WO2019131728A1 - Feuille stratifiée - Google Patents

Feuille stratifiée Download PDF

Info

Publication number
WO2019131728A1
WO2019131728A1 PCT/JP2018/047760 JP2018047760W WO2019131728A1 WO 2019131728 A1 WO2019131728 A1 WO 2019131728A1 JP 2018047760 W JP2018047760 W JP 2018047760W WO 2019131728 A1 WO2019131728 A1 WO 2019131728A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
laminated sheet
color tone
metal
metal oxide
Prior art date
Application number
PCT/JP2018/047760
Other languages
English (en)
Japanese (ja)
Inventor
淳之介 村上
山口　孝弘
Original Assignee
積水化学工業株式会社
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 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2019537318A priority Critical patent/JP6651060B2/ja
Priority to CN201880055438.6A priority patent/CN111051056B/zh
Priority to EP18896405.0A priority patent/EP3733400A4/fr
Publication of WO2019131728A1 publication Critical patent/WO2019131728A1/fr

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2016—Application of electric energy
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • D06Q1/04—Decorating textiles by metallising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • D06P1/67383—Inorganic compounds containing silicon

Definitions

  • the present invention relates to a laminated sheet using a carbonaceous substrate.
  • the carbonaceous substrate is lightweight and has excellent strength. For this reason, carbonaceous substrates are used in various fields such as aeronautical field, space field, motorcycle field, automobile field, construction field, civil engineering field, sports field and leisure field.
  • the surface of the carbonaceous substrate is generally black.
  • the carbonaceous substrate may be subjected to a coloring treatment.
  • Patent Document 1 listed below discloses a pigmented carbonaceous substrate.
  • a colored treated carbonaceous substrate is disclosed.
  • the coating material containing a pigment and dye is used in order to carry out a coloring process.
  • metal layer By forming a metal layer on the surface of the carbonaceous substrate, it may be possible to impart a metallic gloss. However, simply forming the metal layer may discolor the metal layer and change the color tone on the metal layer side. When the metal layer is exposed to high temperatures or exposed to the atmosphere for a long time, the metal layer may be more discolored and the color tone on the metal layer side may be more changed.
  • An object of the present invention is to provide a laminated sheet which can impart a metallic gloss feeling well and can suppress a change in color tone while leaving the designability of the surface of a carbonaceous substrate.
  • a carbonaceous substrate, a metal layer disposed on the surface of the carbonaceous substrate, and a surface of the metal layer opposite to the carbonaceous substrate are disposed. And a metal oxide layer being provided.
  • the metal element contained in the metal layer is titanium, silver or aluminum.
  • the average thickness of the metal oxide layer is 3 nm or more.
  • the average thickness of the metal oxide layer is less than 40 nm.
  • the metal oxide contained in the metal oxide layer is TiO 2 or SiO 2 .
  • metallic glossiness can be favorably provided, and the lamination sheet which can suppress the change of a color tone can be provided, leaving the designability of the surface of a carbonaceous base material.
  • FIG. 1 is a cross-sectional view schematically showing a laminated sheet according to a first embodiment of the present invention.
  • the laminated sheet according to the present invention comprises a carbonaceous substrate, a metal layer disposed on the surface of the carbonaceous substrate, and a surface of the metal layer opposite to the carbonaceous substrate. And a metal oxide layer.
  • the color tone may be able to be changed on the side of the metal layer and the metal oxide layer. Therefore, in the present specification, a layer in which the metal layer and the metal oxide layer are laminated may be referred to as a color tone adjustment layer.
  • the laminated sheet according to the present invention comprises a carbonaceous substrate and a color tone adjusting layer disposed on the surface of the carbonaceous substrate.
  • the color tone adjusting layer is formed of a metal layer (second color tone adjusting layer) on the side of the carbonaceous substrate and a metal oxide layer (on the side opposite to the side of the carbonaceous substrate). And (1) a color tone adjustment layer).
  • the carbonaceous substrate, the metal layer, and the metal oxide layer are laminated in this order.
  • the laminated sheet according to the present invention has a first surface and a second surface opposite to the first surface.
  • the carbonaceous substrate is disposed on the first surface side of the laminated sheet, and the color tone adjustment layer is disposed on the second surface side of the laminated sheet.
  • the carbonaceous base material is disposed on the first surface side of the laminated sheet, and the metal oxide layer (a first one on the second surface side of the laminated sheet).
  • a color tone adjustment layer is disposed.
  • the metallic gloss can be favorably imparted while leaving the designability of the surface of the carbonaceous substrate, and further, the change in color tone can be suppressed.
  • the said carbonaceous base material has glossiness, or has a surface pattern by uneven
  • the metal layer since the metal layer is provided, it is possible to favorably impart a metallic gloss to the laminated sheet.
  • the metal oxide layer is provided, it is possible to suppress the color change of the metal layer, and it is possible to suppress the change of the color tone on the metal layer side of the laminated sheet.
  • the metallic glossiness is favorably imparted while leaving the designability of the surface of the carbonaceous substrate. It is possible to further suppress the change in color tone on the metal layer side of the laminated sheet.
  • the color tone of the laminated sheet can be adjusted.
  • the laminated sheet with the angular dependency of the color tone. Therefore, the color tone can be changed by the angle at which the laminated sheet is viewed.
  • the mechanism by which a color tone such as metallic gloss is imparted to the laminate sheet according to the present invention is (1) the influence of the color (reflection spectrum) of the metal layer, (2) the influence of light absorption by the metal oxide layer, (3) It is considered that the influence due to optical interference generated by the metal layer and the metal oxide layer is involved.
  • the mechanism for imparting a color tone such as metallic gloss to the laminated sheet according to the present invention is not limited to the above (1) to (3).
  • the metal layer may be discolored, and the color tone on the metal layer side of the laminated sheet may be changed.
  • the metal layer may be more discolored and the color tone of the laminated sheet on the side of the metal layer may be more changed.
  • the inventors of the present invention have found that a change in color tone on the side of the metal layer of the laminated sheet can be suppressed by forming the metal oxide layer on the surface of the metal layer. In the present invention, since the above configuration is provided, it is possible to suppress a change in color tone on the metal layer side of the laminated sheet.
  • the color tone of the 2nd surface of a lamination sheet can be adjusted by changing the average thickness of the said metal oxide layer.
  • the color tone can be adjusted precisely by finely adjusting the thickness of the metal oxide layer, so that the color tone suited to the purpose of the user can be imparted to the laminated sheet.
  • the color tone adjusting layer is a layer having a property to make the color tone of the second surface of the laminated sheet different from the color tone of the surface of the carbonaceous substrate.
  • the color tone adjusting layer is preferably a layer which imparts a color tone different from that of the surface of the carbonaceous substrate to the second surface of the laminated sheet.
  • the color tone adjustment layer may have light transmittance or may not have light transmittance. From the viewpoint of further leaving the designability of the surface of the carbonaceous substrate, the color tone adjustment layer preferably has light transmittance. From the viewpoint of effectively imparting a metallic gloss to the laminated sheet, the color tone adjustment layer preferably does not have light transmittance.
  • the metal layer may be light transmissive or may not be light transmissive. From the viewpoint of further retaining the design of the surface of the carbonaceous substrate, the metal layer preferably has light transparency. From the viewpoint of more effectively imparting a metallic gloss to the laminated sheet, the metal layer preferably does not have light transparency.
  • the metal oxide layer may have light transmittance or may not have light transmittance. From the viewpoint of further retaining the design of the surface of the carbonaceous substrate, the metal oxide layer preferably has light transparency.
  • the color tone adjusting layer (the metal layer, the metal oxide layer) has light transparency
  • the second surface of the laminated sheet is carbonaceous via the color tone adjusting layer (metal layer, metal oxide layer)
  • the surface pattern (concave-convex shape) of a base material is visually recognized.
  • the color tone adjusting layer (the metal layer, the metal oxide layer) has light transmissivity
  • the second surface of the laminated sheet is carbonaceous via the color tone adjusting layer (metal layer, metal oxide layer)
  • the surface pattern (concave and convex shape) of the substrate is visually recognized, and it is preferable that the glossiness of the carbonaceous substrate is visually recognized through the color tone adjustment layer (metal layer, metal oxide layer).
  • the fact that the metal oxide layer has optical transparency means that the surface pattern (concave shape) of the carbonaceous substrate or the metal layer is visually recognized through the metal oxide layer on the second surface of the laminated sheet. means.
  • the surface pattern (concave shape) of the carbonaceous substrate or the metal layer is visually recognized through the metal oxide layer on the second surface of the laminated sheet
  • the glossiness of the carbonaceous substrate or the metal layer is visually recognized through the metal oxide layer.
  • the laminated sheet according to the present invention is suitably used as a decorative substrate sheet because it has the above-mentioned performance.
  • FIG. 1 is a cross-sectional view schematically showing a laminated sheet according to a first embodiment of the present invention.
  • a laminated sheet 1 shown in FIG. 1 includes a carbonaceous substrate 2 and a color tone adjustment layer 3.
  • the color tone adjustment layer 3 includes a metal oxide layer (first color tone adjustment layer) 31 and a metal layer (second color tone adjustment layer) 32.
  • the laminated sheet 1 includes a carbonaceous substrate 2, a metal oxide layer 31, and a metal layer 32.
  • the metal layer 32 is disposed between the carbonaceous substrate 2 and the metal oxide layer 31.
  • a metal layer 32 is disposed on the surface of the carbonaceous substrate 2.
  • a metal oxide layer 31 is disposed on the surface of the metal layer 32 opposite to the carbonaceous substrate 2.
  • the metal oxide layer 31 preferably has optical transparency.
  • the laminated sheet 1 has a first surface 1 a and a second surface 1 b opposite to the first surface 1 a.
  • the carbonaceous substrate 2 is disposed on the first surface 1 a side of the laminated sheet 1.
  • the color tone adjustment layer 3 is disposed on the second surface 1 b side of the laminated sheet 1.
  • the metal oxide layer 31 is disposed on the second surface 1 b side of the laminated sheet 1
  • the metal layer 32 is disposed on the second surface 1 b side of the laminated sheet 1.
  • the carbonaceous substrate 2, the metal layer 32, and the metal oxide layer 31 are arranged in this order.
  • the laminated sheet 1 includes one metal oxide layer 31 and one metal layer 32.
  • Each of the metal oxide layer and the metal layer may be a single layer or multiple layers.
  • the carbonaceous substrate is disposed on the first surface side of the laminated sheet in the laminated sheet.
  • the material of the carbonaceous substrate is a carbonaceous material, and the carbonaceous material is generally black. Only one type of the carbonaceous material may be used, or two or more types may be used in combination.
  • the shape of the carbonaceous substrate may be in the form of a flat sheet.
  • the carbonaceous substrate may be woven or knitted. When the shape of the carbonaceous substrate is a flat sheet, a pattern may be present on the surface of the carbonaceous substrate.
  • the carbonaceous substrate generally contains carbon atoms at 90% by mass or more and 100% by mass or less in 100% by mass of the carbonaceous substrate.
  • the carbonaceous material is preferably carbon fiber.
  • the carbonaceous substrate is preferably a carbon fiber substrate.
  • the carbon fiber substrate is preferably a carbon fiber woven fabric, a carbon fiber woven fabric, or a carbon fiber non-woven fabric.
  • As the carbon fiber base material only one of carbon fiber woven fabric, carbon fiber knitted fabric and carbon fiber non-woven fabric may be used, or two or more may be used in combination.
  • the weight of the carbon fiber is not particularly limited, but is preferably 50 g / m 2 or more, more preferably 100 g / m 2 or more, preferably 700 g / m 2 or less, more preferably 500 g / m 2 or less.
  • the filament diameter of the carbon fiber is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the density of the carbon fiber is not particularly limited, but preferably 1 or more, more preferably 2 or more, preferably 50 or less, more preferably Is 20 or less per inch.
  • the weave is not particularly limited, but preferably is plain weave or twill weave.
  • the carbonaceous substrate is a carbon fiber substrate
  • the carbonaceous substrate is a woven fabric of carbon fibers, a knitted fabric of carbon fibers, or a non-woven fabric of carbon fibers, the uneven shape, the pattern, the gloss, etc.
  • the unique design of carbon fiber can be imparted to the laminated sheet. By forming a specific color tone adjustment layer, even if the color tone adjustment layer is disposed on the surface of the carbon fiber substrate, unique design can be visually recognized.
  • the carbonaceous material is a carbon fiber, it is possible to obtain a laminated sheet which is light in weight and excellent in strength.
  • the carbon fiber substrate is preferably a woven fabric of carbon fibers or a knitted fabric of carbon fibers from the viewpoint of significantly developing the uneven shape and pattern of the carbonaceous substrate.
  • the laminated sheet in order to increase the strength of the laminated sheet, may be a carbon fiber reinforced plastic.
  • the carbon fiber reinforced plastic includes the laminated sheet.
  • the carbon fiber reinforced plastic preferably includes the laminated sheet and a plastic.
  • the laminated sheet may be used as a material of carbon fiber reinforced plastic.
  • the carbon fiber base material may be used as a material of carbon fiber reinforced plastic.
  • the color tone adjustment layer is a layer disposed on the surface of the carbonaceous substrate.
  • the color tone adjustment layer is disposed on the second surface side of the laminated sheet in the laminated sheet.
  • the color tone adjustment layer is preferably a layer having a property to make the color tone of the second surface of the laminated sheet different from the color tone of the surface of the carbonaceous substrate.
  • the color tone adjustment layer has a metal oxide layer, and a metal layer disposed between the metal oxide layer and the carbonaceous substrate.
  • the laminated sheet comprises a metal oxide layer and a metal layer.
  • the color tone adjustment layer is a spectral reflectance curve of the second surface of the laminated sheet in visible light, and a spectral reflectance curve of the surface of the carbonaceous substrate in visible light. It is preferable to have the property of making it different from the reflectance curve.
  • the metal oxide layer is formed of the spectral reflectance curve of the second surface of the laminated sheet in the visible light and the visible light of the surface of the carbonaceous substrate. It is preferable to have the property to make it different from the spectral reflectance curve in.
  • the metal layer is a spectral reflectance curve of the second surface of the laminated sheet in visible light, and a spectrum of the visible light of the surface of the carbonaceous substrate. It is preferable to have the property of making it different from the reflectance curve.
  • the color tone adjusting layer preferably does not substantially contain a pigment.
  • the color tone adjustment layer preferably does not substantially contain a dye.
  • a carbonaceous substrate is provided on the second surface of the laminated sheet by forming a color tone adjustment layer substantially free of a pigment or forming a color tone adjustment layer substantially free of a dye.
  • a color tone adjustment layer which does not substantially contain both a pigment and a dye
  • unique designability such as a concavo-convex shape, a surface pattern, and a glossiness which the carbonaceous substrate has on the second surface of the laminated sheet
  • the adhesion between the carbonaceous substrate and the metal layer can be enhanced by forming the color tone adjustment layer substantially free of both the pigment and the dye.
  • the metal layer does not contain or contains a pigment.
  • the metal layer does not contain or contains a dye.
  • the content of the pigment is preferably 0.1% by weight or less, more preferably 0.01% by weight or less in 100% by weight of the metal layer.
  • the content of the dye is preferably 0.1% by weight or less, more preferably 0.01% by weight or less in 100% by weight of the metal layer.
  • the metal oxide layer does not contain or contains a pigment.
  • the metal oxide layer does not contain or contains a dye.
  • the content of the pigment is preferably 0.1% by weight or less, and more preferably 0.01% by weight or less, in 100% by weight of the metal oxide layer.
  • the content of the dye is preferably 0.1% by weight or less, and more preferably 0.01% by weight or less, based on 100% by weight of the metal oxide layer.
  • the light transmittance is low, and the surface of the carbonaceous substrate is hardly visible.
  • the color tone adjusting layer containing a pigment and the color tone adjusting layer containing a dye generally, the light transmittance is low, and the surface pattern of the carbonaceous substrate is hardly visible.
  • a metallic gloss feeling is difficult to be imparted to a color tone adjustment layer containing a pigment and a color tone adjustment layer containing a dye.
  • the metal oxide layer contains a metal oxide.
  • the metal oxide layer preferably comprises a metal oxide represented by MO x, is preferably a metal oxide layer represented by MO x.
  • M in MO x represents an n-valent metal, and x represents a number of not less than n / 2.5 and not more than n / 2. Note that in the MO x, O represents oxygen.
  • the metal oxides may be used alone or in combination of two or more.
  • the metal layer contains a metal element.
  • the metal layer may include, if a small amount of oxygen atoms, but in this case, the metal layer is a compound represented by MO x, M in MO x represents an n-valent metal, And x is a compound that is greater than 0 and less than n / 2.5 (preferably less than n / 20).
  • a metal layer containing such a small amount of oxygen atoms is also called a metal layer.
  • the metal layer contains a metal alone, the metal layer contains a compound represented by M, and M represents a metal.
  • the metal element contained in the metal layer may be used alone or in combination of two or more.
  • the metal layer When the metal oxide layer is not provided, or when the metal oxide layer is replaced with a metal layer, the metal layer may be oxidized. When the metal contained in the metal layer is oxidized, the metal layer may be discolored to change the color tone on the metal layer side of the laminated sheet.
  • the laminated sheet can be favorably imparted with a metallic gloss.
  • the metal oxide layer since the metal oxide layer is provided, it is possible to suppress the color change due to the oxidation of the metal in the metal layer, and as a result, to suppress the change of the color tone on the metal layer side of the laminated sheet. it can. Further, in the present invention, since the metal oxide layer is provided, the color tone of the laminated sheet can be adjusted. Moreover, in the present invention, since both the metal layer and the metal oxide layer are provided, it is possible to impart a good metallic gloss to the laminated sheet while leaving the designability of the surface of the carbonaceous substrate. In addition, the change in color tone can be suppressed.
  • MO x is an incomplete oxide of a metal. Such incomplete oxides of metals are also referred to as metal oxides. It is better that x is closer to n / 2.
  • x is preferably n / 2.5 or more, more preferably n / 2.2 or more, and still more preferably n / 2.
  • MO x is a complete oxide of the metal.
  • M in MO x represents an n-valent metal and x represents a number of n / 2. That is, it is more preferable that the metal oxide layer contains a complete oxide of metal. In this case, since the metal contained in the metal oxide layer is not oxidized, it is possible to suppress the color change of the color imparted to the laminated sheet. In addition, even if the metal oxide layer is exposed to high temperatures or exposed to the atmosphere for a long time, the color change of the applied color can be considerably suppressed.
  • the valence of the oxygen atom for example, the cross-section of the layer containing MO x, FE-TEM-EDX (e.g., manufactured by JEOL Ltd. "JEM-ARM200F") to elemental analysis, the area of the cross section of the layer containing the MO x
  • the valence of the oxygen atom can be calculated by calculating x from the element ratio of M to O per weight.
  • M in MO x is silicon, zinc, silver, gold, titanium, It is preferably aluminum, tin, copper, iron, molybdenum, niobium or indium. M in MO x may contain only one of these metal elements, or may contain two or more. Or suppressing the change in the metal layer side of the color tone of the laminated sheet even more more effectively, from the viewpoint or to better adjust the color tone of the laminated sheet, M in MO x is silicon, zinc, titanium, aluminum, tin More preferably, it is niobium or indium, and more preferably silicon or titanium.
  • the metal oxide contained in the metal oxide layer is preferably TiO y , SiO y , ZnO, Al 2 O y , Nb 2 O y , SnO y , or In 2 O y , and TiO y or SiO It is more preferable that it is y .
  • y is an arbitrary number which is a complete metal oxide or an incomplete metal oxide.
  • the metal oxide contained in the metal oxide layer is preferably TiO 2 , SiO 2 , ZnO, Al 2 O 3 , Nb 2 O 5 , SnO 2 , or In 2 O 3 , TiO 2 or SiO 2 . More preferably, it is 2 . These metal oxides are complete oxides of metals.
  • the metal oxide layer may contain only one of these metal oxides, or may contain two or more.
  • the metal oxide layer contains the above-mentioned preferable metal oxide, the change in color tone can be suppressed more effectively, and the color tone of the laminated sheet can be favorably adjusted.
  • the metal element contained in the metal oxide layer and the metal element contained in the metal layer may be the same or different. From the viewpoint of effectively making the color tone of the second surface of the laminated sheet different from the color tone of the surface of the carbonaceous substrate, the metal element contained most in the metal oxide layer and the metal element in the metal layer most It is preferable that the metal element contained in a large amount is different.
  • the metal element contained in the metal layer is preferably titanium, silver, aluminum, copper, chromium, or palladium from the viewpoint of imparting a specific surface color and metallic luster to the laminated sheet, and titanium, silver, Or more preferably aluminum.
  • the metal layer may contain only one of these metal elements, or may contain two or more.
  • the metal element contained most in the metal layer is preferably silver or aluminum.
  • JIS Z8781-4 2013 of the second surface of the laminate sheet and the surface of the carbonaceous substrate that the metal element contained most in the metal layer is silver or aluminum.
  • the color difference ⁇ E * ab in the L * a * b * color system to be measured can be increased.
  • the metal element contained most in the metal layer is titanium.
  • the metal contained most in the metal oxide layer from the viewpoint of imparting a metallic gloss feeling to the laminated sheet still better and further suppressing the change of color tone on the metal layer side of the laminated sheet more effectively
  • the oxide is TiO 2 or SiO 2
  • the metal element contained most in the metal layer is titanium, silver or aluminum.
  • the visible light transmittance of the metal oxide layer is preferably 5% or more, more preferably 8% or more, preferably 100% or less, and more preferably 90% or less.
  • the visible light transmittance of the metal oxide layer is not less than the lower limit and not more than the upper limit, the uneven shape and the glossiness of the carbonaceous substrate are unlikely to be impaired, and the laminated sheet has a good metal glossiness. It can be granted.
  • the visible light transmittance is an average value of measurement values obtained when the transmittance in the wavelength range of 380 nm to 780 nm is measured at intervals of 5 nm.
  • the visible light transmittance can be measured, for example, using a spectrophotometer (for example, "U-4100" manufactured by Hitachi High-Technologies Corporation).
  • a spectrophotometer for example, "U-4100” manufactured by Hitachi High-Technologies Corporation.
  • an integrating sphere can be used as a detector.
  • the visible light transmittance may be measured by preparing a metal oxide layer having an average thickness equivalent to that of the metal oxide layer of the laminated sheet.
  • the metal oxide layer and the metal layer may be formed by sputtering (reactive sputtering, RF sputtering), vapor deposition (plasma deposition, etc., vacuum evaporation (EB evaporation, ion plating) , IAD method) and the like.
  • the metal oxide layer and the metal layer are preferably formed by sputtering, respectively, from the viewpoint of making it difficult to further impair the design properties such as the concavo-convex shape and the glossiness of the carbonaceous substrate. Is preferred.
  • the metal oxide layer is a sputtered layer, the thickness of the metal oxide layer can be finely adjusted, so that the color tone adjustment of the laminated sheet can be precisely performed. As a result, the user's A color tone suited to the purpose can be imparted to the laminated sheet.
  • the visible light transmittance of the metal oxide layer and the metal layer can be changed, or the color tone of the second surface of the laminated sheet can be varied. Can be changed.
  • the surface on the opposite side to the said carbonaceous base material side of the said color tone adjustment layer is not flat. It is preferable that the surface on the opposite side to the said carbonaceous base material side of the said color tone adjustment layer is an unevenness
  • the laminated sheet preferably has irregularities on the surface of the color tone adjustment layer opposite to the side of the carbonaceous substrate corresponding to the unevenness of the surface of the carbonaceous substrate on the color tone adjustment layer side. Such unevenness of the color tone adjusting layer can be favorably formed by sputtering or the like.
  • the surface of the color tone control layer is usually flat.
  • the average thickness of the metal oxide layer is preferably 3 nm or more, more preferably 5 nm or more, and still more preferably 10 nm or more.
  • the average thickness of the metal oxide layer is preferably 50 nm or less, more preferably 40 nm or less, still more preferably less than 40 nm, particularly preferably 30 nm or less.
  • the designability of the carbonaceous substrate is less likely to be further impaired.
  • the average thickness of the metal oxide layer is less than or equal to the upper limit or less than the upper limit, surface roughness, refractive resistance, and the like of the carbonaceous substrate are less likely to be impaired.
  • the average thickness of the metal oxide layer is less than or equal to the upper limit or less than the upper limit, the color tone and texture of the metal derived from the metal layer can be maintained while maintaining the gloss and the color tone of the metal layer.
  • the thickness of the metal oxide layer to be formed is less than 3 nm.
  • the average thickness of the metal layer is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, particularly preferably 40 nm or more, and most preferably 50 nm or more.
  • the average thickness of the metal layer is preferably 200 nm or less, more preferably 190 nm or less, still more preferably 180 nm or less, particularly preferably 170 nm or less, and most preferably 150 nm or less.
  • a metallic glossiness can be favorably provided to a lamination sheet as average thickness of the above-mentioned metal layer is more than the above-mentioned minimum.
  • the designability of the carbonaceous substrate such as the uneven shape and the gloss, is less likely to be impaired.
  • the average thickness of the metal layer is equal to or less than the upper limit, the surface roughness, the refractive resistance, and the like of the carbonaceous substrate are less likely to be impaired.
  • the average thickness can be measured, for example, by observing each of the metal oxide layer and the metal layer in cross section with an FE-TEM (for example, “JEM-ARM200F” manufactured by JEOL Ltd.). From the cross-sectional TEM image obtained by FE-TEM, arbitrary five or more points separated by 100 nm or more are selected, and the average thickness measured at each point is taken as the average thickness.
  • FE-TEM for example, “JEM-ARM200F” manufactured by JEOL Ltd.
  • the color difference ⁇ E * ab in the b * color system is preferably 10 or more, more preferably 15 or more, and further preferably 20 or more.
  • the color difference ⁇ E * ab between the second surface of the laminated sheet and the surface of the carbonaceous substrate may be 50 or less.
  • the second of the above-mentioned second laminated sheet is preferably 5 or more higher, more preferably 6 or more higher, and still more preferably 7 or more higher than the lightness L * of the surface of the carbonaceous substrate.
  • a lightness L * of the second surface of the laminated sheet, lightness L * and the surface of the carbonaceous substrate may be different in 50 or less.
  • the carbonaceous substrate before the color tone adjustment layer is disposed may be used.
  • the measurement may be performed on the surface of the carbonaceous substrate opposite to the color tone adjustment layer side.
  • the second surface of the laminated sheet and the laminated sheet are allowed to stand for 240 hours under the conditions of a temperature of 85 ° C. and a humidity of 85% RH.
  • the color difference ⁇ E * ab in the L * a * b * color system, measured according to JIS Z8781-4: 2013, of the above-mentioned second sheet of the laminated sheet is preferably 10 or less, more preferably It is 5 or less, more preferably 3 or less.
  • Example 1 Formation of second color tone adjustment layer (metal layer) As a carbonaceous substrate, a carbon fiber substrate ("TR3523 M” manufactured by Mitsubishi Chemical Corporation, thickness 0.21 mm) which is a woven fabric in which carbon fibers (area weight 200 g / m 2 , filament diameter 7 ⁇ m) are woven by twill weave Using. The carbonaceous substrate was placed in a vacuum apparatus and evacuated to a pressure of 5.0 ⁇ 10 ⁇ 4 Pa or less. Subsequently, an argon gas is introduced, and a Ti layer (average thickness 50 nm) is formed as a second color tone adjustment layer on the surface of the carbonaceous substrate by DC magnetron sputtering method. A laminate with the color tone adjustment layer 2 was obtained.
  • a carbon fiber substrate ("TR3523 M” manufactured by Mitsubishi Chemical Corporation, thickness 0.21 mm) which is a woven fabric in which carbon fibers (area weight 200 g / m 2 , filament diameter 7 ⁇ m) are woven by twill
  • first color tone adjustment layer metal oxide layer
  • the laminate of the carbonaceous substrate and the second color tone adjustment layer was placed in a vacuum device, and evacuation was performed until the pressure became 5.0 ⁇ 10 ⁇ 4 Pa or less. Subsequently, an argon gas and an oxygen gas are introduced, and a TiO 2 layer as a first color tone adjusting layer is formed on the surface of the second color tone adjusting layer opposite to the carbonaceous substrate by DC magnetron sputtering. An average thickness of 1 nm was formed to obtain a laminated sheet.
  • Example 2 A laminated sheet was obtained in the same manner as in Example 1 except that the average thickness of the first color tone adjustment layer was changed as shown in Table 1.
  • Example 7 A laminated sheet was obtained in the same manner as in Example 1 except that the average thickness of the first color tone adjusting layer and the material of the second color tone adjusting layer were changed as shown in Tables 1 and 2.
  • Example 11 to 14 A laminated sheet was obtained in the same manner as in Example 1 except that the material and the average thickness of the first color tone adjustment layer were changed as shown in Table 2.
  • Example 15 A laminated sheet was obtained in the same manner as in Example 1 except that the average thickness of the first color tone adjustment layer was changed as shown in Table 2.
  • Example 16 and 17 A laminated sheet was obtained in the same manner as Example 1, except that the average thickness of the first color tone adjusting layer and the material of the second color tone adjusting layer were changed as shown in Table 2.
  • Comparative example 1 The carbon fiber base material ("TR3523 M” manufactured by Mitsubishi Chemical Corporation, 0.21 mm thick) in Example 1 was used as the evaluation target of Comparative Example 1. In Comparative Example 1, both the first color tone adjusting layer and the second color tone adjusting layer were not formed.
  • Comparative example 2 In the same manner as in Example 1, a Ti layer (average thickness: 50 nm) was formed as a second color tone adjustment layer to obtain a laminated sheet. In Comparative Example 2, the first color tone adjustment layer was not formed.
  • Example 3 The carbon fiber base material in Example 1 was prepared. A paint containing a blue pigment is applied to one surface of this carbon fiber substrate to form a colored layer (a color tone adjusting layer having no light transmittance, average thickness 15 ⁇ m), and a colored layer on the second surface side Got a laminated sheet where is placed.
  • a colored layer a color tone adjusting layer having no light transmittance, average thickness 15 ⁇ m
  • Comparative example 4 In the same manner as in Example 1, an Ag layer (average thickness 50 nm) was formed as a second color tone adjustment layer to obtain a laminated sheet. In Comparative Example 4, the first color tone adjustment layer was not formed.
  • Comparative example 5 In the same manner as in Example 1, an Al layer (average thickness 50 nm) was formed as a second color tone adjustment layer to obtain a laminated sheet. In Comparative Example 5, the first color tone adjustment layer was not formed.
  • the surface of the carbonaceous substrate of Comparative Example 1 corresponds to the surface (first surface of the laminate sheet) of the carbonaceous substrate in the laminated sheet obtained in Examples 1 to 17 and Comparative Examples 2 to 5. .
  • the surface of the carbonaceous substrate of Comparative Example 1 corresponds to the surface (first surface of the laminate sheet) of the carbonaceous substrate in the laminated sheet obtained in Examples 1 to 17 and Comparative Examples 2 to 5. .
  • Example 1 to 6, 11 to 15 metal layer: Ti layer, metal oxide layer: TiO 2 layer or SiO 2 layer
  • the second surface of the laminated sheet obtained in Comparative Example 2 metal Layer: color difference with the second surface of the laminated sheet obtained in (Ti) layer
  • Examples 7, 8 and 16 metal layer: Ag layer, metal oxide layer: TiO 2 layer
  • laminated Color difference between the second surface of the sheet and the second surface of the laminated sheet obtained in Comparative Example 4 metal layer: Ag layer
  • Examples 9, 10, 17 metal layer: Al layer, metal
  • Oxide layer color difference between the second surface of the laminated sheet obtained with TiO 2 layer
  • Comparative Example 5 metal layer: Al layer

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

La présente invention concerne une feuille stratifiée qui peut conférer un bel aspect métallique brillant à une surface d'un substrat carboné tout en conservant sa conception, et peut empêcher un changement de ton de couleur. La feuille stratifiée selon la présente invention comprend un substrat carboné, une couche métallique disposée sur une surface du substrat carboné, et une couche d'oxyde métallique disposée sur une surface de la couche métallique sur le côté opposé du substrat carboné.
PCT/JP2018/047760 2017-12-28 2018-12-26 Feuille stratifiée WO2019131728A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2019537318A JP6651060B2 (ja) 2017-12-28 2018-12-26 積層シート
CN201880055438.6A CN111051056B (zh) 2017-12-28 2018-12-26 叠层片
EP18896405.0A EP3733400A4 (fr) 2017-12-28 2018-12-26 Feuille stratifiée

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-254025 2017-12-28
JP2017254025 2017-12-28

Publications (1)

Publication Number Publication Date
WO2019131728A1 true WO2019131728A1 (fr) 2019-07-04

Family

ID=67063757

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/047760 WO2019131728A1 (fr) 2017-12-28 2018-12-26 Feuille stratifiée

Country Status (4)

Country Link
EP (1) EP3733400A4 (fr)
JP (2) JP6651060B2 (fr)
CN (1) CN111051056B (fr)
WO (1) WO2019131728A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022232870A1 (fr) * 2021-05-03 2022-11-10 Survivon Ltd Produit de dépôt en phase vapeur et procédé associé

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60131240A (ja) * 1983-12-20 1985-07-12 豊田合成株式会社 合成樹脂成形品
JPS6194002A (ja) * 1984-10-15 1986-05-12 Hitachi Chem Co Ltd 繊維強化プラスチツク製ミラ−の製造法
JPH0382881A (ja) * 1989-08-22 1991-04-08 Toray Ind Inc 干渉色を有する繊維布帛およびその製法
JPH08253874A (ja) * 1995-03-16 1996-10-01 Kawasaki Steel Corp Ｃ／ｃ複合材料用高密着性耐酸化性被覆およびその形成方法
JPH1170617A (ja) * 1997-08-29 1999-03-16 Fuji Heavy Ind Ltd 炭素繊維強化炭素複合材料の耐酸化多層被膜の被覆方法および被覆材料
JP2000281469A (ja) * 1999-03-31 2000-10-10 Ngk Insulators Ltd 被覆層を有する炭素複合材およびその製造方法
JP2010229587A (ja) 2009-03-27 2010-10-14 Toho Tenax Co Ltd 着色炭素繊維
KR20140080654A (ko) * 2012-12-13 2014-07-01 주식회사 우전앤한단 우수한 외관을 갖는 복합소재 및 이의 제조방법

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2757374C2 (de) * 1977-12-22 1984-06-28 Siemens AG, 1000 Berlin und 8000 München Verfahren zum kontinuierlichen Beschichten eines für Bürstenkontakte in elektrischen Maschinen geeigneten Graphitkörpers sowie Vorrichtung zur Durchführung dieses Verfahrens
JPS62137993U (fr) * 1986-02-24 1987-08-31
JP3069398B2 (ja) * 1991-06-20 2000-07-24 ジャパンマテックス株式会社 複合シートおよびそれを用いた封止部材
JPH068240A (ja) * 1992-06-27 1994-01-18 Kanebo Ltd 繊維強化プラスチック成形体
CA2679401A1 (fr) * 2007-02-27 2008-09-04 Nanocomp Technologies, Inc. Materiaux pour protection thermique et procedes de fabrication de ceux-ci
JP5401741B2 (ja) * 2009-07-29 2014-01-29 長野県 多層伝熱プレート及びその製造方法
TW201318837A (zh) * 2011-11-08 2013-05-16 Shim Lee Print T Shirt Corp 抗磨複合材的製造方法
JP5819181B2 (ja) * 2011-12-26 2015-11-18 豊田合成株式会社 加飾シート及びその製造方法
US20160251749A1 (en) * 2013-11-21 2016-09-01 Hewlett Packard Development Company, L.P. Oxidized Layer and Light Metal Layer on Substrate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60131240A (ja) * 1983-12-20 1985-07-12 豊田合成株式会社 合成樹脂成形品
JPS6194002A (ja) * 1984-10-15 1986-05-12 Hitachi Chem Co Ltd 繊維強化プラスチツク製ミラ−の製造法
JPH0382881A (ja) * 1989-08-22 1991-04-08 Toray Ind Inc 干渉色を有する繊維布帛およびその製法
JPH08253874A (ja) * 1995-03-16 1996-10-01 Kawasaki Steel Corp Ｃ／ｃ複合材料用高密着性耐酸化性被覆およびその形成方法
JPH1170617A (ja) * 1997-08-29 1999-03-16 Fuji Heavy Ind Ltd 炭素繊維強化炭素複合材料の耐酸化多層被膜の被覆方法および被覆材料
JP2000281469A (ja) * 1999-03-31 2000-10-10 Ngk Insulators Ltd 被覆層を有する炭素複合材およびその製造方法
JP2010229587A (ja) 2009-03-27 2010-10-14 Toho Tenax Co Ltd 着色炭素繊維
KR20140080654A (ko) * 2012-12-13 2014-07-01 주식회사 우전앤한단 우수한 외관을 갖는 복합소재 및 이의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3733400A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022232870A1 (fr) * 2021-05-03 2022-11-10 Survivon Ltd Produit de dépôt en phase vapeur et procédé associé

Also Published As

Publication number Publication date
EP3733400A4 (fr) 2021-10-13
JP6651060B2 (ja) 2020-02-19
EP3733400A1 (fr) 2020-11-04
JPWO2019131728A1 (ja) 2019-12-26
JP2020059289A (ja) 2020-04-16
CN111051056B (zh) 2023-03-31
CN111051056A (zh) 2020-04-21

Similar Documents

Publication Publication Date Title
JP6522863B1 (ja) 積層シート、コーティング繊維、コーティング繊維束及び繊維強化プラスチック
JP6664377B2 (ja) 装飾用ガラスパネル
CN102144177A (zh) 黑色覆膜及其制造方法、黑色遮光板及使用它的光圈、光量调节用光圈装置、快门以及耐热遮光带
JP6846053B2 (ja) アルミニウムキャリアと銀反射層とを有する反射性複合材料
US10551529B2 (en) Coloured mirror
US9884783B2 (en) Coated glass ceramic plate
WO2019131728A1 (fr) Feuille stratifiée
WO2015194485A1 (fr) Stratifié
JP2006317603A (ja) 表面鏡
TWI508862B (zh) 光吸收性層狀結構
JP6771425B2 (ja) 積層構造体及び成形体
JP6725636B2 (ja) 積層シート
WO2019230798A1 (fr) Feuille stratifiée
CN114728497B (zh) 层叠体和门或墙壁
KR20220085027A (ko) 반투명 또는 투명 마모 방지 코팅, 이러한 마모 방지 코팅을 갖는 기재 및 그의 제조 방법
JP2005055005A (ja) 調理器用トッププレート
JP6523537B2 (ja) 積層シート、コーティング繊維、コーティング繊維束及び複合材料
JP4347856B2 (ja) 眼鏡フレーム及びその製造方法
JP4443958B2 (ja) 鏡およびその製造方法
JP6525497B2 (ja) 多層膜構造体の製造方法、及び多層膜構造体
JP6622946B1 (ja) 積層シート
WO2022181371A1 (fr) Substrat transparent avec film multicouche et dispositif d'affichage d'image
KR20100077768A (ko) 다색구현용 다층박막 및 그 제조방법
KR20220149614A (ko) 차광 부재
CN115509028A (zh) 一种持久抗菌膜层镜片及其制造工艺

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019537318

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 18896405

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018896405

Country of ref document: EP

Effective date: 20200728