned.
　電離放射線硬化型樹脂は、電離放射線の照射により架橋重合反応を生じ、３次元の高分子構造に変化する樹脂であれば限定されない。例えば、電離放射線の照射により架橋可能な重合性不飽和結合又はエポキシ基を分子中に有するプレポリマー、オリゴマー及びモノマーの１種以上が使用できる。例えば、ウレタンアクリレート、ポリエステルアクリレート、エポキシアクリレート等のアクリレート樹脂；シロキサン等のケイ素樹脂；ポリエステル樹脂；エポキシ樹脂などが挙げられる。 The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more prepolymers, oligomers and monomers having a polymerizable unsaturated bond or epoxy group that can be crosslinked by irradiation with ionizing radiation in the molecule can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.
　電離放射線としては、可視光線、紫外線（近紫外線、真空紫外線等）、Ｘ線、電子線、イオン線等があるが、この中でも、紫外線及び／又は電子線が望ましい。 Ionizing radiation includes visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and / or electron beams are desirable.
　紫外線源としては、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク灯、ブラックライト蛍光灯、メタルハライドランプ灯の光源が使用できる。紫外線の波長としては、１９０～３８０ｎｍ程度である。 As the ultraviolet light source, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet light is about 190 to 380 nm.
　電子線源としては、例えば、コッククロフトワルト型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型等の各種電子線加速器が使用できる。電子線のエネルギーとしては、１００～１０００ｋｅＶ程度が好ましく、１００～３００ｋｅＶ程度がより好ましい。電子線の照射量は、１～１５Ｍｒａｄ程度が好ましく、１～１０Ｍｒａｄ程度がより好ましく、３～５Ｍｒａｄ程度が更に好ましい。 As the electron beam source, for example, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The amount of electron beam irradiation is preferably about 1 to 15 Mrad, more preferably about 1 to 10 Mrad, and further preferably about 3 to 5 Mrad.
　電離放射線硬化型樹脂は電子線を照射すれば十分に硬化するが、紫外線を照射して硬化させる場合には、光重合開始剤（増感剤）を添加することが好ましい。 The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when cured by irradiation with ultraviolet rays.
　ラジカル重合性不飽和基を有する樹脂系の場合の光重合開始剤は、例えば、アセトフェノン類、ベンゾフェノン類、チオキサントン類、ベンゾイン、ベンゾインメチルエーテル、ミヒラーベンゾイルベンゾエート、ミヒラーケトン、ジフェニルサルファイド、ジベンジルジサルファイド、ジエチルオキサイト、トリフェニルビイミダゾール、イソプロピル－Ｎ，Ｎ－ジメチルアミノベンゾエート等の少なくとも１種が使用できる。また、カチオン重合性官能基を有する樹脂系の場合は、例えば、芳香族ジアゾニウム塩、芳香族スルホニウム塩、メタロセン化合物、ベンゾインスルホン酸エステル、フリールオキシスルホキソニウムジアリルヨードシル塩等の少なくとも１種が使用できる。 Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.
　光重合開始剤の添加量は特に限定されないが、一般に電離放射線硬化型樹脂１００質量部に対して０．１～１０質量部程度である。 The addition amount of the photopolymerization initiator is not particularly limited, but is generally about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
　電離放射線硬化型樹脂で凸部を形成する方法としては、例えば、電離放射線硬化型樹脂の溶液をグラビアコート法、ロールコート法、グラビア印刷法、シルクスクリーン印刷法等の塗布法で塗布し、必要により乾燥させた後、電離放射線の照射により硬化させればよい。 As a method for forming a convex portion with an ionizing radiation curable resin, for example, a solution of an ionizing radiation curable resin is applied by a coating method such as a gravure coating method, a roll coating method, a gravure printing method, a silk screen printing method, or the like. After drying by ionizing radiation.
　凸部は、平均粒子径が１１～３０μｍの無機粒子を、上記樹脂１００質量部に対して１０～３０質量部含有する。上記無機粒子の含有量が１０質量部未満であると十分な耐傷性が得られない。また、上記無機粒子の含有量が３０質量部を超えると、塗工適性に劣る。上記無機粒子の含有量は、１５～３０質量部が好ましい。 The convex portion contains 10 to 30 parts by mass of inorganic particles having an average particle diameter of 11 to 30 μm with respect to 100 parts by mass of the resin. If the content of the inorganic particles is less than 10 parts by mass, sufficient scratch resistance cannot be obtained. Moreover, when content of the said inorganic particle exceeds 30 mass parts, it is inferior to coating suitability. The content of the inorganic particles is preferably 15 to 30 parts by mass.
　無機粒子としては特に限定されないが、例えば、シリカ、アルミナ、酸化クロム、酸化鉄、ダイヤモンド、炭酸カルシウム、水酸化アルミニウム、硫酸バリウム、タルク等が挙げられる。中でも、化粧シートに耐擦傷性及び触感を付与することができる点で、シリカが好ましい。アルミナのように硬い無機粒子を添加すると、塗工工程においてドクターブレード等の設備が摩耗してしまい、塗工適性に劣るおそれがある。 The inorganic particles are not particularly limited, and examples thereof include silica, alumina, chromium oxide, iron oxide, diamond, calcium carbonate, aluminum hydroxide, barium sulfate, and talc. Among these, silica is preferable because it can impart scratch resistance and touch to the decorative sheet. When hard inorganic particles such as alumina are added, equipment such as a doctor blade is worn out in the coating process, and the coating suitability may be deteriorated.
　凸部が含有する上記無機粒子は、平均粒子径が１１～３０μｍである。無機粒子の平均粒子径が１１μｍ未満であると、十分な耐傷性が得られない。また、無機粒子の平均粒子径が３０μｍを超えると、加工適性に劣る。上記無機粒子の平均粒子径は、１１～２０μｍが好ましい。なお、本明細書において、平均粒子径は、レーザー回折・散乱法により測定される値である。 The inorganic particles contained in the convex portions have an average particle diameter of 11 to 30 μm. If the average particle size of the inorganic particles is less than 11 μm, sufficient scratch resistance cannot be obtained. Moreover, when the average particle diameter of an inorganic particle exceeds 30 micrometers, it is inferior to workability. The average particle size of the inorganic particles is preferably 11 to 20 μm. In the present specification, the average particle diameter is a value measured by a laser diffraction / scattering method.
　凸部が含有する上記無機粒子の最大粒子径は、３０～５０μｍが好ましく、３５～４５μｍがより好ましい。無機粒子の最大粒子径を上述の範囲とすることにより、本発明の化粧シートがより優れた耐傷性を示す。なお、本明細書において、最大粒子径は、レーザー回折・散乱法により測定される値である。 The maximum particle size of the inorganic particles contained in the convex portions is preferably 30 to 50 μm, more preferably 35 to 45 μm. By making the maximum particle diameter of the inorganic particles in the above range, the decorative sheet of the present invention exhibits better scratch resistance. In the present specification, the maximum particle diameter is a value measured by a laser diffraction / scattering method.
　凸部は、上記平均粒子径が１１～３０μｍの無機粒子を、樹脂１００質量部に対して１０～３０質量部含有する他に、更に、凸部の意匠性を調整することなどを目的として、艶消剤や顔料など平均粒子径が１１μｍ未満の微粒子を含有していてもよい。 In addition to containing 10 to 30 parts by mass of the inorganic particles having an average particle diameter of 11 to 30 μm with respect to 100 parts by mass of the resin, the convex part is used for the purpose of adjusting the design of the convex part. You may contain microparticles | fine-particles with an average particle diameter of less than 11 micrometers, such as a matting agent and a pigment.
　艶消剤としては特に限定されず、例えば、有機粒子、無機粒子等を用いることができる。有機粒子としては、ウレタンビーズ、アクリルビーズ、ナイロンビーズ等を用いることができる。また、無機粒子としては、シリカ、アルミナ、酸化クロム、酸化鉄、ダイヤモンド、炭酸カルシウム、水酸化アルミニウム、硫酸バリウム、タルク等を用いることができる。中でも、より艶消し効果に優れる点で無機粒子を用いることが好ましく、シリカを用いることがより好ましく、表面処理シリカを用いることが更に好ましい。 The matting agent is not particularly limited, and for example, organic particles and inorganic particles can be used. As the organic particles, urethane beads, acrylic beads, nylon beads and the like can be used. As the inorganic particles, silica, alumina, chromium oxide, iron oxide, diamond, calcium carbonate, aluminum hydroxide, barium sulfate, talc, or the like can be used. Among these, inorganic particles are preferably used in terms of more excellent matting effect, silica is more preferably used, and surface-treated silica is more preferably used.
　上記艶消剤の平均粒子径は１～１０μｍが好ましい。艶消剤の平均粒子径が上記範囲であることにより、本発明の化粧シートの凸部が低艶性を示し、優れた意匠性を示すことができる。 The average particle size of the matting agent is preferably 1 to 10 μm. When the average particle diameter of the matting agent is within the above range, the convex portion of the decorative sheet of the present invention exhibits low gloss and can exhibit excellent design.
　凸部は、上記艶消剤を、上記樹脂１００質量部に対して１～３０質量部含有することが好ましく、５～２０質量部含有することがより好ましい。艶消剤の含有量を上記範囲とすることで、本発明の化粧シートの凸部が低艶性を示し、優れた意匠性を示すことができる。但し、上記平均粒子径が１１μｍ未満の微粒子の含有量と、上記平均粒子径が１１～３０μｍの無機粒子の含有量との合計が、上記樹脂１００質量部に対して４０質量部以下、好ましくは１５～４０質量部となるよう適宜設定することが、凸部を形成する樹脂組成物の塗工適性を良好とする観点から好ましい。 The convex portion preferably contains 1 to 30 parts by mass, more preferably 5 to 20 parts by mass of the matting agent with respect to 100 parts by mass of the resin. By making content of a matting agent into the said range, the convex part of the decorative sheet of this invention can show low glossiness, and can show the outstanding designability. However, the sum of the content of fine particles having an average particle diameter of less than 11 μm and the content of inorganic particles having an average particle diameter of 11 to 30 μm is 40 parts by mass or less, preferably 100 parts by mass or less, preferably Setting from 15 to 40 parts by mass is preferable from the viewpoint of improving the coating suitability of the resin composition forming the convex part.
　上記顔料としては、後述の絵柄模様層と同様のものが使用できる。 As the pigment, the same pigments as those described later can be used.
　凸部を形成する樹脂組成物には、発泡剤を添加してもよい。発泡剤としては、アゾジカーボンアミド、アゾビスイソブチロニトリル、Ｎ，Ｎ′－ジニトロソペンタメチレンテトラミン、オキシビスベンゼンスルホニルヒドラジド、炭酸水素ナトリウム、炭酸水素カリウム等の熱分解型、又は塩化ビニリデン、アクリルニトリルまたはこれらの共重合体でできている樹脂球殻中にヘキサン、イソブタン等の熱膨張性気体を封入したカプセル発泡剤（マイクロカプセル型）を用いることができる。その添加量は通常樹脂１００質量部に対し、１～２０質量部である。発泡温度は１００～１８０℃の範囲で発泡するものを選択する。その他、特開昭５７－１９３３２５号公報第２頁右欄に記載されている発泡剤を添加してもよい。 You may add a foaming agent to the resin composition which forms a convex part. Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N'-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium hydrogen carbonate, potassium hydrogen carbonate and the like, or vinylidene chloride. Further, a capsule foaming agent (microcapsule type) in which a thermally expandable gas such as hexane or isobutane is enclosed in a resin spherical shell made of acrylonitrile or a copolymer thereof can be used. The added amount is usually 1 to 20 parts by mass with respect to 100 parts by mass of the resin. The foaming temperature is selected in the range of 100 to 180 ° C. In addition, a foaming agent described in JP-A-57-193325, page 2, right column may be added.
　凸部を形成する樹脂組成物には、必要に応じて、溶剤、染料、顔料等の着色剤、増量剤等の充填剤、消泡剤、レベリング剤、チクソトロピー性付与剤等の各種添加剤を加えることができる。 If necessary, the resin composition for forming the convex portion includes various additives such as solvents, dyes, pigments and other colorants, fillers such as extenders, antifoaming agents, leveling agents, and thixotropic agents. Can be added.
　（化粧シートの層構成）
　本発明の化粧シートは、基材シート上に、樹脂を含む凸部が少なくとも形成されていれば、その具体的構成（層構成）については限定されない。例えば、基材シート上に、少なくとも絵柄模様層及び透明性樹脂層が積層されており、透明性樹脂層上に、樹脂を含む凸部が形成されている化粧シートが挙げられる。図１に本発明の化粧シートの層構成の上記一例を示す。図１において、本発明の化粧シート１は、基材シート２上に、絵柄模様層３、透明性樹脂層４がこの順に積層されており透明性樹脂層４上に樹脂を含む凸部５が形成されている。また、本発明の化粧シートは、図２のように、基材シート２と絵柄模様層３との間に、更に着色隠蔽層６が形成されていてもよい。 (Layer structure of decorative sheet)
As long as the convex part containing resin is formed at least on the base material sheet, the specific structure (layer structure) of the decorative sheet of the present invention is not limited. For example, a decorative sheet in which at least a pattern layer and a transparent resin layer are laminated on a base sheet, and a convex portion containing a resin is formed on the transparent resin layer can be mentioned. FIG. 1 shows the above example of the layer structure of the decorative sheet of the present invention. In FIG. 1, the decorative sheet 1 of the present invention has a pattern layer 3 and a transparent resin layer 4 laminated in this order on a base sheet 2, and a convex portion 5 containing a resin on the transparent resin layer 4. Is formed. In the decorative sheet of the present invention, a colored concealing layer 6 may be further formed between the base sheet 2 and the pattern layer 3 as shown in FIG.
　以下、かかる層構成のシートを代表例として、各層について具体的に説明する。 Hereinafter, each layer will be described in detail by using a sheet having such a layer configuration as a representative example.
　絵柄模様層
　本発明の化粧シートは、基材シート又は後述する着色隠蔽層の上には、必要に応じて絵柄模様層を形成してもよい。なお、本発明の化粧シートにおいては、絵柄模様層と、上記凸部とが同調している構成とすることにより、より意匠性に優れた化粧シートとなる。具体的には、図１及び図２に示されるように、絵柄模様層の絵柄が形成された部分に凸部が同調した構成であってもよいし、逆に絵柄模様層の絵柄が形成されていない部分に凸部が同調した構成であってもよい。 Pattern Pattern Layer In the decorative sheet of the present invention, a pattern pattern layer may be formed on the base sheet or the colored concealment layer described later, if necessary. In addition, in the decorative sheet of this invention, it becomes a decorative sheet excellent in the designability by setting it as the structure which the pattern pattern layer and the said convex part synchronize. Specifically, as shown in FIG. 1 and FIG. 2, a configuration in which convex portions are synchronized with a portion where the pattern of the pattern layer is formed, or conversely, a pattern of the pattern layer is formed. The convex part may synchronize with the part which is not.
　絵柄模様層は、化粧シートに意匠性を付与する。絵柄模様としては、例えば木目模様、石目模様、砂目模様、タイル貼模様、煉瓦積模様、布目模様、皮絞模様、幾何学図形、文字、記号、抽象模様、草花模様等が挙げられ、目的に応じて選択できる。 The pattern layer gives design to the decorative sheet. Examples of the design pattern include a grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, an abstract pattern, a flower pattern, etc. You can choose according to your purpose.
　絵柄模様層は、例えば、絵柄模様を印刷することで形成できる。印刷手法としては、グラビア印刷、フレキソ印刷、シルクスクリーン印刷、オフセット印刷等が挙げられる。印刷インキとしては、着色剤、結着材樹脂、溶剤を含む印刷インキが使用できる。これらのインキは公知又は市販のものを使用してもよい。 The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent can be used. These inks may be known or commercially available.
　着色剤としては特に限定されず、公知の無機顔料又は有機顔料を用いることができる。無機顔料としては、例えば、酸化チタン、亜鉛華、カーボンブラック、黒色酸化鉄、黄色酸化鉄、黄鉛、モリブデートオレンジ、カドミウムイエロー、ニッケルチタンイエロー、クロムチタンイエロー、酸化鉄（弁柄）、カドミウムレッド、群青、紺青、コバルトブルー、酸化クロム、コバルトグリーン、アルミニウム粉、ブロンズ粉、雲母チタン、硫化亜鉛等が挙げられる。また、有機顔料としては、例えば、アニリンブラック、ペリレンブラック、アゾ系（アゾレーキ、不溶性アゾ、縮合アゾ）、多環式（イソインドリノン、イソインドリン、キノフタロン、ペリノン、フラバントロン、アントラピリミジン、アントラキノン、キナクリドン、ペリレン、ジケトピロロピロール、ジブロムアンザントロン、ジオキサジン、チオインジゴ、フタロシアニン、インダントロン、ハロゲン化フタロシアニン）等が挙げられる。顔料の含有量は、樹脂成分１００質量部に対して１０～１００質量部程度が好ましく、１５～５０質量部程度がより好ましい。 The colorant is not particularly limited, and a known inorganic pigment or organic pigment can be used. Inorganic pigments include, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), and cadmium. Examples thereof include red, ultramarine blue, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of the organic pigment include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, Quinacridone, perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine). The content of the pigment is preferably about 10 to 100 parts by mass, more preferably about 15 to 50 parts by mass with respect to 100 parts by mass of the resin component.
　結着材樹脂は、基材シートの種類に応じて設定できる。例えば、アクリル系樹脂、スチレン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、塩素化ポリオレフィン系樹脂、塩化ビニル－酢酸ビニル共重合体系樹脂、ポリビニルブチラール樹脂、アルキド系樹脂、石油系樹脂、ケトン樹脂、エポキシ系樹脂、メラミン系樹脂、フッ素系樹脂、シリコーン系樹脂、繊維素誘導体、ゴム系樹脂等が挙げられる。 The binder resin can be set according to the type of the base sheet. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like.
　溶剤（又は分散媒）としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の石油系有機溶剤；酢酸エチル、酢酸ブチル、酢酸－２－メトキシエチル、酢酸－２－エトキシエチル等のエステル系有機溶剤；メチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、イソブチルアルコール、エチレングリコール、プロピレングリコール等のアルコール系有機溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤；ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル系有機溶剤、；ジクロロメタン、四塩化炭素、トリクロロエチレン、テトラクロロエチレン等の塩素系有機溶剤；水などが挙げられる。これらの溶剤（又は分散媒）は、単独又は混合物の状態で使用できる。 Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents and the like; and water. These solvents (or dispersion media) can be used alone or in the form of a mixture.
　絵柄模様層の厚みは、絵柄模様の種類より異なるが、一般には０．１～２０μｍ程度とすることが好ましい。 The thickness of the pattern layer varies depending on the type of pattern, but is generally preferably about 0.1 to 20 μm.
　透明性樹脂層
　本発明の化粧シートは、絵柄模様層上に艶調整等を目的として、透明性樹脂層を形成してもよい。透明性樹脂層は、透明性のものであれば特に限定されず、無色透明、着色透明、半透明等のいずれも含む。前記透明性樹脂層を構成する樹脂としては、例えば、フェノール樹脂、尿素樹脂、ジアリルフタレート、メラミン樹脂、グアナミン樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、アミノアルキッド樹脂、メラミン－尿素共縮合体、珪素樹脂、ポリシロキサン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリアミド、ポリエチレン、ポリプロピレン、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸共重合体、エチレン・アクリル酸エステル共重合体、アイオノマー、ポリメチルペンテン、アクリル酸エステル、メタアクリル酸エステル、ポリカーボネート、セルローストリアセテート等を挙げることができる。また、上述の電離放射線硬化型樹脂を用いてもよい。これら樹脂は単独で又は２種以上を組み合わせて用いることができる。 Transparent resin layer In the decorative sheet of the present invention, a transparent resin layer may be formed on the pattern layer for the purpose of adjusting gloss. The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. Examples of the resin constituting the transparent resin layer include phenol resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensate. , Silicon resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polymethylpentene , Acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate and the like. Moreover, you may use the above-mentioned ionizing radiation curable resin. These resins can be used alone or in combination of two or more.
　透明性樹脂層には、艶調整の為に、シリカ、アルミナ、カオリン等の微粒子、ウレタンビーズ、アクリルビーズ等のビーズを添加してもよい。 In the transparent resin layer, fine particles such as silica, alumina and kaolin, beads such as urethane beads and acrylic beads may be added for gloss adjustment.
　なお、透明性樹脂層は、透明性を有する限り着色されていても良いが、特に着色剤を配合しない方が望ましい。 The transparent resin layer may be colored as long as it has transparency, but it is particularly desirable not to add a colorant.
　透明性樹脂層の厚みは、通常は５～５０μｍ程度であるが、化粧シートの用途等に応じて上記範囲を超えてもよい。 The thickness of the transparent resin layer is usually about 5 to 50 μm, but may exceed the above range depending on the use of the decorative sheet.
　着色隠蔽層
　基材シート上には、必要に応じて着色隠蔽層を形成してもよい。着色隠蔽層は、基材シート上に全面ベタ印刷層として形成される。着色隠蔽層は、例えば、顔料及び結着材樹脂を含む層とすることができる。この着色隠蔽層は、例えば、着色材、結着材樹脂、溶剤を含む印刷インキを使用し、グラビア印刷、フレキソ印刷、シルクスクリーン印刷、オフセット印刷等の既知の印刷法により形成できる。これらのインキは公知又は市販のものを使用してもよい。 A colored concealment layer may be formed on the colored concealment layer base sheet as necessary. The colored concealing layer is formed as a whole surface solid printing layer on the base material sheet. The colored hiding layer can be, for example, a layer containing a pigment and a binder resin. This colored hiding layer can be formed by a known printing method such as gravure printing, flexographic printing, silk screen printing, or offset printing using, for example, a printing ink containing a coloring material, a binder resin, and a solvent. These inks may be known or commercially available.
　着色材、結着剤樹脂及び溶剤は、上述の絵柄模様層に用いられるものを用いることができる。 As the coloring material, binder resin, and solvent, those used in the above-described pattern layer can be used.
　着色隠蔽層の厚みは、１～４μｍ程度が好ましい。 The thickness of the colored hiding layer is preferably about 1 to 4 μm.
　プライマー層
　基材シート、着色隠蔽性、絵柄模様層又は透明性樹脂層の上には、凸部との密着性を向上させること等を目的として、必要に応じてプライマー層を形成してもよい。 A primer layer may be formed as necessary on the primer layer substrate sheet, the color concealing property, the pattern layer or the transparent resin layer for the purpose of improving the adhesion to the convex portion, etc. .
　プライマー層に含有される樹脂としては、例えば、アクリル、塩化ビニル－酢酸ビニル共重合体、ポリエステル、ポリウレタン、塩素化ポリプロピレン、塩素化ポリエチレン等を使用することができるが、特にアクリル、塩素化ポリプロピレン等が望ましい。 As the resin contained in the primer layer, for example, acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like can be used. Particularly, acrylic, chlorinated polypropylene, etc. Is desirable.
　アクリルとしては、例えば、ポリ（メタ）アクリル酸メチル、ポリ（メタ）アクリル酸エチル、ポリ（メタ）アクリル酸プロピル、ポリ（メタ）アクリル酸ブチル、（メタ）アクリル酸メチル－（メタ）アクリル酸ブチル共重合体、（メタ）アクリル酸エチル－（メタ）アクリル酸ブチル共重合体、エチレン－（メタ）アクリル酸メチル共重合体、スチレン－（メタ）アクリル酸メチル共重合体等の（メタ）アクリル酸エステルを含む単独又は共重合体からなるアクリル樹脂が挙げられる。 Examples of the acryl include, for example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylate methyl- (meth) acrylic acid (Meth) such as butyl copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer An acrylic resin made of a homopolymer or a copolymer containing an acrylate ester may be mentioned.
　ポリウレタンとはポリオール（多価アルコール）を主剤とし、イソシアネートを架橋剤（硬化剤）とする組成物である。 Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).
　ポリオールとしては、分子中に２個以上の水酸基を有するもので、例えば、ポリエチレングリコール、ポリプロピレングリコール、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール等が用いられる。 As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.
　また、イソシアネートとしては、分子中に２個以上のイソシアネート基を有する多価イソシアネートが用いられる。例えば、２－４トリレンジイソシアネート、キシレンジイソシアネート、４－４ジフェニルメタンジイソシアネート等の芳香族イソシアネート、或いはヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等の脂肪族（又は脂環族）イソシアネートが用いられる。 As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate ) Isocyanates are used.
　プライマー層の厚さは限定的ではないが、０．１～１０μｍ程度が好ましく、０．１～５μｍ程度がより好ましい。 The thickness of the primer layer is not limited, but is preferably about 0.1 to 10 μm, more preferably about 0.1 to 5 μm.
　裏面プライマー層
　基材シートの裏面（凸部が形成される面とは反対側の面）には、必要に応じて、裏面プライマー層を設けてもよい。裏面プライマー層は、本発明の化粧シートと被着材とを積層して化粧板を作製する際に効果的である。 You may provide a back surface primer layer in the back surface (surface on the opposite side to the surface in which a convex part is formed) of a back surface primer layer base material sheet as needed. The back primer layer is effective when a decorative sheet is produced by laminating the decorative sheet of the present invention and the adherend.
　裏面プライマー層は、公知のプライマー剤を基材シートに塗布することにより形成できる。プライマー剤としては、例えば、アクリル変性ウレタン樹脂（アクリルウレタン系樹脂）等からなるウレタン樹脂系プライマー剤、ウレタン－セルロース系樹脂（例えば、ウレタンと硝化綿の混合物にヘキサメチレンジイソシアネートを添加してなる樹脂）からなるプライマー剤、アクリルとウレタンのブロック共重合体からなる樹脂系プライマー剤等が挙げられる。プライマー剤には、必要に応じて、添加剤を配合してもよい。添加剤としては、例えば、炭酸カルシウム、クレー等の充填剤、水酸化マグネシウム等の難燃剤、酸化防止剤、滑剤、発泡剤、紫外線吸収剤、光安定剤などが挙げられる。添加剤の配合量は、製品特性に応じて適宜設定できる。 The back primer layer can be formed by applying a known primer to the base material sheet. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set according to the product characteristics.
　プライマー剤の塗布量は特に限定されないが、通常０．１～１００ｇ／ｍ２程度、好ましくは０．１～５０ｇ／ｍ２程度である。また、裏面プライマー層の厚みは特に限定されないが、通常０．０１～１０μｍ程度、好ましくは０．１～１μｍ程度である。 The application amount of the primer agent is not particularly limited, but is usually about 0.1 to 100 g / m 2 , preferably about 0.1 to 50 g / m 2 . The thickness of the back primer layer is not particularly limited, but is usually about 0.01 to 10 μm, preferably about 0.1 to 1 μm.
　２．化粧板
　上記化粧シートを被着材上に貼着することにより、化粧板とすることができる。被着材は、限定的でなく、公知の化粧板に用いられるものと同様のものを用いることができる。上記被着材としては、例えば、木質材、金属、セラミックス、プラスチックス、ガラス等が挙げられる。特に、上記化粧シートは、木質材に好適に使用することができる。木質材としては、具体的には、杉、檜、欅、松、ラワン、チーク、メラピー等の各種素材から作られた突板、木材単板、木材合板、パーティクルボード、中密度繊維板（ＭＤＦ）、チップボード、又はチップボードが積層された複合基材等が挙げられる。上記木質材としては、木材合板、パーティクルボード、中密度繊維板（ＭＤＦ）を用いることが好ましい。 2. Decorative plate By adhering the decorative sheet to an adherend, a decorative plate can be obtained. The adherend is not limited, and the same materials as those used for known decorative panels can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet can be suitably used for a wood material. Specific examples of wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. , Chip boards, or composite substrates on which chip boards are laminated. As the wood material, wood plywood, particle board, medium density fiber board (MDF) is preferably used.
　化粧シートを被着材上に貼着する方法は限定的でなく、例えば接着剤により化粧シートを被着材に貼着する方法等を採用することができる。接着剤は、被着材の種類等に応じて公知の接着剤から適宜選択すればよい。例えば、ポリ酢酸ビニル、ポリ塩化ビニル、塩化ビニル・酢酸ビニル共重合体、エチレン・アクリル酸共重合体、アイオノマー等のほか、ブタジエン・アクリルニトリルゴム、ネオプレンゴム、天然ゴム等が挙げられる。これら接着剤は、単独で又は２種以上を組み合わせて用いる。 The method of sticking the decorative sheet on the adherend is not limited, and for example, a method of attaching the decorative sheet to the adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like. These adhesives are used alone or in combination of two or more.
　このようにして製造された化粧板は、例えば、壁、天井、床等の建築物の内装材；バルコニー、ベランダ等の外装材；窓枠、扉、手すり等の建具の表面化粧板や家具；又は弱電、ＯＡ機器等のキャビネットの表面化粧板等に用いることができる。 The decorative board manufactured in this way includes, for example, interior materials for buildings such as walls, ceilings, and floors; exterior materials such as balconies and verandas; surface decorative boards and furniture for furniture such as window frames, doors, and handrails; Alternatively, it can be used for a surface decorative plate of a cabinet such as a light electric or OA device.
　３．化粧シートの製造方法
　化粧シートの製造方法としては、例えば、基材シートの上に少なくとも樹脂を含む凸部を形成する製造方法が挙げられる。 3. Manufacturing method of decorative sheet As a manufacturing method of a decorative sheet, for example, a manufacturing method of forming a convex part including at least a resin on a base sheet can be mentioned.
　熱硬化型樹脂で凸部を形成する方法は、例えば、熱硬化型樹脂の溶液をロールコート法、グラビアコート法等の塗布法で塗布し、乾燥・硬化させる方法が挙げられる。また、電離放射線硬化型樹脂で凸部を形成する方法としては、例えば、電離放射線硬化型樹脂の溶液をグラビアコート法、ロールコート法等の塗布法で塗布し、電離放射線を照射する方法が挙げられる。 Examples of the method for forming the convex portion with the thermosetting resin include a method in which a solution of the thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method and then dried and cured. Moreover, as a method of forming a convex part with ionizing radiation curable resin, the method of apply | coating the solution of ionizing radiation curable resin by application methods, such as a gravure coat method and a roll coat method, and irradiating ionizing radiation is mentioned, for example. It is done.
　本発明の化粧シートが着色隠蔽層、絵柄模様層、プライマー層及び透明性樹脂層を有する場合には、これらの層を形成するための樹脂組成物を、グラビア印刷、フレキソ印刷、シルクスクリーン印刷、オフセット印刷等の既知の印刷法により塗布して形成した後、最表面層上に凸部を形成すればよい。 When the decorative sheet of the present invention has a colored concealing layer, a pattern layer, a primer layer, and a transparent resin layer, the resin composition for forming these layers is gravure printing, flexographic printing, silk screen printing, What is necessary is just to form a convex part on an outermost surface layer, after apply | coating and forming by known printing methods, such as offset printing.
　以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
　実施例１
　基材シートとして、米秤量３０ｇ／ｍ２の建材用一般紙を用意し、その片面にアクリル樹脂と硝化綿をバインダーとし、チタン白、弁柄、黄鉛を着色剤とするインキを用いて、塗工量５ｇ／ｍ２の（全面ベタ）層をグラビア印刷にて施して着色隠蔽層とした。その上に硝化綿をバインダーとし、弁柄を主成分とする着色剤を含有するインキを用いて、木目模様の絵柄模様層をグラビア印刷にて形成した。 Example 1
As a base material sheet, a general paper for building materials with a weight of 30 g / m 2 is prepared, and an acrylic resin and nitrified cotton are used as a binder on one side of the paper, and ink containing titanium white, petal, and chrome is used as a colorant. A (full-surface solid) layer having a coating amount of 5 g / m 2 was applied by gravure printing to form a colored concealment layer. A woodgrain pattern layer was formed by gravure printing using an ink containing nitrified cotton as a binder and a colorant mainly composed of a petiole.
　次いで、アクリルポリオール樹脂をバインダーとし、シリカ粒子をバインダー１００質量部に対して１０質量部、ウレタンビーズをバインダー１００質量部に対して５質量部配合した塗料組成物を調製し、塗工量５ｇ／ｍ２で全面にグラビア印刷して透明性樹脂層をを形成した。  Next, a coating composition containing acrylic polyol resin as a binder, 10 parts by mass of silica particles with respect to 100 parts by mass of binder, and 5 parts by mass of urethane beads with respect to 100 parts by mass of binder is prepared. A transparent resin layer was formed by gravure printing on the entire surface at m 2 .
　次いで、樹脂成分として、６官能ウレタンアクリレートからなる電離放射線硬化型樹脂１００質量部に対して、アクリルポリマーを５質量部、無機粒子としてシリカ（平均粒子径１２μｍ、最大粒子径４０μｍ）を１０質量部、艶消剤（表面処理シリカ、平均粒子径７μｍ）を７質量部含む凸部形成用組成物をグラビアダイレクトコータ法により塗工した。 この際用いた版は、幅１ｍｍ、版深が６０μｍであった。 Next, 5 parts by mass of an acrylic polymer and 10 parts by mass of silica (average particle diameter: 12 μm, maximum particle diameter: 40 μm) as inorganic particles are used as resin components with respect to 100 parts by mass of ionizing radiation curable resin composed of hexafunctional urethane acrylate. A convex forming composition containing 7 parts by mass of a matting agent (surface-treated silica, average particle diameter 7 μm) was applied by a gravure direct coater method.版 The plate used at this time had a width of 1 mm and a plate depth of 60 μm.
　塗工後、加速電圧１２５ｋＶ、照射線量３０ｋＧｙの電子線を照射して、凸部形成用組成物を硬化させて、高さが１３．５μｍの凸部を形成した。  After coating, an electron beam with an acceleration voltage of 125 kV and an irradiation dose of 30 kGy was irradiated to cure the convex portion forming composition to form a convex portion having a height of 13.5 μm.
　最後に、７０℃で２４時間の養生を行い、化粧シートを得た。 Finally, curing was performed at 70 ° C. for 24 hours to obtain a decorative sheet.
　実施例２～４、比較例１～６
　凸部に含まれる無機粒子の種類及び配合量を表１のように変更した以外は実施例１と同様にして、化粧シートを調製した。 Examples 2 to 4 and Comparative Examples 1 to 6
A decorative sheet was prepared in the same manner as in Example 1 except that the types and blending amounts of the inorganic particles contained in the convex portions were changed as shown in Table 1.
　上記実施例及び比較例で調製された化粧シートの表面に形成された凸部の高さを、以下の方法により測定した。具体的には、小坂研究所株式会社製触針式形状粗さ測定器「ＳＥ－３０Ｋ」（型番）を用いて、測定長さ５ｍｍ、カットオフ値０．８の条件で化粧シートの表面形状を測定した。無機粒子が著しく飛び出た部分を除いて、測定部分のチャートから高さを読み取り、平均値を算出することによって凸部の高さを測定した。 The height of the convex portion formed on the surface of the decorative sheet prepared in the above examples and comparative examples was measured by the following method. Specifically, the surface shape of a decorative sheet was measured using a stylus type roughness measuring instrument “SE-30K” (model number) manufactured by Kosaka Laboratory Ltd. under the conditions of a measurement length of 5 mm and a cutoff value of 0.8. Was measured. The height of the convex portion was measured by reading the height from the chart of the measurement portion and calculating the average value, except for the portion where the inorganic particles jumped out significantly.
　上記実施例及び比較例について、下記評価を行った。 The following evaluations were performed on the above examples and comparative examples.
　触感
　化粧シートの表面を、２０代～４０代の成人男女１５人が手で触って触感を判定し、下記評価基準に従って評価した。なお、下記評価基準において、４以上であれば優れた触感を示すと判断できる。
５：成人男女１０人以上が、触感が良好と感じた
４：成人男女８～９人が、触感が良好と感じた
３：成人男女６～７人が、触感が良好と感じた
２：成人男女４～５人が、触感が良好と感じた
１：成人男女のうち触感が良好と感じたのが３人以下であった The surface of the tactile sensation sheet was touched by 15 adult men and women in their 20s to 40s with their hands to determine the tactile sensation, and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is 4 or more, it can be judged that the outstanding tactile sense is shown.
5: More than 10 adult men and women felt tactile sensation 4: 8-9 adult men and women felt tactile sensation 3: 6-7 adult men and women felt tactile sensation 2: Adult 4-5 men and women felt that tactile sensation was good 1: Less than 3 adult men and women felt tactile sensation
　耐擦傷性
　実施例及び比較例で調製した化粧シートをＭＤＦに貼付して化粧板を調製した。当該化粧板を、マーチンデール摩耗試験機（「Ｍａｒｔｉｎｄａｌｅ　１３００シリーズ　モデル１３０２（型番）」　Ｊａｍｅｓ　Ｈｅａｌ社製）の摩擦テーブル部に取り付け、化粧板の上にスコッチ・ブライト工業用パッド７４４６（スリーエムジャパン（株）製）を重ねて荷重６Ｎを掛けて、摩擦回数１００回の条件でリサージュ図形運動による摩擦試験を行った。試験後の外観を目視により観察し、下記評価基準に従って評価した。なお、下記評価基準において、３以上であれば耐擦傷性に優れると判断される。
５：傷付きなし
４：軽微な艶変化あり
３：軽微な傷付きはあるが、実使用上問題なし
２：傷付きあり
１：著しい傷付きあり A decorative sheet was prepared by sticking the decorative sheets prepared in the scratch-resistant Examples and Comparative Examples to the MDF. The decorative plate is attached to a friction table of a Martindale abrasion tester (“Martindale 1300 series model 1302 (model number)” manufactured by James Heal), and a Scotch Bright industrial pad 7446 (Three M Japan Co., Ltd.) is mounted on the decorative plate. )) And a load of 6 N, and a friction test by Lissajous figure motion was performed under the condition of 100 times of friction. The appearance after the test was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is 3 or more, it is judged that it is excellent in abrasion resistance.
5: No scratch 4: Minor gloss change 3: Slight scratch, but no problem in actual use 2: Scratch 1: Scratch
　塗工適性（転移安定性）
　凸部形成用樹脂組成物を塗工した際の、表面の転移の状態を目視にて観察し、下記評価基準に従って塗工適性を評価した。 
Ａ：塗工面に凸部が安定して転移されている 
Ｂ：塗工面の凸部の抜けが有るか、又は凸部の形状が不安定である
　結果を表１に示す。 Coating suitability (transition stability)
When the convex portion-forming resin composition was applied, the surface transition state was visually observed, and the coating suitability was evaluated according to the following evaluation criteria.
A: The convex portion is stably transferred to the coated surface.
B: The convex part of the coated surface is missing or the shape of the convex part is unstable.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
１．化粧シート
２．基材シート
３．絵柄模様層
４．透明性樹脂層
５．樹脂を含む凸部　
６．着色隠蔽層  1. Cosmetic sheet 2. 2. base material sheet Pattern layer 4. 4. Transparent resin layer Convex part containing resin
6). Colored concealment layer

Claims (5)

  1. 　基材シート上に、樹脂を含む凸部が少なくとも形成されている化粧シートであって、
    （１）前記凸部の高さが１０μｍ以上であり、
    （２）前記凸部は、平均粒子径が１１～３０μｍの無機粒子を、樹脂１００質量部に対して１０～３０質量部含有する、
    ことを特徴とする化粧シート。     On the base sheet is a decorative sheet in which at least convex portions containing resin are formed,
    (1) The height of the convex portion is 10 μm or more,
    (2) The convex portion contains 10 to 30 parts by mass of inorganic particles having an average particle diameter of 11 to 30 μm with respect to 100 parts by mass of the resin.
    A decorative sheet characterized by that.
  2. 　前記樹脂は、電離放射線硬化型樹脂である、請求項１に記載の化粧シート。 The decorative sheet according to claim 1, wherein the resin is an ionizing radiation curable resin.
  3. 　基材シート上に、少なくとも絵柄模様層及び透明性樹脂層がこの順に積層されており、前記透明性樹脂層上に、前記樹脂を含む凸部が形成されている、請求項１又は２に記載の化粧シート。 The pattern pattern layer and the transparent resin layer are laminated in this order on the base sheet, and the convex portion containing the resin is formed on the transparent resin layer. Makeup sheet.
  4. 　前記絵柄模様層と、前記樹脂を含む凸部とが同調している、請求項３に記載の化粧シート。 The decorative sheet according to claim 3, wherein the pattern layer and the convex portion including the resin are synchronized.
  5. 　請求項１～４のいずれかに記載の化粧シートを被着材に貼着してなる化粧板。  A decorative board obtained by attaching the decorative sheet according to any one of claims 1 to 4 to an adherend.
PCT/JP2016/060021 2015-03-30 2016-03-29 Decorative sheet and decorative board WO2016158903A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015067909A JP6617424B2 (en) 2015-03-30 2015-03-30 Decorative sheet and decorative board
JP2015-067909 2015-03-30

Publications (1)

Publication Number Publication Date
WO2016158903A1 true WO2016158903A1 (en) 2016-10-06

Family

ID=57005135

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/060021 WO2016158903A1 (en) 2015-03-30 2016-03-29 Decorative sheet and decorative board

Country Status (2)

Country Link
JP (1) JP6617424B2 (en)
WO (1) WO2016158903A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019069582A (en) * 2017-10-11 2019-05-09 Dic株式会社 Laminate and production method of laminate
JP7003667B2 (en) * 2018-01-05 2022-02-10 凸版印刷株式会社 Cosmetic material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01174574A (en) * 1987-12-29 1989-07-11 Pentel Kk Ink composition for screen printing
JPH1086313A (en) * 1996-09-18 1998-04-07 Dainippon Printing Co Ltd Decorative material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2740943B2 (en) * 1994-10-31 1998-04-15 大日本印刷株式会社 Cosmetic material with wear resistance
JPH10286932A (en) * 1997-04-14 1998-10-27 Dainippon Printing Co Ltd Wear-resistant decorative material
JPH1148415A (en) * 1997-07-31 1999-02-23 Dainippon Printing Co Ltd Decorative material with abrasion resistivity
JP2004050827A (en) * 2002-05-30 2004-02-19 Dainippon Printing Co Ltd Decorative sheet, production method thereof, and decorative member
JP4694944B2 (en) * 2005-10-19 2011-06-08 サカエグラビヤ印刷株式会社 Decorative sheet

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01174574A (en) * 1987-12-29 1989-07-11 Pentel Kk Ink composition for screen printing
JPH1086313A (en) * 1996-09-18 1998-04-07 Dainippon Printing Co Ltd Decorative material

Also Published As

Publication number Publication date
JP6617424B2 (en) 2019-12-11
JP2016187879A (en) 2016-11-04

Similar Documents

Publication Publication Date Title
JP5003086B2 (en) Decorative sheet
US6790525B2 (en) Decorative material
JP7180743B2 (en) Decorative sheets, decorative boards and decorative resin moldings
JP6728568B2 (en) Sheet
JP5145645B2 (en) Decorative sheet and decorative board using the same
WO2017057673A1 (en) Cosmetic sheet and cosmetic plate
WO2016148091A1 (en) Decorative panel and manufacturing method for same
JP2015171810A (en) decorative sheet
JP6627249B2 (en) Decorative sheet and veneer
JP6679834B2 (en) Decorative sheet and veneer
WO2016158903A1 (en) Decorative sheet and decorative board
JP6935163B2 (en) Sheet and veneer
WO2018117260A1 (en) Decorative material
JP6221288B2 (en) Decorative sheet and decorative board using the same
JP6582497B2 (en) Decorative sheet
EP4316812A1 (en) Decorative sheet and decorative material
JP6171459B2 (en) Decorative sheet
WO2020158921A1 (en) Decorative material
JP6278175B2 (en) Decorative sheet
JP5344077B2 (en) Decorative sheet and decorative board using the same
JP6641714B2 (en) Laminate and decorative board
JP2020044817A (en) Decorative material
EP3741557B1 (en) Cosmetic sheet, cosmetic material, and method for producing cosmetic sheet
JP5120308B2 (en) Decorative sheet and decorative board using the same
JP2010229781A (en) Decorative material for insulating floor

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: 16772784

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: 16772784

Country of ref document: EP

Kind code of ref document: A1