WO2020158921A1 - 化粧材 - Google Patents

化粧材 Download PDF

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Publication number
WO2020158921A1
WO2020158921A1 PCT/JP2020/003654 JP2020003654W WO2020158921A1 WO 2020158921 A1 WO2020158921 A1 WO 2020158921A1 JP 2020003654 W JP2020003654 W JP 2020003654W WO 2020158921 A1 WO2020158921 A1 WO 2020158921A1
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WO
WIPO (PCT)
Prior art keywords
resin
decorative material
layer
examples
shape
Prior art date
Application number
PCT/JP2020/003654
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English (en)
French (fr)
Japanese (ja)
Inventor
小川　哲
孝志 土井
宏樹 河西
啓介 鶴田
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
Priority to JP2020568627A priority Critical patent/JP7512899B2/ja
Priority to CN202080011230.1A priority patent/CN113382854A/zh
Priority to KR1020217025688A priority patent/KR20210124264A/ko
Publication of WO2020158921A1 publication Critical patent/WO2020158921A1/ja

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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/02161—Floor elements with grooved main surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements

Definitions

  • the present invention relates to a decorative material.
  • decorative materials are generally used.
  • slip resistance is required from the viewpoint of safety.
  • the surface protective layer has a laminated structure of two or more layers, and by adding resin beads only to the outermost layer, friction is reduced and slip resistance is imparted.
  • a laminate for a flooring surface is disclosed.
  • the present invention solves the above-described problems, and an object of the present invention is to provide a decorative material that is excellent in anti-slip properties not only when it is dried but also when it is wet with water, and is also excellent in design.
  • the present inventors diligently studied to solve the above-mentioned problems, and paid attention to the surface shape of the decorative material.
  • the decorative material has excellent anti-slip properties not only when it is dried but also when it is wet with water, and is also excellent in design.
  • the present invention has been completed and the present invention has been completed.
  • the present invention is a decorative material having a pattern layer, wherein one surface of the decorative material has an irregular asperity shape, and the asperity shape is a void volume of a valley portion measured by a 3D shape measuring instrument.
  • the volume (Vvv+Vvc) represented by the total value of (Vvv) and the void volume (Vvc) of the core portion is 15 mL/m 2 or more.
  • the uneven shape is preferably a continuous shape.
  • the volume (Vvv+Vvc) is preferably 55 mL/m 2 or less.
  • the uneven shape preferably has a ten-point average roughness (RzJ) defined by JIS B 0601 (2001) of 70 ⁇ m or more and 200 ⁇ m or less.
  • the uneven shape preferably has an arithmetic mean roughness (Ra) defined by JIS B 0601 (2001) of 13 ⁇ m or more and 30 ⁇ m or less.
  • Ra arithmetic mean roughness
  • the uneven shape has an average length (AR) of a roughness motif defined by CNOMO of 1.00 mm or more.
  • the present invention can provide a cosmetic material which has excellent anti-slip properties not only when it is dried but also when it is wet with water, and which is also excellent in design.
  • (A) And (b) is a schematic diagram which shows an example of the load curve obtained by measuring a decorative material with a 3D shape measuring machine.
  • (A) And (b) is a schematic diagram which shows the surface shape (irregular shape) of a preferable example of the decorative material of this invention.
  • (A) It is sectional drawing which shows 1 aspect of the cosmetic material of this invention,
  • (b) is sectional drawing which shows another aspect of the cosmetic material of this invention,
  • (c) is the cosmetic material of this invention.
  • the present invention is a decorative material having a pattern layer, wherein one surface of the decorative material has an irregular uneven shape, and the uneven shape has a void volume (Vvvv of a valley portion measured by a 3D shape measuring machine. ) And the void volume (Vvc) of the core portion, the volume (Vvv+Vvc) represented by the total value is 15 mL/m 2 (milliliter/square meter) or more.
  • the uneven shape has a volume (Vvv+Vvc) represented by a total value of a void volume (Vvv) of a valley portion and a void volume (Vvc) of a core portion measured by a 3D shape measuring instrument, It is 15 mL/m 2 or more. Since the decorative material of the present invention has such an uneven shape, not only is it excellent in slip resistance during drying, but even if it gets wet with water, it is possible to reduce the area where the foot and the like come into contact with water, Excellent slip resistance even when wet with water.
  • the volume (Vvv+Vvc) is preferably 20 mL/m 2 or more, more preferably 25 mL/m 2 or more, and 30 mL/m 2 or more, from the viewpoint of more suitably imparting slip resistance when wet with water. Is more preferable.
  • the volume (Vvv+Vvc) is preferably 55 mL/m 2 or less, and more preferably 50 mL/m 2 or less. If the volume (Vvv+Vvc) exceeds 55 mL/m 2 , it may be difficult to remove the dirt that has entered the recesses, and the cleaning performance may deteriorate.
  • VR-H2A manufactured by KEYENCE
  • FIG. 1 is a schematic diagram showing an example of a load curve obtained by measuring a decorative material with a 3D shape measuring machine. As shown in FIGS. 1(a) and 1(b), the function (volume) parameter is calculated using a load curve (a curve representing the height at which the load area ratio is 0% to 100%). The load area ratio at a certain height (c) corresponds to Smr(c) in FIG. 1(a).
  • the void volume (Vvv) of the valley portion is calculated by calculating the void volume in the range of the load area ratio of 80% or more, and the void volume (Vvc) of the core portion has the load area ratio of 10% or more and 80% or more.
  • the void volume in the range below is calculated.
  • FIG. 2A and FIG. 2B are schematic views showing the surface shape (irregular shape) of a preferred example of the decorative material of the present invention.
  • the decorative material 10 of the present invention has an irregular asperity shape as shown in FIGS. 2(a) and 2(b)
  • various designs such as a wood grain pattern, a stone grain pattern, and a texture pattern are applied as the pattern layer. Even if you do, you will not feel any discomfort.
  • a regular uneven shape for example, a geometric pattern
  • applying various designs such as a wood pattern, a stone pattern, and a cloth pattern as a pattern layer causes a feeling of strangeness. I will end up.
  • “irregular uneven shape” means that there is no periodic unevenness, and for example, the surface of a decorative material is measured with a 3D shape measuring machine (product name: one-shot 3D shape measuring machine head “VR- 3100”, controller “VR-3000”, manufactured by KEYENCE, when observing arbitrary 5 places (18 mm ⁇ 24 mm), the area ratio of the convex portion (island portion) and the concave portion (valley portion), or the convex portion It means that the number of parts (islands) is not constant.
  • a 3D shape measuring machine product name: one-shot 3D shape measuring machine head “VR- 3100”, controller “VR-3000”, manufactured by KEYENCE, when observing arbitrary 5 places (18 mm ⁇ 24 mm), the area ratio of the convex portion (island portion) and the concave portion (valley portion), or the convex portion It means that the number of parts (islands) is not constant.
  • the convex portion is obtained by the above-described 3D shape measuring machine under the same measurement conditions as the void volume (Vvv) of the valley portion and the void volume (Vvc) of the core portion described above.
  • the ratio of the surface height to the highest point is 62.5% or more and 100% or less, and the recessed portion (valley) means that the ratio of the surface height to the highest point is 0% or more, 62% or more. It means a region included in less than 0.5%.
  • the above-mentioned "area ratio" is to divide the uneven shape of the measured portion (18 mm x 24 mm) into a convex portion (island portion) and a concave portion (valley portion), measure the area occupied by each, and compare.
  • the number of convex portions (islands) is preferably 50 or more, and more preferably 100 or more, at each of the above-mentioned arbitrary 5 locations (18 mm ⁇ 24 mm). , 150 or more is more preferable.
  • the uneven shape is preferably a continuous shape. Since the uneven shape is a continuous shape, when the decorative material is wet with water, or when dirt is attached, an escape route for water and dirt is secured, so slip resistance and cleanability when wet It can be suitably added.
  • continuous shape means that there is a continuous concave portion without a break, and for example, the surface of a decorative material is measured by a 3D shape measuring machine (product name: one-shot 3D shape measuring machine head “VR- 3100”, controller “VR-3000”, manufactured by KEYENCE Co., Ltd., when observing any 5 points (18 mm ⁇ 24 mm), the total area (100%) of the recesses (valleys) at the points observed It means that the area of continuous (connected) concave portions (valley portions) is 90% or more.
  • the ten-point average roughness (RzJ) defined by JIS B 0601 (2001) is preferably 70 ⁇ m or more and 200 ⁇ m or less.
  • the ten-point average roughness (RzJ) is more preferably 90 ⁇ m or more and 180 ⁇ m or less, and further preferably 110 ⁇ m or more and 160 ⁇ m or less.
  • the arithmetic mean roughness (Ra) defined by JIS B 0601 (2001) is preferably 13 ⁇ m or more and 30 ⁇ m or less.
  • the arithmetic average roughness (Ra) is more preferably 16 ⁇ m or more and 27 ⁇ m or less, and further preferably 19 ⁇ m or more and 24 ⁇ m or less.
  • the uneven shape preferably has an average length (AR) of a roughness motif defined by CNOMO of 1.00 mm or more.
  • the average length (AR) of the roughness motif is more preferably 1.50 mm or more, and further preferably 2.00 mm or more.
  • the average length (AR) of the roughness motif is 5.00 mm or less from the viewpoint of reducing the region where the sole of the foot or the like comes into contact with water and suitably imparting the slip resistance even when wet with water. It is more preferably 4.50 mm or less.
  • the method of forming the uneven shape is not particularly limited, and examples thereof include embossing by heat and a method of transferring the uneven shape by a shaping sheet.
  • examples of the embossing include a method of performing embossing using a well-known sheet-fed or rotary embossing machine.
  • the decorative material of the present invention has a pattern layer.
  • 3A is a cross-sectional view showing one embodiment of the decorative material of the present invention
  • FIG. 3B is a cross-sectional view showing another embodiment of the decorative material of the present invention
  • FIG. It is sectional drawing which shows another aspect of the decorative material of invention.
  • the pattern layer 20 may be provided on the opposite side of the surface of the decorative material 10 having the concave-convex shape 11, and as shown in FIG.
  • the decorative material 20 may be provided on the side having the uneven shape 11, and when the decorative material 10 is composed of a plurality of layers as shown in FIG. ) May be provided, and the place where it is provided is not particularly limited.
  • the pattern layer is a layer that imparts a desired pattern (design) to the decorative material, and the type of pattern is not limited. For example, a wood grain pattern, a leather pattern, a stone grain pattern, a grain pattern, a tile pasting pattern, a brickwork pattern, a grain pattern, a geometrical figure, a character, a symbol, an abstract pattern and the like.
  • the method for forming the pattern layer is not particularly limited, and for example, an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) with a binder resin in a solvent (or dispersion medium) is used. It may be formed at an arbitrary place on the decorative material by a printing method, such as on a base material sheet described later. Further, a part or the whole of the decorative material may be colored, or plural kinds of resins may be mixed. As the ink, an aqueous composition can be used from the viewpoint of reducing the VOC of the decorative sheet.
  • the colorant examples include inorganic pigments such as carbon black, titanium white, zinc white, rouge, dark blue, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine.
  • organic pigments such as pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; luminescent pigments.
  • These colorants may be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.
  • binder resin examples include polyester-based urethane resins that have been hydrophilically treated, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, and rosin. Derivatives, alcohol adducts of styrene-maleic anhydride copolymers, cellulosic resins and the like can also be used together.
  • polyacrylamide resin poly(meth)acrylic acid resin, polyethylene oxide resin, poly N-vinylpyrrolidone resin, water-soluble polyester resin, water-soluble polyamide resin, water-soluble amino Resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides and polysaccharides; and the like can also be used.
  • natural rubber, synthetic rubber, polyvinyl acetate resin, (meth)acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin modified or a mixture of the above natural rubber, etc. Resins can also be used.
  • the binder resin may be used alone or in combination of two or more kinds.
  • the solvent examples include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid- Ester-based organic solvents such as 2-ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene,
  • ketone type organic solvents examples thereof include ketone type organic solvents; ether type organic solvents such as diethyl ether, dioxane and tetrahydrofuran; chlorine type organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene; and inorganic solvents such as water.
  • ether type organic solvents such as diethyl ether, dioxane and tetrahydrofuran
  • chlorine type organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene
  • inorganic solvents such as water.
  • Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method.
  • a gravure printing method a gravure printing method
  • a screen printing method a screen printing method
  • a flexographic printing method a flexographic printing method
  • an electrostatic printing method a printing method used for forming the pattern layer
  • an inkjet printing method examples of the printing method used for forming the pattern layer.
  • roll coating method knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method.
  • Examples include various coating methods such as a method.
  • a hand-drawing method an ink-washing method, a photographic method, a transfer method, a laser beam drawing method, an electron beam drawing method, a partial vapor deposition method of metal or the like, an etching method, or the like may be used, or may be used in combination with another forming method. Good.
  • the thickness of the pattern layer is not particularly limited and can be appropriately set depending on the product characteristics, but the layer thickness is about 0.1 to 15 ⁇ m.
  • the decorative material of the present invention has a surface protective layer on the side having the uneven shape of the decorative material. It is preferable.
  • the resin forming the surface protective layer preferably contains at least one curable resin such as a thermosetting resin or an ionizing radiation curable resin, and among them, an ionizing radiation curable resin is more preferable. From the viewpoint of obtaining higher surface hardness, productivity, weather resistance and the like, the electron beam curable resin is most preferable.
  • 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 into a three-dimensional polymer structure.
  • a prepolymer, an oligomer and a monomer having a polymerizable unsaturated bond or epoxy group in the molecule, which can be crosslinked by irradiation with ionizing radiation can be used.
  • urethane acrylate for example, bifunctional ether urethane oligomer, polyfunctional urethane oligomer, etc.
  • acrylate resin such as polyester acrylate and epoxy acrylate
  • silicon resin such as siloxane
  • polyester resin for example, polyester resin, epoxy resin and the like
  • Examples of the ionizing radiation include visible rays, ultraviolet rays (near ultraviolet rays, vacuum ultraviolet rays, etc.), X-rays, electron beams, ion beams and the like. Among these, ultraviolet rays and electron beams are preferable.
  • a light source such as 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, and a metal halide lamp lamp can be used.
  • the wavelength of ultraviolet rays is, for example, about 190 to 380 nm.
  • the electron beam source for example, various electron beam accelerators such as Cockcroft Wald type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and 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 electron beam irradiation amount is preferably about 2 to 15 Mrad.
  • the ionizing radiation curable resin is sufficiently cured by irradiation with an electron beam, but when it is cured by irradiation with ultraviolet rays, it is preferable to add a photopolymerization initiator (sensitizer).
  • the photopolymerization initiator in the case of a resin system having a radically polymerizable unsaturated group, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl At least one kind of disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N,N-dimethylaminobenzoate and the like can be used.
  • acetophenones for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl
  • disulfide diethyl oxide, triphenylbiimidazole, iso
  • a resin system having a cationically polymerizable functional group for example, at least one kind of an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoinsulfonic acid ester, a fryloxysulfoxonium diallyl iodosyl salt, etc. Can be used.
  • the addition amount of the photopolymerization initiator is not particularly limited, but is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
  • Examples of the method for forming the surface protective layer with the ionizing radiation curable resin include a method of applying a solution of the ionizing radiation curable resin by a coating method such as a gravure coating method or a roll coating method.
  • thermosetting resin examples include unsaturated polyester resin, polyurethane resin (including two-component curing polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, Examples thereof include melamine-urea co-condensation resin, silicon resin, polysiloxane resin and the like.
  • a crosslinking agent, a curing agent such as a polymerization initiator, and a polymerization accelerator can be added to the thermosetting resin.
  • a curing agent isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resin, polyurethane resin, etc., organic amine, etc. can be added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile etc.
  • a radical initiator can be added to the unsaturated polyester resin.
  • Examples of the method of forming the surface protective layer with the thermosetting resin include a method of applying a solution of the thermosetting resin by a coating method such as a roll coating method or a gravure coating method, and drying and curing.
  • the thickness of the surface protective layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 20 ⁇ m.
  • an inorganic filler may be blended.
  • the inorganic filler for example, powdery aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, Examples thereof include diamond, Kongosa, talc, glass fiber and the like.
  • the addition amount of the inorganic filler is about 1 to 80 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
  • the decorative material of the present invention may be a decorative sheet.
  • the decorative sheet include a structure in which at least a base sheet, a pattern layer, a transparent resin layer, and a surface protective layer are laminated in this order in the thickness direction. At that time, the pattern layer is provided on the base material sheet.
  • the decorative sheet will be described below.
  • the substrate sheet is not particularly limited, but preferably contains a halogen-free thermoplastic resin.
  • the non-halogen thermoplastic resin include low density polyethylene (including linear low density polyethylene), medium density polyethylene, high density polyethylene, ethylene- ⁇ olefin copolymer, homopolypropylene, polymethylpentene, polybutene, ethylene- Propylene copolymers, propylene-butene copolymers, ethylene-vinyl acetate copolymers, saponified ethylene-vinyl acetate copolymers, olefinic thermoplastic resins such as mixtures thereof, polyethylene terephthalate, polybutylene terephthalate, Thermoplastic ester resin such as polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, etc., acrylic such as methyl polymethacrylate, ethyl polymethacrylate, ethyl poly
  • thermoplastic resins examples thereof include thermoplastic resins, polyamide thermoplastic resins such as nylon-6 and nylon-66, polyimide, polyurethane, polystyrene, acrylonitrile-butadiene-styrene resin, and the like.
  • these non-halogen thermoplastic resins may be used alone or in combination of two or more.
  • the olefinic thermoplastic resin is preferable because it is excellent in printability and embossability of the pattern layer and is inexpensive.
  • the base sheet may be colored.
  • a coloring material pigment or dye
  • a coloring material for coloring, for example, inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. These may be selected from known or commercially available ones or two or more thereof. Further, the addition amount of the coloring material may be appropriately set according to a desired color shade or the like.
  • various additives such as a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, and a light stabilizer are added. May be included.
  • the thickness of the substrate sheet is not particularly limited, but is preferably 40 to 100 ⁇ m.
  • the base sheet may be composed of either a single layer or multiple layers.
  • the transparent resin layer is not particularly limited and includes any of colorless transparent, colored transparent, translucent and the like.
  • the material of the transparent resin layer is not limited, but it is preferable to contain a non-halogen thermoplastic resin.
  • non-halogen thermoplastic resin examples include low density polyethylene (including linear low density polyethylene), medium density polyethylene, high density polyethylene, ethylene- ⁇ olefin copolymer, homopolypropylene, polymethylpentene, polybutene, ethylene- Propylene copolymers, propylene-butene copolymers, ethylene-vinyl acetate copolymers, saponified ethylene-vinyl acetate copolymers, olefin-based thermoplastic resins such as mixtures thereof, polyethylene terephthalate, polybutylene terephthalate, Thermoplastic ester resin such as polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, etc., acrylic such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, polybutyl acrylate, etc.
  • low density polyethylene including linear low density polyethylene
  • thermoplastic resins examples thereof include thermoplastic resins, polyamide thermoplastic resins such as nylon-6 and nylon-66, polyimide, polyurethane, polystyrene, acrylonitrile-butadiene-styrene resin, and the like.
  • these non-halogen thermoplastic resins may be used alone or in combination of two or more.
  • the olefinic thermoplastic resin is preferable because it is excellent in printability and embossability of the pattern layer and is inexpensive.
  • the transparent resin layer may be colored.
  • a colorant may be added to the thermoplastic resin.
  • a pigment or dye used in the pattern layer can be used.
  • the transparent resin layer includes a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft component (for example, rubber. ) And other various additives may be included.
  • the thickness of the transparent resin layer is not particularly limited, but is preferably 90 ⁇ m or more and 300 ⁇ m or less, more preferably 150 ⁇ m or more and 300 ⁇ m or less, and further preferably 200 ⁇ m or more and 250 ⁇ m or less.
  • the decorative sheet may further have a transparent adhesive layer, a primer layer, a backer layer, etc., if necessary.
  • Transparent adhesive layer examples include polyurethane, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer and the like, as well as butadiene-acrylonitrile rubber and neoprene. Examples thereof include rubber and natural rubber. These adhesives are used alone or in combination of two or more.
  • the thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 ⁇ m, more preferably about 1 to 5 ⁇ m.
  • the primer layer can be formed by applying a known primer agent on the surface of the transparent resin layer.
  • 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 resin-based primer agent composed of a block copolymer of acrylic and urethane. You may mix
  • additives 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 amount of the additive compounded can be appropriately set according to the product characteristics.
  • the thickness of the primer layer is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 1 ⁇ m, for example.
  • backer layer examples include a synthetic resin backer layer and a foamed resin backer layer, and it is preferable that the backer layer is provided on the lowermost layer (the side opposite to the side having the uneven shape) of the decorative sheet.
  • the backer layer By having the backer layer, the scratch resistance and impact resistance of the decorative material of the present invention can be further improved.
  • Examples of the resin forming the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, and polyalkylene terephthalate having high heat resistance [eg, a part of ethylene glycol is 1 Polyethylene terephthalate substituted with 4-cyclohexanedimethanol or diethylene glycol, so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, Examples thereof include amorphous polyester (A-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide and ABS. These resins can be used alone or in combination of two or more.
  • the synthetic resin backer layer may contain hollow beads.
  • the type, particle size, content and the like of the hollow beads those described in JP-A-2014-188941 can be applied.
  • the thickness of the synthetic resin backer layer is not particularly limited, but for example, 100 to 600 ⁇ m is preferable, and 150 to 450 ⁇ m is more preferable.
  • Examples of the method for forming the synthetic resin backer layer include calender molding and extrusion molding of molten resin. Of these, extrusion molding of a molten resin is preferable, and for example, extrusion molding using a T die is more preferable.
  • the foamed resin backer layer may be provided below the synthetic resin backer layer (on the side opposite to the side having the uneven shape). As the foamed resin backer layer, those described in JP-A-2014-188941 can be applied.
  • the method for producing the decorative sheet is not particularly limited, and examples thereof include a method in which the above-mentioned layers are laminated via the transparent adhesive layer, the primer layer, and the like.
  • the decorative material of the present invention may be a decorative board.
  • the decorative plate include a structure in which at least a support, a pattern layer, and a surface protective layer are laminated in this order in the thickness direction. In that case, the pattern layer is provided on the support.
  • the decorative plate will be described below.
  • the support is not particularly limited, and various papers, plastic films, wood-based boards such as wood, ceramic materials, etc. can be appropriately selected according to the application. These materials may be used alone, or may be a laminate of any combination such as a composite of paper and a composite of paper and plastic film.
  • Examples of the above papers include thin paper, kraft paper and titanium paper. These paper base materials are used to strengthen the interlaminar strength between the paper base fibers or other layers of the paper base material and the paper base material.
  • a resin such as a melamine resin or a urethane resin may be added (impregnated with resin after paper making or internally filled during paper making).
  • inter-paper reinforcing paper resin-impregnated paper and the like.
  • various papers often used in the field of construction materials such as linter paper, paperboard, gypsum board base paper, vinyl wallpaper stock with a vinyl chloride resin layer provided on the surface of the paper, and the like can be mentioned.
  • coated paper art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, or Japanese paper used in the field of business, ordinary printing, packaging, etc.
  • woven or non-woven fabrics of various fibers having an appearance and properties similar to paper can also be used as the substrate.
  • various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, or carbon fibers, or synthetic resin fibers such as polyester fibers, acrylic fibers, or vinylon fibers.
  • thermosetting resin for example, unsaturated polyester resin, polyurethane resin (including two-component curing type polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine- Examples thereof include urea co-condensation resin, silicon resin, polysiloxane resin and the like.
  • a layer obtained by impregnating the above papers with a thermosetting resin is also referred to as a thermosetting resin layer.
  • the thermosetting resin may eventually serve as a surface protective layer.
  • thermosetting resin layer examples include a method of impregnating a porous substrate with the thermosetting resin when the support has a porous substrate.
  • the impregnation can be performed by supplying the thermosetting resin from either the front side or the back side of the porous base material, or both.
  • This method is not particularly limited, and for example, a method of immersing it in a bath containing a thermosetting resin from the surface of the porous base material on which the release layer is formed or the surface opposite thereto; a coater such as a kiss coater or a comma coater.
  • thermosetting resin By applying the thermosetting resin to the surface of the porous substrate on which the release layer is formed, the opposite surface, or both surfaces thereof; a thermosetting resin is applied to the porous substrate by a spray device, a shower device, or the like.
  • a spray device By applying the thermosetting resin to the surface of the porous substrate on which the release layer is formed, the opposite surface, or both surfaces thereof; a thermosetting resin is applied to the porous substrate by a spray device, a shower device, or the like.
  • the surface of the material on which the release layer is formed, the surface opposite to the surface, or a method of spraying on both surfaces thereof may be mentioned.
  • the resin that constitutes the plastic film include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins, vinylidene chloride resins, phenol resins, polyvinyl alcohol, vinyl resins such as ethylene-vinyl alcohol copolymers, and polyethylene.
  • Polyester resins such as terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate, etc.
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • a polyolefin resin, a vinyl chloride resin, a polyester resin, or an acrylic resin is preferable from the viewpoints of various physical properties such as weather resistance and water resistance, printability, moldability, and price.
  • the thickness of the support is not particularly limited, but when the support is a plastic film, it is preferably 20 to 200 ⁇ m, more preferably 40 to 160 ⁇ m, still more preferably 40 to 100 ⁇ m. If the support is paper, the basis weight, usually preferably 20 ⁇ 150g / m 2, more preferably 30 ⁇ 100g / m 2.
  • the shape of the support is not limited to a flat plate, but may be a special shape such as a three-dimensional shape.
  • one or both surfaces may be subjected to an easy adhesion treatment such as a physical treatment or a chemical surface treatment on the support.
  • the decorative board may be laminated with phenol resin-impregnated paper, if necessary.
  • the phenol resin-impregnated paper may be laminated on the surface of the porous substrate opposite to the side on which the abrasion resistant layer and the release layer are formed.
  • the above-mentioned phenol resin-impregnated paper is kraft paper having a basis weight of about 150 to 250 g/m 2 impregnated with phenol resin at an impregnation rate of about 45 to 60% and dried at about 100 to 140° C. It is a paper manufactured by A commercial item can be used for the phenol resin-impregnated paper.
  • the back surface of the porous substrate may be subjected to corona discharge treatment or the back surface primer layer may be formed by applying the above-mentioned primer layer, if necessary. ..
  • a sealer layer When a base material having an impregnating property such as paper is used as the support, a sealer layer may be provided between the support and the pattern layer or between the pattern layer and the surface protective layer.
  • the above-mentioned sealer layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, among which a cured product of a thermosetting resin composition is included. Is more preferable.
  • the content of the cured product of the curable resin composition is preferably 50% by mass or more, and more preferably 65 to 95% by mass based on the total solid content of the sealer layer.
  • the thermosetting resin composition and the ionizing radiation curable resin composition of the sealer layer include the same as those exemplified for the surface protective layer.
  • the thermosetting resin composition is preferably a two-component curable resin of polyol and isocyanate, and more preferably a two-component curable resin of acrylic polyol and hexamethylene diisocyanate.
  • the sealer layer preferably contains particles from the viewpoint of drying suitability and viscosity adjustment.
  • the content of the particles is preferably 5 to 50% by mass of the total solid content of the sealer layer, more preferably 5 to 35% by mass.
  • the particles of the sealer layer are preferably inorganic particles, of which silica is preferred.
  • the average particle size of the particles is preferably 0.1 to 2.0 ⁇ m, more preferably 0.2 to 1.5 ⁇ m.
  • the thickness of the sealer layer is preferably 0.5 to 5 ⁇ m, more preferably 1 to 3 ⁇ m, from the viewpoint of the balance between impregnation prevention and cost effectiveness.
  • the decorative board may further have a transparent adhesive layer, a primer layer, etc., if necessary.
  • a transparent adhesive layer As the transparent adhesive layer and the primer layer, the same ones as those mentioned for the decorative board can be preferably used.
  • the method for producing the decorative board is not particularly limited, and examples thereof include a method in which the above-mentioned layers are laminated via the transparent adhesive layer or the primer layer.
  • FIG. 4 is a sectional view showing an embodiment in which the decorative material of the present invention is laminated on an adherend.
  • the decorative material 10 of the present invention is laminated on the adherend 30 such that the surface having the uneven shape 11 is in contact with the surface on the opposite side.
  • the material of the adherend include wood veneer, wood plywood, particle board, wood board such as MDF (medium density fiber board); gypsum board such as gypsum board and gypsum slag board; calcium silicate board, asbestos slate board.
  • Cement boards such as lightweight expanded concrete boards and hollow extruded cement boards; fiber cement boards such as pulp cement boards, asbestos cement boards and wood chip cement boards; ceramics boards such as pottery, porcelain, earthenware, glass, enamel; iron plates, zinc plating Metal plates such as steel plates, polyvinyl chloride sol-coated steel plates, aluminum plates, and copper plates; thermoplastic resin plates such as polyolefin resin plates, polyvinyl chloride resin plates, acrylic resin plates, ABS plates, styrene resins, and polycarbonate plates; phenol resin plates, Thermosetting resin plate such as urea resin plate, unsaturated polyester resin plate, polyurethane resin plate, epoxy resin plate, melamine resin plate; phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, diallyl Examples include so-called FRP plates obtained by impregnating and curing a resin such as a phthalate resin into glass fiber non-woven fabric, cloth, paper, and other various fibrous base materials
  • thermoplastic resin plate and the thermosetting resin plate are, if necessary, a coloring material (pigment or dye), a filler such as wood powder and calcium carbonate, a matting agent such as silica, a foaming agent, a flame retardant, and talc.
  • a coloring material pigment or dye
  • filler such as wood powder and calcium carbonate
  • matting agent such as silica
  • foaming agent such as silica
  • flame retardant such as talc
  • talc a matting agent
  • additives such as lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers may be contained.
  • the thickness of the adherend is not particularly limited.
  • the method for laminating on the adherend is not particularly limited, and examples thereof include means for laminating via the above-mentioned primer layer and means for laminating via an adhesive.
  • the adhesive may be appropriately selected from known adhesives according to the type of the adherend. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer and the like, as well as butadiene-acrylonitrile rubber, neoprene rubber and natural rubber.
  • the decorative material of the present invention includes, for example, interior materials for buildings such as walls, ceilings, floors; fittings such as window frames, doors and handrails; furniture; housings for home appliances, office automation equipment, etc.; exterior materials such as front doors.
  • Example 1 A polypropylene sheet having a thickness of 60 ⁇ m is prepared as a base material, and after corona discharge treatment is applied to both surfaces of the base material, gravure is applied to the surface (one surface) of the base material by using a printing ink made of an acrylic-urethane resin. Printing was performed to form a pattern layer (stone pattern). In addition, a primer layer was formed on the back surface of the base material. Then, a urethane resin-based adhesive was applied onto the pattern layer so that the thickness after drying was 3 ⁇ m, to form a transparent adhesive layer.
  • a polypropylene resin was melt-extruded by heating with a T-die extruder to form a transparent resin layer made of polypropylene so as to have a thickness of 80 ⁇ m.
  • the surface of the transparent resin layer was subjected to corona discharge treatment, and then coated with a coating solution containing a resin composition containing a resin component made of a urethane acrylic copolymer so that the coating amount was 7 g/m 2.
  • a primer layer was formed.
  • the coating liquid is a mixture of a resin composition containing a resin component made of a urethane acrylic copolymer and an isocyanate (curing agent) in a mass ratio of 100:6.
  • the thickness of the primer layer formed by applying the above coating solution on the transparent resin layer was about 2 ⁇ m.
  • 100 parts by mass of a mixture of a bifunctional ether-based urethane oligomer and a polyfunctional urethane oligomer was added with 1 part by mass of a reactive triazine compound as an ultraviolet absorber, and the mixture was subjected to a gravure coating method.
  • a gravure coating method To form a coating film.
  • an electron beam was irradiated under the conditions of 175 keV and 5 Mrad (50 kGy) to crosslink and cure the coating film, thereby forming a surface protective layer (15 g/m 2 ).
  • the surface protective layer was embossed with a rotary embossing machine to obtain a sheet-shaped decorative material having a surface with irregularities.
  • an adherend MDF, thickness 2.5 mm
  • one side of the adherend was coated with 80 g/m 2 of a water-based two-component curable adhesive (BA-10).
  • the adhering material and the obtained decorative sheet were attached so that the surface having the base material sheet was in contact with each other, and cured at 25° C. for 3 days (load: 100 kg/m 2 ).
  • Examples 2-6 Comparative Examples 1-2 It was produced in the same manner as in Example 1 except that the embossing plate was changed so as to have the uneven shape shown in Table 1.
  • Example 7 to 8 White titanium paper (“KW-1002P (trade name)”, manufactured by KJ Tokushu Paper Co., Ltd., weighing: 100 g/m 2 ) was used as the base paper, and a printing ink made of urethane-cellulose resin was used on the surface of the base paper. Gravure printing was performed to form a pattern layer (grain pattern). Further, a liquid uncured composition of a thermosetting resin consisting of 60 parts by mass of melamine formaldehyde resin, 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied onto the pattern layer by using an impregnating device for impregnation.
  • KW-1002P trade name
  • a thermosetting resin consisting of 60 parts by mass of melamine formaldehyde resin, 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied onto the pattern layer by using an impregnating device for impregnation.
  • An impregnated decorative sheet was obtained by impregnating the base paper so that the cured composition had a ratio of 80 g/m 2 (when dried) and drying.
  • the obtained impregnated decorative sheet was laminated on three pieces of phenol resin-impregnated core paper (Ota core, manufactured by Ota Sangyo Co., Ltd.) having a basis weight of 245 g/m 2 in which kraft paper was impregnated with a resin liquid containing a phenol resin.
  • the formed laminate is sandwiched between an embossing plate and a mirror surface plate, and heat-molded using a heat press machine at a pressure of 100 kg/cm 2 at a molding temperature of 150° C. for 10 minutes to thermoset the uncured composition.
  • Example 7 a cured resin containing a melamine resin was formed.
  • Vvv Valley and Void Volume (Vvc) at Core>
  • a 3D shape measuring machine product name: one-shot 3D shape measuring machine head "VR-3100", controller "VR-3000", manufactured by KEYENCE
  • the void volume (Vvv) in the valley and the void volume (Vvc) in the core were measured using the following measurement conditions to determine the volume (Vvv+Vvc).
  • VR-H2A An analysis application (“VR-H2A”, manufactured by KEYENCE) was used to calculate the void volume (Vvv) in the valley and the void volume (Vvc) in the core from the function (volume) parameters.
  • the function (volume) parameter is calculated using a load curve (a curve representing the height at which the load area ratio is 0% to 100%), and the void volume (Vvv) of the valley portion. Is the void volume in the range where the load area ratio is 80% or more, and the void volume (Vvc) of the core part is the void volume in the range where the load area ratio is 10% or more and less than 80%. It is a thing.
  • ⁇ Average length of roughness motif (AR)> For the decorative materials and floor sheets according to the examples, comparative examples and reference examples, a surface roughness measuring machine (“SURFCOM-FLEX-50A”, manufactured by Tokyo Seimitsu Co., Ltd.) was used and the average length of the roughness motif was measured under the following measurement conditions. (AR) was measured.
  • SURFCOM-FLEX-50A manufactured by Tokyo Seimitsu Co., Ltd.
  • ⁇ Roughness irregularity and continuity> Regarding the decorative materials and floor sheets according to the examples, comparative examples and reference examples, a 3D shape measuring machine (product name: one-shot 3D shape measuring machine head "VR-3100", controller “VR-3000”, manufactured by KEYENCE) was used. Using the same measurement conditions as those of the void volume (Vvv) of the valley portion and the void volume (Vvc) of the core portion described above, arbitrary 5 places (18 mm ⁇ 24 mm) were observed. In addition, the area included in the ratio of 62.5% or more and 100% or less to the highest point is defined as a convex portion (island), and the ratio of the surface height to the highest point is included in 0% or more and less than 62.5%.
  • the region to be formed is a concave portion (valley portion), and the number of convex portions (island portions) and the area occupied by the convex portions (island portions) and the concave portions (valley portions) were obtained. Further, the number of convex portions (islands) was counted at the above-mentioned arbitrary 5 locations (18 mm ⁇ 24 mm), and the average value thereof was obtained. The irregularity and continuity of the uneven shape were judged according to the following criteria.
  • the decorative materials according to the examples have excellent slip resistance not only when dried but also when wet with water.
  • the concavo-convex shape has a continuous shape
  • the volume (Vvv+Vvc) is 55 mL/m 2 or less
  • the ten-point average roughness (RzJ) is 70 ⁇ m or more and 200 ⁇ m or less
  • the arithmetic average roughness (Ra) is 13 ⁇ m or more and 30 ⁇ m or less.
  • the decorative materials according to Examples 1 to 3 in which the average length (AR) of the roughness motif was 1.00 mm or more were also particularly excellent in cleanability.
  • the decorative material of the present invention includes, for example, interior materials for buildings such as walls, ceilings, floors; fittings such as window frames, doors and handrails; furniture; housings for home appliances, office automation equipment, etc.; exterior materials such as front doors.
  • interior materials for buildings such as walls, ceilings, floors
  • fittings such as window frames, doors and handrails
  • furniture such as window frames, doors and handrails
  • furniture such as housings for home appliances, office automation equipment, etc.
  • exterior materials such as front doors.
  • it can be used more preferably as a floor material, and among them, it can be most preferably used as a floor material for kitchens, dressing rooms, etc. around water.

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Floor Finish (AREA)
  • Laminated Bodies (AREA)
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